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CONTENTS

Page Nos.
MATHEMATICAL TABLES
1-4
NCERT CONCEPT
UNIT 1 Solutions
UNIE2Electro Chemistry 5-49
UNIT 3 Chemical Kinetics 50-94
UNIT 4 The d- and f- Block 95-131
Elements
UNIT 5 Co-ordination Compounds 132-159
UNIT 6 Haloalkanes and 160-193
Haloarenes
UNIT 7 Alcohols, Phenols 194-234
and Ethers
UNIT 8 Aldehydes, Ketones 235-272
and Carboxylic acids
UNIT 9 Amines 273-313
UNIT 10Biomolecules 314-339
Passing Package 340-372
373-376

HAND BOOK
Previous years Karnataka
PUBoard Annual and
Supplementary Examination 379-411
Solved Question papers.

Three Model question papersissued

by Karnataka School Exmination 412-443
and Assessment Board (KSEAB) 41249
with complete solutions alony
with the Blue prints,

March 2025 State Board

Annual Examination Question 444-450
with Complete solutions Paper
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UNIT
Solutions 1

1.1 Types of Solutions

1. What is asolution?
Ans: A solution is a homogeneous mixture of two or more components (substances).
2. Give any two characteristics of solution.
Ans: () Composition is same throughout the mixture
(i) Properties are uniform throughout the solution.
3. What is solvent?
Ans: The component which is present in larger quantity in solution is called solvent.
4. What is solute?
Ans: The component which is present in smaller quantity in Solution is called solute.
5. Name the component of the solution which determines the physical state of the solution.
Ans: Solvent
What is binary solution? Give an example. [July-2014]
Ans: A solution containing only two components is called binary solution.
Example: Glucose dissolved in water or Glucose watert
7. Whát is solid solution?
Ans: A solution in which solid acts as a solvent is called solid solution.
8. What is liquid solution?
Ans: A solution in which liguid acts as a solvent is called liquid solution.
9. What is gaseous solution?
Ans: A solution in which gas acts as a solvent is called gaseous solution.
10. Name the types of binary solutions? Give examples. [March-2016]
Ans: Binary solutions are of three types:
SI. No. Type of solution Solute Solvent Common examples
i. Solid solutions Solid Solid Copper dissolved in gold
Liquid Solid Amalgam of mercury with sodium (Na/Hg)
Gas Solid Solution of H, in Pd
i. Liquid solutions Solid Liquid Glucose in water, NaCl in water
Liquid Liquid Ethanol in water
Gas Liquid Oxygen in water, CO; in water
iii. Gaseous solutions Solid Gas Camphor in nitrogen gas
Liquid Gas Chloroform in nitrogen gas
Gas Gas Mixturé of O, and N

gas. [July 2015]

11, Give an example for liquid solution in which solute is
Ans: Oxygen dissolved in water.

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Solutions

Concentration of a Solution
1.2 Expressing
concentration ofa
solution?
What is of the solution is callcd its concentration.
givcn quantity
1.
amount of solute present in the solutions.
Ans: The
to express concentration of
2 Name the units uscd (ii) Molality (m)
Ans: () Molarity (M) (iv) Mass percent (w/w)
(i) Mole fraction (r) (vi)
percent (VV) Mass by volume percent(m/V)
(v) Volume
(ppm)
(vii) Parts per million
Concept of molarity
K Define molarity (M)
Deline [March-2014, July
ioles of solute dissolved in T
litre (I dm') or 1000 cm a
2014, July 2020]
denoted by 'M'.
It is
of solution is called molarity.
Molarity is calculated by the equation,
Number of moles of solute
=
Molarity
Volume of the solution in litres Or Molarity = WX1000 cm
or Molarity = xlL W

Where WB mass
of solute, MB Molar mass of
M, xV
Note: Molarity depends on, solute, V= yolume of
temperature. As the solution.
because volume the the temperature increases,
of solution increases. molarity of solution decreases
How does molarity
varies
s: Molarity varies inversely with temperature?
with temperature. [March - 2017]
Molarity varies inversely
s: Due to increase in volume with temperature. Give reason.
of the solution by increasing temperature or vice-versa.
Write the unit of molarity of solutions.
1s: MoVLit

Eoncept of molality
Define molality (m).
ns: The number of moles of solute dissolved one or
in kg 1000 g of a solvent is called molality.
It is denoted by m'.
Molality is calculated by the equation. L

Number of moles of solute

Molality (m) =
Mass of the solvent in kg
or
W; x1000g or
Molality = M
Molality = Wp
Xx

Ikg
XWA
Mg xWA
Where WB = mass of solute, Mp= Molar mass
of solute, WA = mass of solvent.
Note: Molality is independent on temperature mass
because the is independent of temperature.

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Jeevith Publications 7

Concept of mole fraction

8. Define mole fraction (1).
Ans: It is the ratio of number of moles
componcnts in the solution.
ofa particular componcnt to the total number of moles of all the
Mole fraction of a componcnt = Number of moles of acomponcnt
Totalnumber of moles of all components
a
In binary mixture, if 'np'moles of solute is present in
'n'
moles of solvent, then
Mole fraction of solute, p n
+np
Mole fraction of solvent, x=
Note: Sum of mole fractions of all components present in solution is equalto one i.e.,
For a solution containing i number of components
x +xp =1.

n, n
n +ng +nç..... +n,
9. Define mass percentage (w/w).For which type of solutions this unit is useful?
Ans: Mass percentage ofa solution is defined as the mass of the solute dissolved in 100g of the solution.

Mass percentage(w/w) of a component Mass of a compönent in the solution

-x100
Total mass of the solution
Note: This unit is useful when both the solute and solvents are solids.
10. What the meaning of 10% glucose in water by mass?
Ans: It means 10g of glucose is dissolved in 90g of water resulting in 100g of a solution.
11. Define volume percentage. For which type of solutions this unit is useful?
Ans: Volume percentage of a solution is defined as the volume of the solute dissolved in 100 mL ofthe solution.
component in the solution
Volume percentage(V/V) of a component = Volume of the -x100
Total volume of the solution
Note: This unit is useful when both the solute and solvents are liquids.
12. What is the meaning of 10% ethanol solution in water?
Ans: It means 10ml ethanol is dissolved in water such that the total volume of the solution is 100 mL.
13. Define mass by volume percentage. Give an expression to calculate. the volume percentage for the
given mass and volume of solute and solvent.
Ans: Mass by volume percentage of a solution is defined as mass of the solute dissolved in 100 mL of the
solution.
Mass of the solute
Mass by volume percentage = -x100
Volume of the solution
Note: This unit is useful when solute is solid and solution is liquid. This unit is commonly used in medicine and
pharmacy.
14. Define parts per million.
Ans: It is defined as the number of parts of solute dissolved in one million parts of the solution.
Number of parts of the solute
Parts per million(ppm) = -x10
Number of parts of all components of the solution
Parts per million are also expressed in w/w, V/V and w/V.
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Solutions

Note: This unit is suitablc when solutes arc prescnt in tracc quantitics.
reasone
15. Divide the following units into temperáture dependent and temperature independent with
() Molarity (M) (ii) Molality (m)
(li)Mole fraction (r) (iv) Mass percent (w/w)
(v) Mass by volume percent (m/N) (vi) Parts per million (ppm)
Ans: (1) Mass percent, ppm, mole fraction and molality are independent of temperature because
mass
s
independent on temperature.
(ii)) Molarity and mass by volume percent depends on temperature because volume depends on
temperature.

Multiple Choice Questions (MCQs)

1. In a solution larger component is named as 8. Molarity of the solution is
number of moles of
a) solvent b) solute the solute dissolved in
) liquid d) solid a) 1 kg of solvent b) 1 kg of solution
2, A solid solution in which solute is c) 1 Lof the solvent d) 1
L of the solution
a) Solid only b) liquid only 9. Molarity of a solution
c) gas only d) solid or liquid or gas a) Increases with increase
in temperature
3. The following is the exanple for solid solution b) Decreases with increase
in which solute is gas c) Remains same at
in temperature
all temperature
a) oxygen dissolved in water d) May increase or decrease
b) mixture of O; and nitrogen with increase with
temperature depending
c) solution of hydrogen in palladium of the solvent
10. Unit for molarity is
d) glucose dissolved in water
a) g Litl b) mol Lit!
4. Which of the following is not a c) mol kg
gaseous d) molLit
solution? 11. Molality of a solution
a) camphor in nitrogen gas is number of moles of
b) chloroform mixed with nitrogen gas the solute dissolved in
a) 1 kg of solvent
c) solution of hydrogen
in palladium b) 1 kg of the solution
d) mixture of oxygen and nitrogen
c) 1 Litre of the solvent
5. Which one of the given below d) 1Litre of the solution
is the liquid
solution 12. Unit for molality
a) amalgam of mercury and sodium is
b) chloroform mixed with nitrogen gas a) mol L! b) mol kg
c) glucose dissolved in water c) mol kg d) gkg
d) copper dissolved in gold
13, The concentration term of a solution does not
6. Which one of the
following is not a solid changes with change in temperature is
solution a) Molality
a) camphor in nitrogen gas
b) Molarity
b) solution of hydrogen in palladium c) Mass by volume percent
c) amalgam of mercury and sodium
d) Volume percerntage
d) Copper dissolved in gold
7. Type of the solution 14. If the solute is present in trace quantities in
obtained when copper generauy
dissolved in gold is solution, its concentration is
a) Heterogeneous mixture expressed as
b) Gaseous solution a) Molarity b) Molality
c) Liquid solution c) parts per million d) Mole fraction
d) Solid solution

Chemistry
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Jeevith Publications

1
Answer Keys
6 7 10 1112 13 14
b a b a C

Numerical Problems
1. Caleulate the molarity of a solution .. Volume of solution is given by
containing 5g of NaOH in 450 mL solution.
(NCERT Solved Problem) Mass of solution
V=
Ans: Molar mass of NaOH = M, = 23 + 16+1 = 40 density of solution

g mol-l 100g
1.504 g/mL
=66.5 mL
Molarity= W Xl000
Molecular mass of HNO,
M,xV = M, =1+14+3x16= 63 g mof-!
5x1000
=0.278 M
40x450 : Molarity = 68x1000
63x 66.5
-=16.231 M.
2 Calculate the molarity of each of the
following solutions 4. Calculate the amount of benzoic acid
[CGH;COOH] required for preparing 250
(a) 30 g Co(NO:)2. 6H,0 in 4.3 L solution. mL of 0.15 M solution in methanol
(b) 30 mL of 0.5 MHSO, diluted to WB X1000
500 mL. [NCERT intext question] Ans: Molarity =
MxV
Ans: Molar mass of Co(NO,)2 Molar mass of C&H,COOH,
6H,0 = M, =58.9+2(14+ 48) + 6x18= 290.9 g mol! M
=7x12 +6x1+2x16=122 g mol

W, =30g, V=4.3L= 4300 mL 0.15-W X1000

(a) Molarity 122x 250
WB X1000 30x1000 0.15x122x 250
=0.02398 M.
-=4.575g
MxV290.9x4300 1000
(b) MV, MV2 5. Caleulate molality of 2.5 g of ethanoic acid
(CH,COOH) in 75 g of benzene [NCERT
After dilution Before dilution solved problem]
M, x500 0.5 x 30
Ans: Molality = Wp X1000
0.5x30 M
M= 500 =0.03 M.
Wa=2.5 g, WA =75 g
3. Concentrated nitric acid used in laboratory Molar mass of aceticacid,
work is 68% nitric acid by mass in aqueous
solution. What should be the molarity of M, =2%12+4x1+ 2x16=60 g mol

such a sample of the acid if the densityy of 2.5x1000,

the solution is 1.504 g mL. Molality =0.5556 m.
60x75ST
[NCERT Exercise problem] 6. Calculate the mass of urea (NH,CONH;)
= Wp X1000 required in making 2.5 kg of 0.25 molal
Ans: Molarity aqueoussolution. (NCERT Intext question)
M, xV
Ans: WB =?,
68% nitric acid means 68 g nitric acid present
in 100 g solution Molar mass ofof urea,
.:. Mass of nitric acid = Wa = 68 g M,B =2x14+4x1+12+16
Massof solution = 100 g =60 g/mol
Density of solution = 1.504 g mL

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Mass solution 2,5 kg = 2500 g

of For 466.5x 10g nalorophene, solution
molality = 0.25 molal. required =1000+ 466.5x 10
=1000.04665 g
i.e., 0.25 moles of solute in 1000 g of solvent. 466.5× 10 g nalorophene requires
Mass of solute = nmoles of solute x Molar 1000.4665
1.5 x 10g nalorophene requires
Imass
Mass of solute = 0.25x 60 = 15g xg solution
Mass of solution= 1000+15 =1015g 1000.4665×1.5x 103
=3.216 g
1015 g of
solution contains ----15 g ofurca. 466.5x103
.. 2500g of solution contains ----x'g of urea
9. In a binary solution, mole fraction ofa
component is 0.85. What is the mole fraction
15x 2500
-=36.9 =37 g of urea. of the other component?
1015 Ans:
7. If of some lake wvater is 1.25 g
the density 0.85 +
x, =1
mL and contains 92 g of Na" ions per kg of
water. Calculate the molarity of Na" ions in i.
X = 0.15
the lake. INCERT exercise problem] 10. Calculate the mole fraction of ethylene
Ans: MB = Atomic mass of Na = 23 g mol! glycol (C,H,0:) in a solution containing
W
=92g 20% of CH,0, by mass. (NCERT Solved
Problem)
WA (mass of water) = 1000 g
Ans: 20% ethylene glycol means 20 g ethylene
Density =1.25 g/mL
glycol present in 100g solution
.. Volume of solution = Mass of solution .. = 20 g W

Density of solution
W, =100-20 =80 g
1000
=800 mL McHo, =62 g mol, MHO =18 g mol
1.25
Number of moles of
MolarityWp X1000
M, xV, WB 20
C,H,0, =np M
-=0.322 mol
62
92x1000
Number of moles of
23x 800
Molarity =5 M H,0=na WA 80 =4.444 mol
M, 18
8. Nalorphene (CGHNO) similar to
morphine, is used to combat withdrawal> Mole fraction of ethylene glycol
symptoms in narcotic usersS. Dose of 0.322 =0.0676.
nalorphene generally given is 1.5 mg. 4.444+0.322
natnB
Calculate the mass of 1.5 × 10° m aqueous 11. Calculate the mole fraction of benzene in
solution required for the above dose.
solution containing 30% by mass of it in
[NCERT Exercise problem) (NCERT Intext
carbon tetrachloride.
Ans: M, =19x 12+2lx1+14+3 x16=311 g mol!
Question)
1.5×10 molal means 1.5×10 moles
water. Ans: Molar mass of
present in 1000g of g mol
Mass of solute = moles of solute x molecular CH, =6x12 +6xl=78
mass Molar mass of
.. mass nalorphene =
154 g mol"
of CCI, =1x12+4x35.5
Wh =1.5 x 10° x311= 466.5x 10g
Chemistry
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30% benzene by mass means 30 g benzenc in (c) Calculation of mole fractionof KI

100 g solution
.:. Mass of
benzene = 30 g
n, +np
Mass of CCl4 = 100- 30 = 70 g
0.12048
30 =0.02639.
=0.385 mol 4.444+ 0.12048
78 13. A solution of glucose in water is labelled as
70 10% w/w. What would be the molality and
Nçci, 0.454 mol
154 mole fraction of each component in the
solution? If the density of solution is 1.2 g
ncl, 0.385
+ ncc, 0.385+ 0.454 mL', then what shallbe the molarity of the
solution. (NCERT Exercise problem)
=0.4588
12. Calculate (a) molality (b) molarity and () Ans: 10% glucose solution means 10 g glucose
mole fraction of KI if the density of 20% present in 100 g solution
g Mass of glucose = WB = 10g
(mass / mass) aqueous KI is 1.202 mL.
[NCERT intext question] Mass of solution = 100 g
means 20 g Mass of water (w,)=100g-10g =90g
Ans: 20% (w/w) aqueous KIsolution
100
KI is present in 100 g of the solution. Volume of solution = V= =83.33 mL
1.2
Mass of KI=Wp= 20 g,
g= 80g Molecular mass of glucose
Mass of water WA = 100 g-20
=

= M, =180 g mol-!
mass of solution
Volume of solution (V) = Number of moles of glucose
density of solution
10
100 g = n = =0.0555 mol
=83.1947 mL 180
1.202 g /mL
90
Molar mass of KI=Mp= 39+127.= 166 g mol, Number of moles of water =n, 18
-=5 mol
= g
Molar mass of H,0= MA 18 mol!
Calculation of molality
Number of moles of KI Wa X1000
Molality =
20 M
xWA
=n, = =0.12048 mol
166 10x1000
water =0.6173 m
Number of moles of 180x 90
80 Calculation of mole fraction
=4.444 mol ng
18
glucose
+ng
(a) Calculation of molality of KI
X1000 0.0555
W
=0.01097
Molality = 5+0.0555
M,XWA
20x1000
XH,0
t ghu cose =1
=1.506 m
=
=1-Xglucose = |–0.01097 0.989
166x 80
Caleulation of molarity
(b) Calculation of molarity of KI W
X1000
=:
Wp X1000 Molarity
Molarity= M, xV
M xV 10×1000
=0.6667M.
20x1000 -=1.448 M 180x 83.33
166x 83.1947

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Solutions
12
cthylene glycol = g mol
Molar mass =62
M
of

14. An antifrecze solution is prepared rom

222.6 g of cthylene glycol (CH,0,) and
200 Calculation of molality
of water. Calculate the molality of
the = W, x1000
Molality
solution. If the density of the solution
is MxWA
1.072 g mL' then what shall be the 222.6x1 000
-=17.95 m
molarity of the solution. 62× 200
|NCERT Exercise problen]
Calculation of molarity
Ans: Mass of ethylene glycol = Wh =222-6g 1000
Molarity =
Wh X

Mass ofwater W, =200 g

=
M,xV
Mass of solution = 222.6 + 200 = 422.6 g 222.6x1000
=9.107 M
Volume of the solution 62×394.22
Mass 422.6
V= =394.22 mL
Denisity 1.072

1.3 Solubility
K Define solubility.
Ans: The maximum amount of a substance that can be dissolved in a specified amount of solvent at a snecif
temperature is called solubility.
On what factors does the solubility of a substance depend?
Ans: (i) Nature of solute
(ii) Nature of solvent
(iii) Temperature
(iv) Pressure
3. What is the basic rule (principle) to decide the solubility
Ans: "Like dissolves like" iie., polar solutes are
of solute in solvent?
dissolved in polar solvents and non polar solutes are dissolved
non polar solvents.
4. Sugar is dissolved in water but not in benzene.
Ans: Sugar can form' hydrogen bond with water.
Explain.
Therefore, sugar is dissolved in water. But benzene is non pol
solvent and hence sugar is not soluble in benzene.
5. What is dissolution?
Ans: When a solute is added to the solvent, some
solute dissolves and its concentration increases in solution. TE
process is called dissolution.
6. What is crystallisation?
Ans: Some solute particles in solution
collide with the solid solute particles and get
process is called crystallisation. separated out of solution. IE
K What is saturated solution?
Ans: A solution in which no more solute can
be dissolved at the same temperature
saturated solution. and pressure s
What is unsaturated solution?
Ans: A
solution in which some more calle
solute can be dissolved under pressure is
unsaturated solution. the same temperature and
What is the effect of temperature on
Ans: ()
solubility of a solid in liquid?
Solubility of a solid in liquid increases as process
temperature increases if the dissolution
endothermic (AH
=tve).
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Jeevith Publications 13

(ii) Solubility of solid in liquid decreases as temperature incrcascs if the dissolution process is exothermic
(AH =-
ve)
10. What is the effect of pressure on solubility of solid in liquid?
Ans: Pressure doesnot have any significant cffect on solubility of solids in liquids.
11. What is the effect of temperatureon the solubility of a gas in liquid? Give reason.
Ans: Solubility of agas in liquid decreases when temperature is increased. Due to cxothermicin nature.
12. Solubility of gasin liquid deereases as temperature increases. Why?
Ans: Because dissolution of a gas in liquid is exothermnic process.
State Henry'slaw. Write its mathematical form. |March - 2018, July 2018, July 2020]
Ans: It states that, at constant temperature, the solubility of a gas in a liquid is directly proportional to the partial
pressure of the gas present above the surface of liquid or solution.
or
The partialpressure of the gas in vapour phase (p) is proportional to the mole fraction () of the gas in the
solution.
i.e., p = KHx,.
where KH=Henry's law constant, x = mole fraction of the gas
p
Partial pressure of the gas in vapour phase.
What isthe significance of Henry's law constant?
Ans:The higher the value of Ky lower is the solubility.
15. At constant temperature different
gases have different Ky value.What does this statement suggest?
[April 2022/

Ans: KHvalue depends on nature of gas.

a temperature pressure nitrogen gas is,more soluble in water than Helium gas. Which
16. At given and
one of them has higher Ky Value? March –2015, July 2020|
Ans: Helium.
0.413 / k bar
KH Values for the gases argon and methane
in water at 298K are 40.3 /k bar and
17.
respectively. Which gas is more soluble at this temperature?

Ans: Methane Solubility a Kyvaue

gas in liquid solvent
Henry's law constant for a particular
18. “As the temperature increases, the
increases?. What is the inference of this statement?
solvent decreases.
Ans: Solubility of gas in particular warm water. Give reason.
in cold water rather than in
19. Aquatic species are more comfortable more than warm water.
oxygen (0;) in cold water is
Ans: Solubility of
law.
Give any three applications of Henry's beverages (To increase the solubility of CO,
in soda water, soft
çarbonated
Ans: (i) It is used in the preparation of
sealed under high pressure).
drinks and in beer, the bottle is respiration (To avoid bends and toxic
effects of nitrogen
or deep sea divers for
(ii) It is used by scuba divers
under deep sea). pressure of oxygen is less.
for respiration. (At high altitudes the partial
climbers to become weak unable to think
(ii) It is used by mountainoxygen blood and tissues causes climbers
in the
The low concentration of
clearly which causes anoxia) under high pressure. [March - 2016]
dissociation of CO; in softdrinks
21. Name the law behind the
Ans: Henry's law.
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22. Explain the cause for the discase bends in scuba (decp sea) divers.
Ans: As scuba divers go down in the sca, pressure increases underwatcr. Increascd pressurc increases the
solubility of nitrogen in blood. When the diver comes to the surface, the pressure gradually decreases. Thi
releases dissolved gascs and lends to the formation of bubbles of nitrogen in the blood. This blo.
capillaries and creates a medical condition called bends which is painful and dangerous to life.
23. How to control the disense bends and toxic effects of high concentration of nitrogen in the blond t.
scuba divers during deep sen diving?
Ans: To avoid the bends the tanks uscd by scuba divers arc fillcd with air diluted with hclium
(11.7%), nitroge
(S6.2°%) and oxygen (32.1%) becausc of the low solubility of helium in the blood than
nitrogen.
24. Name the disease causcd to the sca divcrs if they carry atmospheric
air.
Ans: Bends
25. Name the disease caused to the pcople living at high altitudes or
mountain climbers.
Ans: Anoxia
26. People living at high altitudes or mountain climbers suffering
Ans: At high altitudes, the partial pressure from anoxia. Give reason.
of oxygen is less than that at the ground level. This results in loy:
concentration of oxygen in the blood and tissues
causes the disease called anoxia. of the people living at high altitudes or climbers, Thi
27. What is the symptoms of anoxia in peoples living at high
Ans: The people living at high altitudes are weak altitudes?
and unable to think clearly. These are the symptoms
of anoxia.
Multiple Choice Questions (MCQs)
1 Solubility of a solid in a liquid does not 5. According to Henry's Law, the
depend on pressure of the gas partia
a) nature of the solute in the vapour phase
proportional to its i
b) nature of the solvent
a) Molarity b) Molality
c) presSure c) mole fraction d) mass percentage
d) temperature
6. A solution in which no. more solute can
be
If the process of dissolution of a solid in liquid dissolved at the same temperature and
is an endothermic, its solubility
pressure is called
a) Decrease with increase in temperature a) Saturated solution
b) Increase with increase in temperature. b) Unsaturated solution
c) Remains same at all temperature c) Super saturated solution
d) cannot be predicted d) Dilute solution
Solubility of a gas in a liquid 7. An unsaturated solution in which
a) Increases with increase in temperature a) Some more quantity of solute can be
b) Decrease with increase in temperature dissolved in it
c) Unaffected on changing the temperature b) Precipitation takes place
d) Decrease with increase in pressure c) Dynamic equilibrium is attained between
Solubility of gas in liquid decreases with solute and solvent
increase in temperature. Thisis because d) Solubility of this solution does not depends
a) Dissolution of gas in liquid is exothermic on temperature
process 8. The name of the disease caused to the people
living at high.altitudes or mountain
b) Dissolution of gas in liquid is endothermic climbers
oxygen in blood 1S
proceSS due to low concentration of
c) Dissolution of gas in liquid is exothermic or a) Anoxia b) Bends
endothermic process d) Beri Beri d) Goitre
d) No heat change occurs during its
dissolution
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Jeevith Publications 15

9. To avoid the bends during scubn diving, the c) Charle's law d) Dalton's law
tanks used by scuba divers are flled with air 12. When non volatile solute is added to volatile
diluted with vapour pressure
a) 11.7% helium, 32.1% Oxygen and 56.2%
solvent, the of solvent at
constant temperature
nitrogen
a) decreases
b) 32.1% helium, 11.7% oxygen and 56.2%
b) increases
nitrogen c) may decrease or increase
c) 11.7% nitrogen, 32.1% helium and 56.2% d) nochange in the vapour pressure
OXygen
13. The solutions which obey Raoult's law over
d) 11.7% helium, 56.2% Oxygen and 32.1% the entire range of concentration are known
nitrogen as
10. In a solution containing two volatile liquids, a) ideal solutions
b) dilute solutions
the partial vapour pressure of each
c) concentrated solutions
component in the solution is directly
d) non ideal solutions
proportional to its mole fraction present in
the solution. This statement is called 14. Ku value is the function of the nature of gas.
a) Henry's law If the KH value of the gas is more, the gas is
b) Raoult's law of liquid solutions a) more soluble
c) Dalton's law of pressure b) less soluble
c) No change in its solubility
d) Boyle's law
d). cannot be predicted
11. Raoult's law as a special case
a) Henry's law b) Boyle's law
Answer Keys
2 3 45678 1011
r
12 13 14
b b a a a a a b

Numerical Problems
-1. If nitrogen gas is bubbled through water
gas Mass of 1L water 1000
at 293 K, how many millimoles.of N2 ny,o 855.55 moles
Molecular. mass 18
woulddissolve in litre of water? Assume
1

nN,
that N2 excerts a partial pressure of 0.987 1.29 x10s
55.55+ nN,
bar. Given that Henry's law constant for
N2 at 293 K is 76.48 k bar. In denominator is neglected as ny, <<55.55
[NCERT solved problem]
.. 1.29 x105
Ans:. According to Henry's law 55.5
-55.55 1.29×105=71.6610 moles
x

p=Kyx ..
0.987 bar -=1.29x10-5
n=0.716 m mol.
P
76,48 x10° bar 2. H,S, a toxic gas with rotten egg smell, is
Ku used for the qualitative analysis. If the
m,
nN, solubility of H,S in water at STP is 0.195
XN. constant
calculate Henry's law
|NCERT intext question]
Ans: Solubility of H,S = 0.195 m=0.195 mole in
1000g water
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16
Solutions
Mass ofwater 1000 g
no
m

Number of moles of water

Sincc >
nco,, nuo + nco,
no
1000 nco
-$$.S5 moles
18

Mole fraction of
H,S=Ns ns But
500
n0 = 18 =27.78 moles
(:: 500 ml = 500 g)
0.195 H0
=0,003498
55.55 +0.195 ..
Pressure at STP= 0.987 bar 1.517x10-3co,
According to Henry's law . 27.78
nco, =27.78 x 1.517×10
p=Kx =42.14x 10mot
K,
P
0.987 = Mass of CO, = nco. X mass
molecular of CO,
0.003498 282.16
bar.
= 42.14x10
3. Henry's law constant for C0, in water is x44 = 1.854 g

1.67 x 10 Pa at 298 K.
4. Henry's law constant for the molality of
Calculate the methane in benzene at 298 K is 4.27 x 109
quantity of CO; in 500 mL of soda water mm Hg, Calculate
when packed under 2.5 atm CO; pressure the solubility of methane
at in benzene at 298
K under 760 mm He.
298 K. INCERT intext question]
INCERT exercise problem
Ans: According to Henry's law
Ans: According to Henry's law
Pco, = Kuco, But Pct, =KHCH,
Pco 2.5x101325 Pa Pct. 760 mm Hg
Ku 1.67x 10 Pa =1.517x103 CH, =
KH 4.27x10 mm Hg =1.78x10-3
nco, renreset
Note: Mole fraction represents
Xco; the solubility of
nH,o +nco, methane in benzene.

1.4 Vapour Pressure of Liquid

1. What vapour is
Solutions
pressure or equilibrium vapour
Ans: The pressure exerted by the vapours pressure?
above the- liquid surface at constant temperature
cquilibrium with the liquid is called vapour pressure when they are in
or saturated vapour pressure or equilibrium vapour
pressure.
Vapour pressures of chloroform
and dichloromethane are 200mmn of Hg and 415mm
respectively. Which one is more volatile? of Hg at 298K
Ans: Dichloromethane [Higher
the vapour pressure, more volatile]
3.
State and explain Raoult's law of liquid
solutions. (July-20171
Ans: It states that in a solution
of volatile liguids, the partial vapour pressure
directly proportional to its mole fraction. of eah component of the solution 1S
Consider a solution containing two
volatile components 1 and 2.
According to Raoult's law, p,
c x or P, Px,
Similarly P:
=Px;
Pi = vapour pressure of the component 1
in the pure state,
=mole fraction ofthe component
1,

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Jeevith Publications 17

P partial vapour pressureof the component 1

from the solution
P:= partial vapour prcssure of component 2 from the solution.

P== Vapour pressure of component 2 in pure state

*2 mole fraction of component 2 in the solution.
.. Total vapour pressure of solution =Potal
=P, +P,

4. 1Vrite the mathematical form of Raoult's law for solution containing two volatile liquids.
Ans: Protal= P
+px,
5. Give the conclusions drawn from Raoult's law for solution containing two volatile liquids.
Ans: () Total vapour pressure over thc solution can be related to the molefraction of any one component.
(ii) Total vapour pressure over the solution varies linearly with the molefraction of component 2.
(i1) Depending on the vapour pressures of the pure components and 2, total vapour pressure over the
1

solution decreases or increases with the increase of the mole fraction of component 1.
6. How do you determine the composition of components in the vapour phase in equilibrium with the
solution?
Ans: The composition of vapour phase in equilibrium with the solution is determined by the partial pressures of
the components.
If y and y, are the mole fractions of the components 1
and 2 respectively in the, vapour phase, then using
Dalton's law of partial pressures,
X Protal
P)
=I
P22 x Protal

Numerical Problems
1. Vapour pressure of chloroform (CHCI;)
and dichloromethane (CH;Cl,) at 298 K =XCH,Cl,
nCH,CL,

are 200 mm Hg and 415 mm Hg nCH,C, tnCHCI

respectively. i) Calculate the vapour .0.47
pressure of the solution prepared by CH,CI, =0.688
0.47+0.213
mixing 25.5 g of CHCI, and 40 g CH,CI, Mole fraction of CHCI, = XCHC,
=1-XCH.C,
at 298 K and (ii) mole fractions of each
=1-0.688=0.312
component in vapour phase.
Ans: Molecular mass of
Proal P +pn
CHCI, =lx12+1x1+3×35.5 =119,5 g = PCH,C, X Cn,Ci, + PCHC, XFCHCI,
Molecular mass of =415x0.688+200× 0.312
g mol
=

CH,CI, =1x12+2x1+2x35.5 85 = 285.52+62.4 =347.92 mm Hg

Number of moles of CHCl,
Mole fractions in gas phase
25.5 =0.213mol
PCH,Ch
119.5 YCH,C,
40 P.total
Number of moles of CH,CI, = -0.47 mol
85 PCH,C, = PCH,C, X XcH,CI,

Mole fraction of CH,CI, =415x0.688 =285.52 mm Hg

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18

285.52 n+np
yn 0,8206
347.92
-0,8206 0.1794
= 5.556 = 0.886
Yoo, 1-yoya, 5.556+ 0.714,
an idcal solution.
2. Hcptane and octane form =
=500 x0.886 443 torr
vapour prcssures of the two p, =pn Xp
At 373 K, the
are 105.2 kpa and 46.8
liquid componcnts
the vapour
Ptotal
kpa respectivcly. What will be =
potal - PB
=
475–443 =32 tor
pressure of a mixtureof 26 g heptane and 35
PA

gof octane? (NCERT exercise

qucstion) X= 1-Xp=1-0.886=0.114
Ans: According to Raout's law Pa =Px
Poctane Noctane X Poctane
PA.
Pheptane =heptane X Pheptane PA

Molar mass of octanc (CgHs)

g
=8 x 12 +
18 x |=l14 mol 32 = 280.7 torr
Molar mass of heptane (C,H6) -1
0.114
=7x 12 +1 16= x 100 g mol 4. The vapour pressure of pure liquids A an
B are 450 and 700 mm Hg respectively, a
Number moles of octane
350 K. Find out the composition of the
W 35
=0.307 mol liguid mixture if total vapour pressure j
M 114
600mm Hg. Also find the composition of th
Number of moles of heptanes vapour phase. [NCERT intext question]
W 26
=0.26 mol Ans: It is given that: p
=450 mm of Hg,
M 100
Mole fraction of octane mmof Hg, Ptotal = 600 mm of Hg
p=700
noctane 0.307
=Xoctane =0.5414 =p
n octane t heptane 0.307+0.26 From Raoult's law, p, and
=
=l-Xocane =10.5414 0.4586
heptane
PB=Pg Protal PA +PB
Poctane 0.5414 x 46.8 kpa = 25.337 kpa
= 0,4586 x 105.2 kpa = 48.244 kpa
Pheptane Prota!
PAA +P(1-x)
Total vapour pressure
PiotalpPoctane Pheptane
Piotal
PAA +P;-PA
=
25.337+ 48.244 =73.581 kpa Piotal =(PA -PB)xA+P
3. 100 g of liquid A (molar mass 140 g mo")
was dissolved in 1000 g of liquidB (molar 600 = (450– 700)r+700
mass 180 g mol). The vapour pressure of -100 =-250x4
pure liquid B was found to be 500 torr. A4
0.4

Caleulate the vapour of pure liquid A and Therefore, X

=1 -X4
its partial vapour pressure in the solution if =|-0,4
= 0.6
the total vapour pressure of the solutioni is
475 torr. |NCERT exercise question] Now, PA =PåA
mm ofHg
Ans: Number of moles of liquid =450 x 0.4 =180
= mm of Hg
=Pra =700 x 0.6 420
A
=n= 100 =0,714 mol
PB
140 Now, in the vapour phase:
Number of moles of liquid 180 =0.3
A=
PA
Mole fraction of PA +PB 180+ 420
1000
B=n,= -=5.556 mol of B= 1-0.3= 0.7
180 Mole fraction
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Jeevith Publications 19

1.5 ldeal and Non Ideal Soltions

1. What are idealsolutions? Give examples.
Anss The solutions which obey Raoult's law at all concentrations are called ideal solutions.
Examples: () Benzene and Tolucne
(i) Bromocthane and chloroethane
(i) n-hexane and n-heptane
2. "Ideal solutions obey Raoult's law". What does it mean?
Ans: It means that the vapour pressure of solution measured by the experiment is equal to the vapour pressure
calculated from Raoult's law.
3. Give any four general characteristics to form ideal solutions. March - 2014]
Ans: () They should obey Raoult's law.
(ii) AVmix = 0, i.e., there should be no change in volume on mixing.
(ii) AHmiy = 0, i.e., there should be no change in enthalpy (heat) on mixing.
(iv) The forces of attraction between A and B (solvent and solute) molecules will be
sane as that of A-A
(solvent - solvent) and B -B (Solute solute) molecules.
4. Mention the enthalpy of mixing (AHmi) value to form an ideal solution. [March -2019)
Ans: Zero.
5. Draw the graph of vapour pressure against mole fraction of an ideal solution.

Ans:
PA Pe.
preSsure
Po II

Vapour
P

X,
=1 Mole fracetion
6. What are non-ideal solutions give examples.
are called non-ideal solutions.
The solutions which do not obey Raoult's law at all concentrations
Ans:

Examples: (i) HCl and water (ii) Ethyl alcohol and water, (iii) Ethanol and acetone (iv) CS; and acetone
7. Give any four conditions to form non-ideal solutions.
Ans: (i) They should not obey Raoult's law.
(ii) AV0
(ii) AHmiy #0 - A and
or
(iv)The forces of attraction between A and B molecules will be greater lesser than that of A
B-B molecules.
8 Give differences between ideal and non-ideal solutions.
Áns:
SI. Ideal solution Non-ideal solution
i. They obey Raoult's law. They do not obey Raoult's law.
ii. AVi =0
AV
mix
#0
111., AHmi, 0 AH,mix 0
The forces of attraction between A and B molecules
The forces of attraction between A
and B molecules will be greater or lesser than that of A - A and
iv.
will be same as that of A

–A and B -B molecules. B-B molecules.

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20
Solutions
Name the (ypes of non-ideal solutions.
Ans: Non ideal solutions are two
of types.
(i) Non idealsolution showing positive deviation from Raoult's law.
(i) Non idcal solution showing negative dcviation from Raoult's law.
10, Which typeof solutions show positive deviation?
Ans: Vapour pressure of the solution is highcr than that Give examples
calculated from Raoult's law shows positive deviation
Eample: ())Mixturc of cthanol andacctonc (ii) Mixture of carbon disulphide and acetonc.
11, On mixing cqual volume of acctone and ethanol what type of
Ans: Positive deviation. deviation from Raoult's is expected.
12, Mixture of acetone and cthanol shows
Ans: In pure ethanol, molecules are hydrogen positive deviations from Raoult's law. Give reason (April 20221
bonded. On adding acetonc, its molecules get in
molecules and break hydrogen bonds between between the ethanel
them. Due to weakening of interactions, the
positive deviations from Raoult's law. solution shoe
13. Solution of carbon disulphide and acetone
shows positive deviations
Ans: When carbon disulphide is added to acetone, the dipolar interactions from Raoult's law. Why?
weaker than the respective interactions among solute-solute, between solute -solvent molecules ara
solvent-solvent molecules.
14. Using the graph answer the following:
i) What type of non-ideal solution
shows such a behaviour?
ii) What can youinfer about
the molecular interactions before & after
iii) What type of azeotrope will the mixing A and B?
mixture of A and B form?
Vapour pressure of solution

pressure

Vapour

Mole fraction
X,=0

B
Ans: () Non ideal solution with positive deviation.
(i1) A- interactions are weaker than A -Á and
B

B-B interactions.
(ii) Minimum-boiling point azeotrope.
15. Which type of solutions show negative deviation from
Raoult's law?
Ans: Vapour pressure of the solution is lower than that calculated by Raoult's law shows negative deviation from
Raoult's law.
Examples: Phenol and aniline, Chloroform and acetone.
16. Solution of phenol and aniline show negative deviation from
Ans: This is because the intermolecular hydrogen bonding between Raoult's law. Give reason.
phenolic proton and lone pair on nitrogen
atom of aniline is stronger than the respective intermolecular hydrogen
bonding between similar molecules.
So, vapour pressure of the solution becomes less than the expected.
17.) A mixture of chloroform and acetone forms a solution wvith negative
deviation from Raoult's e
/Why?
Ans: This is because chloroform molecule is able to' form hvdrogen bond with acetone mmolecule. This decreas
the escaping tendency of molecules for each comiponent and hence vapour pressure decreases nan
expected.
Chemistry
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21
Jeevith Publications

18. Draw the graph to show non ideal solutions with nerative deviations.
Ans:

pressure

-Ideal solution
Vapour

Non-ideal solution
with negative deviation

0.2 0.4 0.,6 0.8 1.0

I=0 Mole fraction X,=1

deviation from Raoult's law.

19. Give differences between solutions showing positive deviation and negative
[March - 2017|
Ans:
Non ideal solution with negative deviation
Sl.o. Non ideal solution with positive deviation
AV =+ve (i.e., volume increases on mixing two AV=-ve (volume decreases on mixing two
i components)
components)
=+ve (heat absorbed on mixing) (heat is liberated on mixing)
AHi =-ve
ii. AH,
vapour pressure is lower than that calculated
The vapour pressure is higher than that calculated The
iii. from Raoult's law. from Raoult's law.
between A and B molecules will
Forces of attraction between A and B molecules will Forces of attraction of
be less than that of - A and B B molecules. -A and B B molecules.
A

iv. A be greater than that

non ideal solution containing two liquids

20. How does the enthalpy change during the formation of
showing positive deviation from Raoult's law?
Ans: AH =+ve
reason for a solutiòn of
A

and B to shoW positive

21. Based on inter molecular interactions, give the
deviation from Raoult's law.
Ans Due to weaker A- B molecular interactions.
an example,
22. What are azeotropes or azeotropic mixtures? Give at a constant
having the same composition in liquid and vapour phase and boil
Ans: Binary liquid mixtures
temperature are called azeotropic mixtures. 32% water by mass.
alcohol and 59% water by volume (ii) 68% nitric acid and
Example: (i) 95% ethyl
components cannot be separated by fractional distillation.7
Note: In azeotropic mixtures the
23. Name the types of azeotropes or azeotropic mixtures. azeotropes.
types: (i) Minimum boiling azeotropes (i1) Maximum boiling
-Ans: Azeotropic mixtures are of two
24.) What are minimum boiling azeotropes?
Give an example. azeotropes.
which show large positive deviation from Raoult's law are called minimum boiling
Ans: The solutions
boiling point of the components.
They boil at lower temperature than the boils at 78.15°C which
Example: 95% Ethyl alcohol and 5%
water by volume (rectified spirit), This mixture
and pure water (100°C)
s lower than that of pure ethyl alcohol(78.5°C)
25. What are maximum boiling azeotropes?
Give an example.
azeotropes.
large negative deviation from Raoult's law are called maximum boiling
Ans: Solutions which show the
mass with a boiling point of 393.5K.
Example: 68% nitric acid and 32% water by
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26. Componcnts of a non ideal binary solution cannot be completely separated

by fractional distillation
Why?
Ans: Duc to the formation of azcotropic mixturc.

Multiple Choice Questions (MCQs)

1. Raoult's law is a special case of Which of the following is an example for
a) Henry's law 7.
b) Boyle's law non ideal solution
c) Van't Hoff's law d) Charle's law with negative deviation
a) Phenol + Aniline
According to Raoult's law of liquid solutions
for any solution, the partial vapour pressure b) n-hexane + n-heptane
of each volatile component in the solution is c) Carbon disulphide + Acetone
directly proportional to its d) Ethanol + Acetone
a) more fraction b) molarity 8. Azeotropes are binary mixtures having
c) molality d) ppm a) same composition in liquid
and vapour
3. Which of the following is not the property phase and boil at constant temperature
of b) different composition in
ideal solution liquid and vapour
a) A,mis H=0 phase and boil at constant temperature
c) same composition in liquid
b) A,mix V=0 and vapour
phase and boil at different temperature
c) They obey Raoult's Law d) different composition
d) They form azeotropic mixture in liquid and vapour
phase and boil at different temperature
4. Vapour pressure of a liquid át constant 9. The solutions which show. a large positive
temperature deviation from Raoult's law form
a) Increases when a solid is dissolved a) Minimum boiling point azeotrope
b) Decrease when a non volatile solid is b) Maximum boiling point azeotrope
dissolved in it c) Minimum or maximum boiling point
c) Decrease with increase in temperature azeotrope
d) Always remains same at all temperature d) No azeotrope
Which is an example for ideal solution 10. The solutions that show large negative
a) Acetone + chloroform deviation from Raoult's law form
b) Phenol + Aniline a) Minimum boiling azeotrópe
c) Ethanol + Acetone b) Maxinmum boiling azeotrope
d) Benzene + Toluene c) Minimum or maximum boiling azeotrope
Which of the following is a non ideal d) No azeotrope
solution 11. According to Raoult's law, total vapour
a) n-hexane + n-heptane pressure -of the solution containing to
b) carbon disulphide + Acetone
c) bromoethane + chloroethane volatile liquid (p) is equal to
d) Benzene + toluene: a) P=px+PåB
b) P=p1-x)+P
c) P=påx +P(l-x)
d) All of these
Answer Keys
3 4
10: 11
5678
d b d b b d
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1.6 Colligative Properties

1. What arecolligative propertics?
Ans: The properties of dilute solutions depend only on the number of solute particles present in the dilute solution
but not on their nature are called colligative properties.
2. On what factor does the colligative property value depends. (July - 2015]
Ans: It depends on the number of solute particles but not on their nature.
3. Name the four colligative propertics.
Ans: (i) Relative lowering of vapour pressure
(ii) Elevation in boiling point or Ebullioscopeor increase in boiling point.
(iüi) Depression in freezing point or Cryoscope or decrease in freezing point.
(iv) Osmotic pressure.

() Relative Lowering of Vapour Pressure

What happens to the vapour pressure of the pure liquid when non volatile solute is dissolved in it?
a
4.
Ans: Vapour pressure of liquid decreases.
5. Define lowering of vapour pressure.
vapour pressure of the solution decreases.
Ans: When a non volatile solute is added in to the pure solvent, the
p vapour pressure of the solution, then,
Let p° be the vapour pressure of the pure solvent and be the
Lowering of vapour pressure =p°-p
vapour pressure of thepure solvent and that of
So, lowering of vapour pressure is the difference between the
the solution.
6. Define relative lowering of vapour pressure.
pressure to the vapour pressure of solvent.
Ans: It is the ratio of lowering of vapour
PA -PA
Relative lowering of vapourpressure PA

pressure.
7. State Raoult's law of relative lowering of vapour
states in a solution containing non volatile solute, the relative lowering of vapour pressure is equal to
Ans: It that
the mole fraction of the solute in dilute solutions.

i.e., P-PA
PA n, +ng
relative lowering of vapour pressure.
8. Write the mathematical form for Raoult's law of
PAPA
Ans:
PÅ n +nB
to calculate the molar mass or molecular mass OR molecular weight using relative
9. Derive the relation,
lowering of vapour pressure.

Ans: We know that from Raoult's law

PÅ-PAE
PÃ
n +ng
present in the solution.
na n, are the number of moles of solvent and solute respectively
where and
For dilute solutions n<<n:

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24
n
PA-PA
n,
Wp
But, n WA, nn Mn
MA
x M

P-PAW, x MR
W,
PA

W, x(P -PA)
vapour pressurc.
10. Among pure water and sea water which has highest
Ans: Purc watcr
I1. Which of the following has lowest vapour pressure?
(ii) 1
M urea
) Pure water
(iii) 1 M NaCI (iv) 1
M BaCI,
Ans: IM BaCl,
12. The mole fraction of a solvent is 0.95. What is the relative lowering of vapour pressure?
Ans: 0.05

(ii) Elevation of boiling point (Ebullioscopy)

13. What is boiling point?
Ans: The temperature at which liquid is converted into vapours is called boiling point. OR
The temperature at which vapour pressure of a liquid is equal to the atmospheric pressure.
14. When does liquid boils?
Ans: Liquid boils when vapour pressure of the liquid becomes equal to the atmospheric pressure.
15. What happens to the boiling point of a liquid when a non volatile solute is dissolved in a pure sovent
Ans: Boiling point of solvent increases.
16. Define elevation in boiling point.
Ans: It is the difference between the boiling point of the solution and that of the pure solvent.
i.e., AT, =T, -T
where AT, = elevation in boiling point, T, = boiling point of the solution,
T = boiling point of the p
solvent.
17. Give the relation between elevation in boiling point and molality.
Ans: AT, m

AT, =K •m
where AT,= elevation in boiling point, m = molality, Ky = molal- elevation constant or ebulliosco
constant.
18. Define Ebullioscopic constant or molal elevation constant.
ns: It is the increase in the boiling point produced when one mole of non volatile solute is dissolved in 1 Kg

pure solvent.
9. What is the value of K, for water?
ns: 0.52 K kg mol',
What is the SI unit of K,?
ns: K kg mol

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21. How is the molar mass of a solute caleulated by cbullioscopic method (elevation in boiling point).
Ans: We know that, AT, =Km ...(1)
Let Wp be the mass of the solute of molecular mass M, dissolved in w, gram of the solvent, then molality
(m) of the solution is given by the cquation:
Wn x1000
m
M, xWA
Substituting the value of m
in equation 1, we get,
Wa X1000
AT, =K,X
M, xwA
The molar mass of the solute (M) is calculated using the equation,
=
K, xwa x1000
Mp
AT, ×WA
Thus, in order to determine Mp, molar mass of the solute, known mass of solute in a known mass of the
solvent is taken and AT, is determined experimentally for a known solvent whose K, value is known.
22. Give the relation to calculate molal elevation constant with respect to enthalpy of vapourisation.
RxM x 1; (solvent)
Ans: K=
1000 x A Hap
where R= gas constant, MA = molar mass of the solvent, Tsolvent boiling point of pure solvent,
AHan the enthalpy of vapourisátion.
23. Draw the graph of vapour pressure with temperature to show elevation in boiling point of solvent and
solution.
Ans:
Boiling point of
Solvent Solution

1
atm

Solvent
Solution

AT, I

Temperature K

or 0.01
24. Which of the following aqueous solutions should have higher boiling point? 0.01M NaCI
Na,SO4 (assume both undergo almost complete ionisation)
Ans: 0.01M Na,SO, (: i=3)

(iii) Depression of freezing point (Cryoscopy)

25. What is freezing point?
OR
Ans: The temperature at which the liquid changes or converted into solid is called freezing point.
vap
The temperature at which the vapour pressure
of
the substance in its liquid phase is equal to its
pressure in the solid phase.

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26
to the vapour pressure of the solid
When docs liquid reczes? cqual
26. vapout pressurc of the liquid becomes solute is dissolved in it?
when the when a non volatile
Ans: Liquid frces of a pure solvent
to the freezing point
27. 1hat happens
decreasCs.
Ans: Frrczing point solution.
point. and that of the
Define depression in freczing
28.
betwecn the frcezing
point of the pure solvent
Ans: 1tis the diference
-
ic..
AT, T -T, T = freczing point of the pure solvent,
where AT, depression in freezing point,
freczing point ofthe solution
I vapour pressure with temperature to show depression in freezing
point
of solvent
29. Draw the graph of
and solution.
Ans:
solvent
4JsstodeA solventLiquid
solution

Frozens

T, T

Temperaturc K
0. Give the relation between depression in freezing point and molality.
ns: AT, o or AT, =K,·m
m

where Kfis called molal depression constant or cryoscopic constant.

Define cryoscopic constant or molal depression constant.
s: It is the decrease in the freezing point produced when one mole of non volatile solute is dissolved in one k
or 1000g of a pure solvent.
What-isthe value of K, for water?
:
K=1.86 K kg mol"" for water.
Whatis-the SI unit of Kf?
: K kg mol-!
Molal cryoscopic constant of acetic acid is 3.9 K kg mol', What does this mean?
:
Freezing point of acetic acid is decreased by 3.9 K by adding one mole
Derive the relation between depression in freezing point
of solute in 1000 g of acete au
and the molar mass of a solute.
We know that

AT,= Km ..(1) depressior

where m
is the molality of the point
solution and K, is the molal depression constant orfreezing.
constant or cryoscopic constant.
But for the given mass of solute and solvent, molality W x1000
is given by m= M
xWA
AT, =K, Wp X1000
M, xWA lety
<br>

x Wn x1000
= K,
M, AT, ×WA

36. Give the relationto caleulatemolar depression constant with respect to enthalpy of fusion.
R×M, xTf(ovent)
Ans: K,=
1000x AHp
where R= universal gas constant, Ma = molecular mass of solvent, Tr= freczing point of solvent,
AHfisEnthalpy of fusion.
37. Among pure water and sea water which has high boiling point and lowest freezing point.
Ans: Sea water.
38. Give reason: The freczing point of sea water is less than 0°C ( 273 K).
Ans: Due to dissolved salts.
39. GiveReason: To clear the snow covered roads and hilly areas salt is sprinkled.
Ans: When salt is sprinkled on the snow covered roads and hilly areas, snow starts melting due to depression in
freezing point. As a result formation of water takes place which helps to clear roads.

(iv)Osmosis and Osmotic Pressure

40.hat is osmosis? Give one application of it.
a
Ans: The flow of solvent molecules from lower concentrated solution to higher concentrated solution through a
semipermeable membrane is called osmosis. OR The flow of solvent from solvent to solution through
semipermeable membrane is called osmosis. Used in kidney dialysis.
(41,What is semipermeable membrane?
it but not the solute particles is
Ans: A membrane which allows the movement of only solvent molecules through
called semipermeable membrane.
membrane.
42. Give an example for natural semipermeable
Ans: Pig's bladder, parchment paper etc.
Give an example for synthetic or artificial semipermeable
nembrane.
43.
Ans: Cellophane.
44. Give reason for the following
+ water) solution
(a) Raw mangoes shrivel when pickled in brine(salt
Blood cells collapse when suspended in saline
water
(b)
water
(c) Wilted flowers revive when placed in fresh
mango enters into brine solution.
Ans: (a) Due to exosmosis, water molecules of
saline.
molecules of blood cells enter into the
(b) Due to exosmosis, water
enter into the flowers.
(c) Due endosmosis, water molecules solution.
aqueous solution of sodium chloride is called brine
Note: (i) Saturated
saline.
(ii) 0.9% NaCl in water is called
A5. Whatis osmotic pressure? pressure (II ).
pressure on the concentrated solution to stop osmosis is called osmotic
applied
KAns: The external
property. Explain. (July - 2016)
Osmotic pressure is colligative
a
46. pressure is a

on solute particles not on their nature. Hence osmotic

Ans: Osmotic pressure depends number of
colligative property.
to calculate the molar mass of solute by osmotic pressure experiment.
47. Derive an expression
Ans: IIc C II PUChemist
<br>

Solutions

28
.. I1=CRT

but C- and n,
M,
M
RT
WRT
as that of gas constant.
where R solution constant whosc value is samc mass of a solute like polymers, proteins and
The above cquation is uscd to calculate thc molecular
macromolccules.

4S.What are isotonic solutions? Give an example.

Ans: Two solutions having the same osmotic pressure at a given temperature are called isotonic solutions.
Example: RBC (Red blood cells) is isotonic with 0.9% NaClsolution which is called normal saline Ir i
in injections instead of distilled water.
49. What are hypertonic solutions?
Ans: The solution whose osmotic pressure is higher than that of the given solution is called hypertonic solution
Example: When RBC is placed in sea water, water passes out
of the cell due to osmosis and the cell shrinbe
50. What are hypotonic solutions?
Ans: The solution whose osmotic pressure is
lower than that of given solution is called hypotonic solution
Example: When RBC is placed in hypotonic solution
they swell and even burst due to the inflow of wat
due to osmosis.
1. What the observation made when blood cells are placed in
saturated salt solution? What are suc
solutions called?
ns: Water will flow out the
of cells and they would shrink. Such a solutions are called hypertonic.
Which solution would exhibit lower osmotic
pressure? Aqueous solution of urea or aqueous solution
common salt, both of same concentration.
o

ns: Aqueous solution

of urea.
JAcarrot that has become limp due-to water loss
in to the atmosphere can be placed into the wate
making it firm once again. Give reason.
s: Due to osmosis water will move into the carrot.
People taking a lot of salt or salty food
experience water retention in tssue cells and inter celluls
spaces. Give reason.
5
Because of osmosis.
What is edema?
5:
People taking a lot of salt or salty food experience water retention in tissue cells
and inter cellular spae
because of osmosis. This results in puffiness or
swelling called edema.
What is the partial cause for the water movement from soil into plant roots
upper portion of the plant and subsequenuy
s:
Partially due to osmosis.
Preservation of meat by salting and of action. Explai
fruits by adding sugar protects against bacterial
5:1 hrough the process of osmosis., a bacterium on salted meat or candid fruit loses water, shrivesa

Chemist
Jent's illuminator I| PU
<br>

Jeevith Publications 29

58. What is reverse osmosis? Give onc important application of it. (April - 2022)
Ans: When a pressure more than the osmotic pressurc is applicd on a concentrated solution, solvent flows from
concentrated solution to dilute solution through a semi permcable membrane. This phenomenon is called
reverse osmosis. Reversc osmosis is uscd in the desalination of sea water to obtain fresh drinking water.
59. Explain the desalination of sea water (purification of sea water) by reverse osmosis.
Ans: The process of reversing the direction of osmosis by Pressure >1
pressure pressure piston
applying the higher than the osmotic to
the solution of higher concentration is called reverse
osmosis. During reverse osmosis, the pure solvent flows Purc water Salt water
out of the solution through the scmi petmeable membrane.
Reverse osmosis is used in desalination of sea water. When
Water!
outlct
pressure, more than osmotic pressure (30 atm at 25°C) is
applied to the sea water, pure water is squeezed out of the SPM
sea water through the semipermeable membrane as shown
in figure.
13
reverse osmosis.
60. Name the semipermeable membrane used in
Ans: Cellulose acetate.
are more often determined by measuring oSmotic pressure
61. Molecular mass of polymers or proteins
rather than by any other colligative property. Give two reasons.
over other colligative properties that
Ans: The osmotic pressure method has advantages
() This method uses molarities instead of molalities. masses
Osmotic pressure can be measured at room temperature. This is useful to determine the molar
(ii)
are not stable higher temperatures.
of biomnolecules as they even for very dilute solutions.
compared to other colligative properties, its magnitude is large
(iii) As solution?
to when RBC is placed in 1% NaCl solution and 0.5% NaCl
you expect happen even
62. What do (hypertonic). In 0.5% NaCl solution RBC will swell and may
Ans: In 1% NaCl solution RBC will shrink NaCl solution.
(hypotonic). The above phenomenon is because RBC is isotonic with 0.9%
burst

Multiple Choice Questions (MCQs)

a) mole fraction b) molarity
Colligative properties depend on c) molality d) parts per million
1.
to volatile
a) Nature of solvent 4. When non volatile solute is added
b) Nature of solute solvent, the boiling point of solvent
present in the
c) Number of solute particles a) Decreases
solution b) Increases
present in the No change
d) Number of solvent particles d) Either decreases or increases
solution
Elevation in boiling (AT, ) point is directly
the colligative 5.
2, Which of the following is not proportional to
property? of the solute in the
vapour pressure a) Molar concentration
a) Relative lowering of solution
b) Elevation in the
boiling point the solute in the
b) Mass percentage. of
c) Freezing point solution
d) Osmotic pressure percentage of the solute in the
c) Volume
vapour pressure of solution
3. Relative lowering of the solute in the
non volatile solute is d) Molal concentration of
solution containing
of solute solution
equal to II PUChemistry
Shdont's illuminator
<br>

Solutin
30

c) no movcmcnt of solvent molecules

6. The unit of molal clevation constant (K) is d)
solute molccules arc moving from high
a) Mole per dm' b) mole per kg concentrated solution to lower concentrat
c) JK'mol d) K kg mol
solution.
7. The formula cbullioscopic
calculnte 12. The movement solvent molecules can
of
constant (K») is stopped during osmosis by applying
a) K, =
RxM, x T(solvent) pressure on
1000x AH yap a) lower concentrated solution
1000x RX M,Th(olvent) b) higher concentrated solution
b) Ky = c) on either side of the solution
AHyap
d) osmosis cannot be stopped
1000x M, xTh(solvent)
The external pressure applied
c) K, 13 to hinl
Rx AHvap concentrated solution to stop osmosi,
Rx M, x AHyap called
=
d) K,
1000x Tp(solvent) a) osmotic pressure
b) vapour pressure
8. Depression in freczing point (AT) is c) dynamic pressure
directly proportional to d) atmospheric pressure
.
a) Molar concentration of the solute in the
14. Raw mangoes shrivel when
solution pickled in hr
b) Mass percentage of the solute in. the
(0.9% NaCl in water) due to
solution a) osmosis b) diffusion
c) vapourisation d) condensation
c) Volume percentage of the solute in the
solution 15. Which of the following is naturz
d) Molal concentration of the solute in the occurring semipermeable membrane
solution a) pig's bladder b) parchment
9. The unit of molal depression constant (K) is c) cellophane d) both (a) and (b
a) mole per dm b) mole per kg 16. Two solutions having same osmotic press
c) JK"mol! d) K kg mol! at given temperature are called
10. The formula to calculate cryoscopic a) Hypertonic solutions
constant (K) is b) Hypotonic solutions
RxM, xTf(golvent) c) Isotonic solutions
a) K,= 1000 x AHAs d) Dilute solutions
1000× RxM,T(solvent) 17. A solution having more osmotic pressi
b) K, = (more concentrated) with respect to ot.
AHfus
solution is called
1000x M
xlf(solvent) a) Hypertonic solutions
c) K= RxAHus b) Hypotonic solutions
Rx M, x AHfus c) Isotonic solution
d) K= d) Dilute solutions
1000x T(Solvent)
18. Hypotonic solution has
to ot
11. During osmosis, OSmotic pressure with respect
a) solvent molecules moving from lower
concentrated solution to higher
concentrated solution through
semipermeable membrane
b) solvent molecules moving from
higher
concentrated solution to lower concentrated d) either less or more
solution through semipermeable membrane
Chemi
IIPU
Student's illuminator
<br>

31
Jeevith Publications

19. Wilted flowers revive when placed in fresh 22. The direction of osmosis can be reversed
water due to (reverse osmosis) by
a) osmosis b) osmotic pressurc a) applying pressure larger than the osmotic
c) diffusion d) vapourisation pressure tothe higher concentrated solution.
20. People taking lot of salt or salty food b) applying pressure lesser than the osmotic
pressure tothe higher concentrated solution.
experience water retention in tissue cclls
and intercellular spaces (edema) because of c) by increasing temperature of the solution
d) by decreasing temperature of the solution
a) vapourisation b) diffusion
c) osmosis d) osmotic pressure 23. Example for reverse osmosis is
Water nmovement from soil into plant root a) Desalination of sea water
21.
and into upper portion of the plant is partly b) Raw mangoes shrivelwhen pickled in brine
c) blood cells collapse when suspended in
due to
a) osmosis b) diffusion saline water
d) wilted flowers revive when placed in fresh
c) high pressure d) lowpressure
water

Answer keys
2 5 678 10 11 12
C a b d
13 1415 16 17 18319 20 2122 23
a C a

Numerical Problems
pure water at 298 PÅ-PA
1. The vapour pressure of g of Urea
is 23.8 mm Hg, 50
K

NH,CONH) is added. to 850 g of water. 23.8-23.3802

=0.0176.
Calculate the vapour pressure of water 23.8
for this solution and its relative lowering. 2. The vapour pressure of water is 12.3 kpa
at
mm ofHg 300 K. Calculate vapour pressure of molal
1
Ans: Vapour pressure of water p=23.8
solution of non volatile solute in it.
Weight of water taken, WA =850g
Ans: According to the Raoult's law
Weight of urea taken, WB=50 g PA-PA
g mol =XR
Molecular weight of water,
M 18 PA
Here Pa =Vapour pressure
of solution and
g
Molecular weight of urea, Mg =60
mol

pa =Vapour pressure of solvent

From Raoult's law,
(A=H,O
PA-PA Wx:Ma PÅ-PA
(B=solute)
M
WA PÃ ng tn
23.8-PA 50 18 molal means mole of non volatile solute
1 1
X
23.8 60 850 present in 1000 g H,0
23.8-PA0.01764 Molar mass of H,O= 18gmol
23.8
23.8-p, =0.4198 Number of moles in
mm Hg 1000 55.56 moles.
P, =23.3802 1000g H,0:
18
Relative lowering of vapour pressure
<br>

32
Solutions
Number of oles of solute I nol. PA-PA
12.3-DN n+n
12,3 1+55.56 mol, n 114
40 =| mol
12,3-pa 0.0177 × 12.3 114
W
12.3-0,2177
PA 12.08 kpa PA-0.8pA
40
3. Vapour pressure of water ant 293 K is 17.535 WB
mm Hg. Caleulate tlhe vapour pressure +1
of 40
water at 293 K when 25 g of glucose is
dissolved in 450 g water P-0.8p,
p
WB
(NCERT exercise question) W+40
Ans: Molar mass of glucose (CoH;O%)
0.2 = W

=6x 12+ 12 x | +6x 16= 180 g

mol! WR +40
W
Number of moles of glucose =10g
5. The vapour of pure
25 8
benzene
180 g mol! =0.139 mol temperature is 0.85 at certain
electrolyte solid bar. A
non-volatile,
Number of moles of water to 39 g of weighing 0.5 g non-

benzene (molar mass when added

450g mol). Vapour pressure 78
18 g mol! 25 mol is 0.845.bar. of the solution then
solid What is the molar mass
According to Raoult's law,; sbstance. (NCERT ofthe
solved problem).
PA-PA Ans: M
= WxMA XPA
PA WA(P-P)
PA=Vapour pressure of water and: 0.5×78×0.85
PA= Vapourpressure of solution 39x(0.85-0.845) =170g mol!
6. An aqueous solution
of
17.535-PA 0.139 solute exerts a pressure 2% non-volatile
of 1.004 bar at the
17.535 0.139 + 25 normal boiling point of
the solvent. What is
molar mass of the solute?
17.535-PA 0.139 x 17.53S
(NCERT exercise question)
25.139 Ans: Vapour pressure of the solution at
normal
17.535PA0.097 boiling point (Pa) = 1.004
p,=17.535 – 0.097 = 17.44 mm Hg
br
Vapour pressure of pure yater at normal
Calculate the mass of a boiling point (P)=1.013 bar
non-volatile solute
(molar mass 40 g molr)
dissolved which should be 2% solution =2g non volatile solute presentin
in 114 g octane to
vapour pressure to 80%. reduce its 100-g solution.
.:. Mass of solute, (We)
=2g
ns: Molecular mass (NCERT exercise question) Mass of solvent (water), (wA)= 100-2=98 g
= MA of octane (CgH1s)
x
=8 12 + 18 x 1 =114 g Molar mass of solvent (water),
mol'
Vapour pressure,
of octane after dissolving (M) = 18 g mol
solute According to Raoult's law
0.8p
100 Wa XM
Ma =
WA (PÅ-PA
<br>

Jeevith Publications 33

2x18 1.013 g The boiling point of benzene is 353.23 K.

41.35 mol-!
98 1.013-1.004 When 1.8 g of non-volatile solute was
dissolved in 90 g of benzene, the boiling
7. 5.8 g of non-volatile, non-clectrolyte solute
was dissolved in 100 g of carbon disulphide point is raised to 354.11 K. Caleulate the
(CS;). The vapour pressurc of thc solution molar mass of the solute. K, for benzene is
was found to be 190 mm of Hg. Calculate 2.53 K kg mot!. [NCERT solved problem]
molar mass of the solute.
Ans: M,= K, w, x1000
x
Given : Vapour pressure of pure CS, is 195
mm of Hg and molar mass of CS, is 76 AT, ×W A

g/mol. (July -2018, March - 2016) But AT, =T,

-T
XM xp
Ans: M, =
W

:. M

w.(På-PA) (T, -T)xWA

5.8x76x195 2.53x1.8×1000
x =171.91g mol-! Mg
100 (195-190) (354.11-353.23) x90
8. Vapour pressure of benzene is 200 mm of 2.53x1:8x1000
=57.5 g mol.
Hg. When 2 gram of a non-volatile solute 0.88×90
dissolved in 78 gram benzene, benzene has
vapour pressure of 195mm of Hg. 11. Boiling point of water at 750 mm Hg is
Calculate the molar mass of the solute. 99.63°C. How much sucrose is to be added
[molar mass of benzene is 78 gram mor'] to 500 g of water such that it boils at 100°C.
x
Ans: M, = W; XM, P Molal elevation constant for water is 0.52 K
W, x(P-PA) kg mor
Ans: Elevation of boiling point
2x78×200 =80g molI:!
78x(200-195) AT,=(100 +273)-(99.63 + 273) = 0.37 K
Molar mass of sucrose (C:2H20),
9. 18 g glucose (C,H,,0) is dissolved in 1 kg ME =
12 x 12+22 x 1+ 11 x 16=342 gmol
of water in saucepan. At what AT, X Mg XWA
W
=
temperature will water boil at 1.013 bar? K
K, x1000
for water is 0.52 K kg mo-.
WB = 0.37x342× 500 = 121.67 g
[NCERT solved problem] 0.52×1000
Ans: AT,: KxWB x1000 12. The molecular weight
MxWA of an organic
compound is 58 g mo. Calculate the
T-T°=A,XW, X1000 boiling point of a solution containing 24 g
of
MgxWA the solute and 600 g of water. The boiling
point of water=373 K. K, for water=0.52
T =373.15 K, K, =0.52K kg mol', b

Ws =18g, w, =1 kg =1000g K kg mo,

I,-373.15.52x18x1000 Ans: AT, - K,XWx1000
180x1000: Mp XW,
T,-373.15 =0.052
T,=373.15+0.052 =373.202 K T,-T= 0.52x 24x1000-=0.358
58x600
T, =0.358+ T
=0.358+373 =373.358 K
Student's ilt
<br>

34
Solution
13, A solution containing 0.51 26 g naphthalene 0.51×3.46×1000
128 g mot-) in 50 g of carbon
=147.0S gmol-!
(mol. wt 0.12× 100
tetrachloride gives n boiling point clevntion 16. On dissolving 2.34 g of
of 0.402K while a solution of 0.6216 g of an non-electroly
solute in 40 g of
benzenme,
unknown solute in the same weight of the solution was higher than the boiling point
solvent gives a boiling point elevation of benzene
K, value for benzene by 0.81
0.647 K. Find the molccular weight of the
Calculate the molar mass
is 2.53 K
kg mot
unknown solutc. mass of benzene of solute.
is 78 g mol1. [Mola
Ans: Step 1: Calculation of K, for CCl4
Ans: M, K, x w, x1000
AT, X WA X M
K,
=
AT, XW,
Wa X1000
2.53× 2.34×1000
0.402x 50×128 0.81x 40 =182.72g mol!
1000× 0.5126 =5.02
K kg mol-! 17. 45 g of ethylene
glycol
Step 2: Calculation of molecular mass
of. with 600 g of water. (CH,0,) is mixe
unknown solute. freezing point Calculate (a) th
freezing point depression
M, =X W x1000 and (b) t
of the solution
AT, XWA kg mol-l)(NCERT (K,= 1.86
solved problem)
5.02 x
0.6216x1000 Ans: Freezing
point depression
0.647x 50 (^T;) is given by
=96.46g mol K,xwx1000
14. The boiling point MXWA
of a solution containing Molecular mass
0.20g of a solute B
in 20 g of ether is 0.17 K of ethylene glycol
higher than that of pure (C,H,0,)= 2x12-+6x1+2x16
ether. Calculate the
molar mass of solute =62 g mor!.
B. Boiling point 1.86x4
<45x1000
elevation constant of AT, =
ether is
2.16 K kg mol-1. 62x 600
AT, =2.25K
Ans: M
Wp XK x1000
AT,
AT, XWA =T-I,
0.2×2.16x1000 T = freezing point of water = 273.15
K
0.17x20 T,=freezing point of solution

=127.06 g mol I, =T-AT,

15. On dissolving 3.46 g of non-volatile
1000 g of water, solute in = 273.15- 2.25 =270.9
K.
the boiling point of solution 18. g a non
was raised to 1.00 of electrolyte solute dissolved
that of pure water by 0.12 K. g
50 of benzene lowered the freezing poir
Calculate the molar mass
of non-volatile of benzene by 0.4 K. The freezing poin
solute.
depression constant of benzene is 5.12 K
k
(Given : Ky of water = 0.51
K kg mol). mol. ind the molecular máss of the solute
(March - 2022) (NCERT solved problem, May-2023,
Mare

Ans: M,= K, X WR X1000 - 2017)

AT, XWA
K, x Wa x1000
Ans: M,= AT, x W,

Chemistr
udent's illuminator I| PU
<br>

Mp xw,A
×
S.12x1.00 1000 AT, X
=256 g mol! W
=
K,x1000
0.4x 50
19. 1.4 g of acetone dissolved in 100 g benzene
1.5x×176x75
gave a solution which frcezes at 277.12 K. =5.0769 g
3.9x1000
Pure benzene freezes at 278.4 K. 2.8 g of a A 5% solution (by mass) of cane sugar in
22.
solute dissolved in 100 g benzene gave a
water has freezing point of 271 K. Calculate
solution which froze at 277.76 K. Calculate
the freezing point of 5% glucose in water if
the molecular weight of solute. freezing point of pure water is 273.15
K.

Ans: K, =
AT, X
WxM [NCERT Exercise]
W
X1000
=278.4 - 277.12 =1.28
K
Ans: (a) Calculation of Kf
AT, =T-T,
1.28x 100× 58 AT, =T -T,
=5.3 Kkg mol-!
1.4x1000
K xWa x1000 AT(= (273.15 – 271)K = 2.15 K
M =
AT, xWA Molar mass of sugar (C2H2011)
5.3x 2.8x 1000 =231.87 g mol! = 12 × 12+ 22 x 1 + 11 x 16=342 g mol
0.64× 100
20. Addition 0.643 g of a compound to 50 mL
of 5% solution (by mass) of cane sugar in water
of a bemzene (density = 0.879 g/mL) lowers means 5g of cane sugar is present in 100 g
the freezing point from 5.51°C to 5.03°C. solution.
Calculate the mnolar mass of the compound.
(K, for benzene =5.12 K kg mol-. Mass of water =100-5=95 g,

K, XW X1000 mass of cane sugar = 5g

Ans: M, = AT,
xWA AT, × M, XWA
W
=50x0.879= 43.95g
K= WB X1000

(:: mass = volume x density) 2.15x342x95 =13.9707 K kg mol

5x1000
AT, = T; -T,
Calculation of freezing point of
(b)
=
278.66- 278.18=0.48 K
glucose solution
5.12 x 0.643 ×1000 Molar mass of glucose (C.H206)
.:.
M, = 0.48x43.95 g
mol
=6X 12 12 xl +6x 16= 180
+

=156.056 g mol"l
5% glucose in water means 5 g
of glucosei

21. Calculate the mass of ascorbic acid present in 100g of 'solution.

g
(Vitamin C, CH,0) to be dissolved in 75
Mass of water = 100 – S =95 g,
of acetic acid to lower its melting point by
1.5° C. K,=3.9 K kg mol-1. mass ofglucose =WB =5g
(NCERT exercise question)
AT, =
K, xWp x1000
M
XWA
Ans: Molar mass of ascorbic acid (CçH,O%),
x
16= 176
g
mol 13.9707x5x1000 =4.085 K
Mp
=6x 12 + 8 x 1+6
K
180× 95
Lowering of melting point, AT= 1.5
solution
The freezing point of 5% glucose
AT, =
K, XWp x1000
given by
MWA
<br>

36 Soluion

AT, =T;-T, W,RT

- AT, Ans: M,=
IIV
T=T
Wa
MIIV
=273.15 -4.085 269.065K RT
180 g mnol
x7.65 atm ×1L
23. of an unknown material is dissolved in
31 g
0.0821L atm mol"K x310
500 g of watcr. The resulting solution K

freezes at 271.14 K. Calculate the molar =54.10g

mass of the material. 27. 450 cm° of an aqueous
solution
IGiven: K, for water = 1.86 K kg mol", T° contains 1.0 g of the protein. of a prote
for water = 273 K (July – 2022, March - pressure of such a solution The osmot
at 310 K
2019) to be 3.1x104
K,X WR X1000 bar. Calculate is found
Ans: Ma mass of theprotein. the mola
AT, XWA
(R=0.083 bar: mol L
1.86x31x1000
=62 g mol Ans: V=450 cm =0.450 L
K) March -2023)
1.86x500
24. 200 cm° of an aqueous solution of a protein w=1g, T
=310K
contains 1.26 g of the protein. The osmotic
pressure of such a solution at 300
Kis found Il=3.1x10 bar
to be 2.57 × 10 bar, Calculate
the molar M,= We xRxT
mass of the protein.
IIV
(R=0.083L bar mol K) 1×0:083×310
WgRT
Solution: M, = V=200 cm =0-2 L 3.1×10x0.450 =184444g mol'
IIV 28. What is the osmotic pressure
1.26x 0.083×300 solution in water of 0.05% ura
atm mol K, at 20°C? =
0.0821 FR

2.57×10x0.2 molar mass of urea =

61039 g mol. mor'] 60:
5. Calculate the Ösmotic pressure Ans: 0.05% urea means
in pascals 0.05 g urea present in 100
excerted by a solution mL water.
prepared by
dissolving 1.0 g of polymer
of molar mass W,RT V=100 mL=0-1L
185000 in 450mL of water
at 370C MV =0:05 g
W

(R=0.0821 L atm K1 mor').

0.05x0.0821x 293
(NCERT Intext question) =0.2 atm
WRT 60x0.1L
ns:
V=450 mL0.45L 29. 300 cm of an aqueous solution of a proteI
M,V
contains 2.12 g of the protein, the osmoti
lx0.0821 x310 pressure of such a solution at 300 K is found
=0.00030572 atm
185000x0,45 to be 3.89 × 10 bar. Calculate the molar
[1 atm =101325 pal
mass of the protein. (R=0.0823L bar mo
0.00030572 x101325 =30.9768 Pa. (July - 2016)
The osmotic pressure of blood is 7.65
37° C. How much glucose atm at Ans: MB
WBRT

per litre for an intravenous should be used IIV

injection that is
to have the same osmnotic pressure 2.12x 0.0823x300
as blood? 3.89 x10x0.3
(Molar mass of glucose = g
180 mo) mol
=44852.4g
<br>

Jeevith Publications
37

1.7 Abnormal Molar Masses

1. What is abnormal molar mass?
Ans: The molar mass determined by colligative propertics is found to be lower or higher than the expected or
normal molecular mass. Such a molecular mass is called
abnormal molecular mass.
2. What is van't Hoff's factor?
Ans: It is the ratio of normal molar mass to the abnormal molar mass.
normal molar mass
i=
abnormalmolar mass
observed colligative property
OR i=
calculated colligative property
Total number of moles of particles after association or dissociation
OR i
Number of moles of particles before association or dissociation
3. Give the significance of van't Hofrsfactor.
Ans: (i) If i= 1,the solute doesn't undergo either
dissociation or association.
(ii) If i>1, solute undergo dissociation.
iiü) If i<l solute undergo association.
4. Write the colligative properties for solutes undergo dissociation or association.
Ans: (i) Elevation in boiling point, AT, =ik,m
(ii) Depression in freezing point, AT, =ik,m
(111) Osmotic pressure II =iCRT
(iv) Relative lowering of vapour pressure, p-p
5. What is the conclusion drawn when van't Hofffactor of a solution is less than one? March - 2018]
Ans: The solute in the solution undergoes association.
6. When is the value of van't Hoff factor more than one? (July-2017]
Ans: When solute in the solution undergoes dissociation.

Additional information
Relation between degree of dissociation (a) and van't Hoff factor ()
The degree of dissociation is the fraction of the solute that is dissociated. It is usually indicated by the Greek
symbol a. There is a simple relationship between this parameter and the van't Hoff actor (I). If a fraction.
a of the solute dissociates into n ions, then
C = i-1
n-1
Relation between degree of association (a) and van't Hoff factor ()
Degree of association defined as the fraction of the solute which associates or combines together esulting in
the formation of a bigger molecules. It is also usually indicated by the Greek symbol
. There is a simple
relationship between this parameter and the van'tHoff factor (1). If a fraction, a of the n' solute particles
associates, then
-1
-1
<br>

Multiple Choice Questions (MCQs)

1. Which of the following is not the reason for 6. When blood cells are put in hypoton<
the abnormal molar mass measurcd by its solution (conc. of NaCI 0.9% mass
they by vo
colligative properties?
a) Association of the solute a) swell b) shrink
b) Dissociation of the solute c) remains same in size d) none
c) Either associationor dissociation 7. When blood cells are put in
d) No association or dissociation hyperton
solution (conc. of NaCI > 0.9% mass
2. The value of van't Hoff factor for NazSO, by they by
assuming complete dissociation in the a) swelI b) shrink
solution. c) remains unchanged in size
a) 7 b) 3 d) none
c) 2 d) 6 8. The colligative property
3. If the solute dissociates in the solution van't measuring the molar mass
generally used
Hoff factor is proteins and biomolecules is of polymer
a) >1 b) <1 a) Osmotic pressure
c) =0 =1 d) b) Elevation of boiling
4. If the solute neither dissociates nor associates c) Relative lowering point
in the solution, van't Hoff factor is of vapour pressure
d) Depression of freezing
a) >1 point
b) <1 9. In which of the following case
c) =1 d) =0 i#1in the
solution
5. When blood cells are put in a) Glucose
0.9% (mass b) Urea
volume) sodium chloride solution then c) Sucrose
d) NaCl
a) shrink b) swell 10. The value of
Van't Hoff factor (i) for ethano
c) remains same in size d) they burst acid in benzene is nearly
(March 2023)
a) 2
b) 1
c) 0.5 d) 0
Answer keys
d b a
78910
a b

Numerical Problems , 2n
0.6 mL of acetic acid (CH,COOH)
having W,=1litre =1000g water
density 1.06 g mol is dissolved in 1 litre
of
water. The depression in M
=60 gmol
freezing point
observed for this strength of acid was
0.02050C. Calculate the van't 0.636x1000
Hoff factor m= -=0.0106 m
and the dissociation constant of acid. 60x1000
K
for
water = 1.86 K kg mol, [NCERT solved AT,
i=
problem] K,m
AT,=iKm 0.0205 =1.04
i=:
1.86x0.0106
m = WB X 1000 CH,COOHCH,CO0 +H"
MB WA

W =0.6x1.06=0.636 g .". n=2

Chemis
IIPU
<br>

Jeevith Publications
39
i-1
4.9×2x1000 =
n-1 242 gmol
1.62× 25
1·04-1 Experimental molar mass = 242 g
=0-04 moles mol.
2-1
Normal molar mass of C;H,COOH
Ca?
K, = =7x12+6x1+2x16=122 g molr
(1-«)
Van't Hoff factor
0.0106x (0.04)
1-0.04 i:
Normal molar mass 122
=0.504
Experimental molar mass 242
0.0106x 0.04 x 0.04
=1.77x10-5
0.96 2C,H,CO0H (C,H,COOH),
2. 2g benzoic acid (C,H,CO0H) dissolved .:.n=2
in 25 g of benzene shows a depression in Degree of association
freezing point equal to 1.62 K. Molal
depression constant for benzene is 4.9 K
kg mor! What is the percentage --1
n
association of acid if it forms dimer in 0.504-1 -0.496
solution. [NCERT solved problem] 1:

Ans: Mp K, xWa X1000

AT, X WA =0.496x 2 =0.992
Percentage of association, 0.992 x100 = 99.2%

Fill in the blanks by choosing the appropriate word from those

given in the brackets:
Set - 1
(pressure, positive, liquid, directly, camphor, inversely)
1. According to Henry's law, the value of KH is 3. Maximum amount of a solid solute that can be
proportional to the solubility of dissolved in a specified amount of a given
liquid solvent does not depend upon
solute in solution.
Ans: inversely
2. in nitrogen gas is the example for Ans: pressure
gaseous solution. 4. A solution of acetone in ethanol shows
deviation from Raoult's law.
Ans: camphor
Ans: positive
5. During depression of freezing point in a
solution, an equilibrium exists between
solvent and solid solvent.
Ans: liquid
Set- 2
(inversely, Henry's, anoxia, solid, lower, liquid)
an example for 2. Molarity varies with temperature
1. Oxygen dissolved in water is
solution. Ans: inversely
Ans: liquid
I| PUChemistry
Student's illuminator
<br>

40 Soluion

3 Higher the value of Henry's law constant Ans: anoxia

(K)
is the solubility. 5. law explain
Ans: lower th
dissolution of C0; gas in soft drinks unde
4. The discase causcd to the people living at high high pressure.
altitudcs or maintain climbers is Ans: Henry's
Set-3
(remains same, K
kg mol', non ideal, AV > 0 and AH>0, decreases, increases)
1
Ethyl alcohol and water is an example for Ans: increases
solution. 4. is the SI
Ans: non ideal unit
cbullioscopic constant (Ky).
2. is the condition for non ideal Ans: K kg mol
solutions with positive deviation. 5. When non volatile solute is
Ans: AV>0 and AH>0 added to the Dir
solvent, the freezing
point of pure solven
3. The boiling point of a liquid
when a non volatile solute is dissolved in it. Ans: decreases
-4
Set
(osmosis, two, solvent, one, maximum boiling
point, more, shrink)
When RBC is placed in 1% NaCl solution, the
Ans: maximum boiling
cell will
4. Aquatic species are
Ans: shrink comfortable in cold water
2. Raw mangoes shrivel when pickeled in brine rather than in war
water.
solution due to
Ans: more
Ans: oSmosis
5. Binary solution -contains
3. Solution which shows the large negative
Components.
deviation from Raoult's law is called
Ans: two
azeotrope.

Higher Order Thinking Skills (HOTS)

1. Which of the following statement is false?
2. Which one of the statements given belc
a) The relative lowering of vapour pressure
of concerning properties of solutions, deserib
solution is equal to the mole fraction of the a colligative effect?
solute present in the solution. a) Vapour pressure of pure water decreases
b) Passage of solute molecules towards solution
the addition of nitric acid
side through semipermeable membrane is b) Boiling point of pure water decreases by t
called osmosis. addition of ethanol
c) The boiling point of solution with non c) Boiling point of pure benzene increases
volatile solute is always higher than the the addition of toluene
pure benzene decreas
solvent d)· Vapour pressure of
d) The boiling point of a liquid is the by the addition of naphthalene
temperature at which its vapour pressure,
becomes equal to 760 mm Hg.
<br>

Jeevith Publications
41

3. Molar solubility of helium, nitrogen

oxygen are plotted against and Reason: Dimerization of benzoic acid in
partial pressure of solution.
the gas at constant temperaturc.
a) Both assertion and reason are true and the
rcason is the correct explanation of the
assertion.
b) Both assertion and reason are true, but reason
is not the correct explanation of the assertion.
c) Assertion is true, but reason is false
-He d) Both assertion and reason are false
8

Partial Pressure The mole fraction of solvent is 0.9. The

relative lowering of vapour pressure is
Henry's law constant for these gases will lie in
a) 0.1 b) 0.9
the following sequence? c) 1
a) O2> N, > He d) 0
b) O, < N < He
9. Dissolution of calcium chloride in water is
c) O2 =Ny=He d) O, > N < He exothermic process while that of ammonium
nitrate is endothermic process, the
4. II,, II,, II,, II, are the osmotic pressures of observation is
5% (w/v) solutions of urea, fructose, .ren a) solubility of calcium chloride decreases with
sucrose and increase in temperature and that of
KCI respectively at certain
ammonium nitrate increases with increase in
temperature. The correct order of their temperature
magnitude is ieb) solubilities of both decrease with increase in
a) II, >II, > II, >
II, b) II,<II,<II,<II, temperature
c) solubilities of both increase with increase in
c) II, >II,>Il, >I1, d) I, >In>I1;>I, temperature
5. The mixture which shows positive deviation d) solubility of calcium chloride increases with
from Raoult's law is : increase in temperature and that of
a) Chloroethane + Bromoethane ammonium nitrate decreases with increase in
b) Ethanol + Acetone temperature.
c) Benzene + Toluene 10. When acetone and chloroform are mixed
d) Acetone + Chloroform together, which of the following observation
6. Concentration terms like mass percentage, is correct?
ppm, mole fraction and molality do not Ci
H,C
depend on temperature. However, molarity is
a function of temperature because
C-0+CI--H
H,C C1l

a) volume depends on temperature and molarity (A) (B)

involves volume a) A-A and B-B interactions are stronger thar
b) molarity involves non-volatile solute while
A-B interactions.
allother terms involve volatile solute b) A-A and B-B interactions are weaker tha
c) number of moles of solute change with
A-B interactions
change in temperature c) A-A, B-B and A-B interactions are equal.
d) molarity is used for polar solvents only
d) The liquids form separate layers and ar
7. Assertion : Molecular mass of benzoic acid immiscible
when determined by colligative properties is
found high.
Answer Keys
12 4N
5
678 910
b d b C b

Student's illuminator II PU Chemis

 Que
<br>

PU Board
(MCQs)
Multiple Choice Questions
The vapour pressure of
two liquids
9.
1. Which of the following is dependent On
Rn80 and 60 torr, respectively. P and
temperature? Th
vapour pressure of solution tot
a) Molarity b) Mole fraction obtained
mixing3 mole of P and 2 mol
c) Weight percentage d) Molality of Q would
can be a) 72 torr b) 140 torr be
2. Which of the following compounds c) 68 torr d) 20 torr
used as antifrecze in automobile radiators? 10. The mixture which shows
a) Methyl alcohol b) Nitrophenol positive deviatig
d) Ethyl alcohol from Raoult's law is
c) Glycol a) ethanol + acetone
3. The dissolution of gas in a liquid is governed
b) benzene + toluene
a) Raoult's law
c) acetone + chloroform
b) Henry's law d) chloroethane+ bromoethane.
c) Dalton'slaw of pressure
11. The mixture
d) van't Hoff factor that forms maximum
4. The mole fraction of the solute in one molal azeotrope is boiig
aqueous solution is a) heptane + octane
a) 0.009 o.018 b) water + nitric acid
c) 0.027 d) 0.036 c) ethanol + water
5. Out of following which one is not an example d) acetone + carbon
12. Which disulphide.
of a solution. of the following statements
a) Air b) Brass regarding a solution is core
c) amalgam dYbenzene in water and B exhibiting positive of two components !
6 If one mole of a substance is present in one kg deviation from ite
behaviour?
of solvent, then a) Intermolecular
a) It shows molar attractive forces between A!
concentration and B-B are stronger
b) It shows molal concentration than those between A
B.
c) It showsnormality b)AVmiyH = 0 at constant
d) It shows strength g/g andP. T

c) AVmix V=0at constant

7.
Statement I: On adding NaCl.to water d) Intermolecular attractive
and P. T

its forces between A#

Vapour pressure increases and B-B are equal to those between A-B.
Statement II: Addition of non-volatile 13 Which
of the following statements about tt
solute
incrases the vapour pressure. composition of the vapour over an ideal 1:!
a) Both statement I and Il are correct molar mixture of benzene and toluenei
b Both statement Iand statement are wrong
II correct? Assume that the temperature I
c) Statement I is correct
and statement II is constant at 25°C. (Given, vapour pressu
incorrect
d) Statement I is incorrect data at 25°C, benzene 12.8 kPa, toluene'
and statement II is 3.85 kPa).
Correct
PA and pB are the vapour pressures a) The vapour will contain equal amounts
liquid components, A of pure benzene and toluene.
an ideal binary and B, respectively of
b) Not enough information is given to
make!
solution. If xA represents
mole fraction of component the prediction.
pressure of the solution A, the total contain a higher percenit3
will be ) The vapour will
a) pAt xA(PB of benzene.
PA) b) Pat xAPA-PB) vapour will contain a higher
percentä#
c) PBtxA(Ps-PA) a) The
d) pgtxa(PA-PB)
of toluene.
Cheist
ent's illuminator IIPU
<br>

Jeevith Publications 43

14. A solution containing components A and B

21. The relationship between osmotic pressure at
follows Raoult's lavw. 273 K when 10 g glucose (p:), 10 g urea (p:).
a) A-B attraction force is greater than A - A and and 10 g sucrose (p) are dissolved in 250 mL
B-B of water is.
b) A-B attraction force is less than A - A and
a) p:>pi> P3 b) p:> pP;> P:
B- B
c) A-B attraction force remains same as A - A c) p>P2> P d) py> p:> P:
and B-B 22. Blood cells retain their normal shape in
d) volume of solution is different from sum of solution which are
volume of solute and solvent. a) hypotonic to blood b) isotonic to blood
15. Allform ideal solution except c) hypertonicto blood d) equinormalto blood
a) CH, and C;H, CH, 23. Of the following 0.10 m aqueous solutions,
b) C,H, and CaH,I which one will exhibit the largest freezing
c) CaHsCl and CGH„Br point depression?
d) C-Hsl and CaH,OH a) KCI b) CçH;0%
16. An ideal solution is formed when its d)
c) Al,(S0) K,SO:
components 24. An aqueous solution is 1.00 molal in KI.
a) have no volume change on mixing. Which change will cause the vapour pressure
b) have no enthalpy change on mixing.
of the solution to increase?
c) have both the above characteristics.
a) Addition of NaCI
d) have high solubility.
b) Addition of Na,SO4
17. If molality of the dilute solution is doubled,
c) Addition of 1.00 molal KI
the value of molal depression constant (K)
will be d) Addition of water
same
b) tripled 25. Which of the following salts has the
a) halved as that of
c) unchanged d) doubled.: value of Van't Hoff factor (i)
a
18. During osmosis, flow of. water through K,[Fe(CN)J?
b) Al(NO:)s
semipermeable membrane is a) Na,SO4
d) NaClI
concentration c) Alz(S04):
a) fromn solution having lower pressure is
only 26. At 25°C the highest osmotic
concentration
b) from solution having higher exhibited by 0.1 M solution of
only a) Glucose b) urea
semipermeable membrane d) KCI
c) from both sides of c) CaCl,
with equal flow rates aqueous solution has
semipermeable membrane 27. Which of the following
d) from both sides of minimum freezing point?
with unequal flow rates. a) 0.01 m NaCl b) 0.005 m CH,OH
19. Pure water
can be obtained from sea water d) 0.005 m MgSO4
c) 0.005 m Mgl, , colligative property
by
b) plasmolysis 28. For 0.1 M solution the
a) centrifugation will follow the order
d) sedimentation.
c) reverse osnosis properties of solution, a) NaCl> Na,SO4>
Na,PO4
20. From the colligative method for the b) NaCl< Na,SO,<Na,PO4
which one is the best NasPO4
molecular weight of proteins c) NaCl > Na,SO4
determination of
d) NaCl Na,SO,= Na,P04
<

and polymers? blood cells were removed

29. Statement I: If red pure water,
a) Osmotic pressure placed in
pressure from the body and
b) Lowering in vapour pressure inside the cells increases
c) Lowering in freezing point Statement II: The
concentration of salt
d) Elevation in boiling point content inthe cells increases.correct
statement Iand II are
a) Both
II PUChemistry
<br>

Solute

Jeevith
1. What is Two marks questions azcotrog
saturatcd What arc the different types of
\What is the cffect and
unsaturated solution? 14. 9.
of temperature
and pressure mixtures? Explain with example.
on the solubility?
15. What arc colligative properties?
Define the following
tens i) Solution i1)
Mole fraction iii) Molarity
cxamplcs.
mathematical
iv) Molality 16.
Write the relation tetwe,
3./ \Which of the two molality and elevation in boiling point.
molarity or molality, docs
vary with temperature?
4 and how? happens to boiling point of water when
State Henry's law. Write dissolved in it? Which one will have 1.
its mathematical
statement. What is boiling point: 0.1 NaCI, 0.1 M BaClh?
M
t
the significance of
Henry's Constant? Write
S. 17. the mathematical relation betwe
Mention any two applications molality and depression in
6. of Henry's law. freezing point.
Why do gases always tend to be less is sodium chloride to clear
W Ans:
soluble in used
liquids as the temperature increases ? roads?
srnow
7. What Explain. [Ans: Because NaC]
decreases
is Vapour pressure of liquids? Name a
law which helps us to detemine freezing point of ice]
pressure ofa volatile component
partial vapour 18. Write a note on osmotic pressure.
8.
in solution. 19. Define osmosis
State Raoult's law as applied to a and semi permeab
binary membrane.
solution of Non-volatile solute in a
volatile 20. Give reasons:
solvent.
9. What are ideal and non-ideal solutions? i) Cutting onions taken
from the
10. more
comfortable than fridgei
Give an example of Ideal solution . cutting
and Iving at room temperature oniog
non-ideal solutions.
11, What causes deviations from ideal do
that (Ans: At Iwould rat
behavior of vapour pressure low temperatu
solutions? Why do the. vapour
pressures is low. Hence
of vapours
certain solutions show
negative or positive of the producing chemicals s
deviations from the Raoult's
law? less at low temperaturel] z 2.
12. Derive the relation ii) When fruits
between molar mass and
solute and relative
lowering vapour pressure.
of dried are placed vegetables that baa
Swell and return in water they sloxh
13. What is azeotropic
mixture? Giveexample.
to
[Ans: Due to osmosis]the original forn Ans
1
Define the following Three marks questions
terms
i) Mass percentage 6. What is abnormal
ii)volume percentage
Van't- Hoff's factor. molar mass? Defre
i)
Parts per million
(ppm). What would be the valz
2. Give any three of Van't Hoff.factor
differences between for a dilute solution
non-ideal solutions. ideal and K,SO4 in water d
3. Give any three dissociation? if it undergoes complez
differences 7.
showing positive between solutions With the help of vapour pressure
ideal behaviour. and negative diagram, -temperatir
deviation from explain 3.
4. the depression d
Define the term freezing point of a solution a
molal elevation of non-volatit
molaldepression constant solute in a volatile solvent.
5. constant. and How would yt
What is an Give
isotonic, hypertonic,their SI unit. determine the molar masses
of solute using t:
solution? and above properties? A
hypotonic
8. What
is reverse
osmosis? Mention One of is
practical uses and give an artificial
example for:
Student's illuminator semipermeable membrane.
 UNIT
<br>

Electrochemistry
2
1. What is letrochemistry?
Anss Eltchemistry deals with the study of production of electricity from energy released during spo

chemical rrtions and use of electrical energy tobring non-spontaneous chemicalreactions.

2. Gire any two importance of electrochemistry.
Ans: ) A lage number of metals, NaOH, C, F; etc are prepared by electrochemical methods.
() The reactions crried out electrochemically can be energy efficient and less polluting.
3. 1hat type of reactions are fundamental reactions of electrochemistry?
Ans: Redor reactions.

2.1 Electrochemical Cells:

Thse ae devices used -to interconvert electrical and chemical energies. There are two
electrochemical cells
) Galvanic cells () Electrolytic cells
4. What are galvanic cells or voltaic cells? Give examples.
Ans: The cells n which chemical energy of spontaneous redox
reaction is converted into electrical e
called gaivanic cells.
Eramples: Daniel cell, dry cell (Leclanche cell), mercury
Iithium ion cell (mobile cell).
-
cell, lead- storage battery, nickel cad

3. Mention the accepted IUPACconvention while

representing the symbolic notation of galvani
Ans: () Keep anode on the left and cathode on the right
(n) single vertical line is written between metal
A

and electrolyte solution

(iiü) A double vertical line is
written between the two electrodes to
Anode || Çathode indicate the salt bridge.
M, | M H
M |M,.
6. What is a sat bridge?
Ans: It is a U-shaped glass tube
filled with a gel called agar-agar containing
7. What is the role of salt bridge KCl or KNO; or NH4NO3.
in connecting anode and cathode or two
Ans: (i) It maintains electrical half cells?
neutrality on both sides.
() t prevents the accumulation charges
of in the half cell.
(ii) It avoids liquid-liquid junction
potential.
8. What happens when a salt bridge
is removed from theelectrochemical
Ans: The potential drops zero. cell?
to
<br>

Jeevith Publications 51
9. Why is KCl used in thepreparation of salt bridges?
Ans: The transport number or the velocities of both K' and CI ions arc almost samc.
10. Explain the construction and working of
Daniell cell. [Marcl 2015) Voltmeter
Ans: Daniell cell consists of a zinc rod dipped in 1M
ZnSO4 solution and a copper rod dipped in IM
CuSO, solution. The two solutions are
interconnected using a salt bridge and the two rods +

are externally connected using a metallic wire. It 2e Current

starts toproduce electricity. Zinc anode K+ Copper cathode

Electrons are liberated at the anode and received at Salt bridge
cathode. Hence electrons flow from zinc electrode
to copper electrode and electric current flows from
copper to zinc. The total cell reaction in Daniel
SO
cell is as shown below. C
Anode (oxidation) Zn(s) Zn (aq)+ 26 so
-
Cathode (Reduction) Cu? (ag) + 26 Cu(s)
Net cell reaction Zn(s) + Cu(aq) Zn(aq) +Cu(s)
Thus the loss of electrons i.e., chemical energy is converted into electricity or electrical energy. The cell
potential (emf) (voltage) of the Daniel cell 1.10 V.
11. What is the standard cell potential of the Daniell cell?
Ans: 1.1V
cell.
12. Write the half cell reaction occurs in the cathode of the Daniell
Ans: Cu* (aq) +
2eCu(s)
cell.
13. Write the half cellreaction occurs in the anode of the Daniell
Ans: Zn(s)- Zn*(aq) + 2e
happens to the cell potentialwhen concentration of cathodic solution is increased?
14. What
Ans: Cell potential increases. during the
direction of the current flow when electrons are moving from anode to cathode
15. Mention the
working of Galvanic cell.
opposite to that of electron flow.
Ans: The direction of current flow is
16. Write the symbolicnotation of
Danielcell.
2

Ans: Zn(s) | Zn) I| Cug) Cu)

cell when
17. Explain the functions of Daniell
If applied potential is less than
1.1V (Eext <1.1 )
1.
= 1.1 )
applied potential is equal to 1.1 V (Eext ,
2. If >1.1 V)
the applied potential is more than 1.1,V (Eext
3. If <1.1V):
1. If applied potential is less than 1.1V (Eext
Ans:
as galvanic cell
i) It continues to function copper to zinc.
copper rod and hence current flows from
ii) Electrons flow from zinc rod to
at anode and copper deposites at cathode.
ii) Zincdissolves
II PUChemistry

Student's Illuminator
<br>

nte cerrrnt athete

brtt

Zaso, CuSO,
2. If appliedpotential is cqualto 1.1V (Eext
1.1V)
i) Noflow of clectrons or curent.
i) No chemicalreaction (the cell reaction attains cquilibrium)

-Cu

ZnSO, CuSo,
3.
If the applied potential is more than 1.1 V (Eext>1.1
V)
The cell reaction gets reversed
and the cell functions as electrolytic
Electrons flows from copper to cell.
zinc and hence current flows
Zinc is deposited at from zinc to copper.
the zinc electrode and copper
Ea >1.1 V dissolves at copper electrode.

cathode
+ve current anode
-Ve
Zn
-Cu

ZnSO, CuSO,

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Jeevith Publications 53

2.2 Galvanic Cells

1. What is oxidation?
Ans: Removal of clcctrons is callcd oxidation
Zn(s) Zn'(aq) + 2e
2. Name theclectrode at which oxidation takes place.
Ans: Anode.
3. What is reduction?
Ans: Addition of clcctrons is called reduction
Cu
(aq) + 2e Cu(s)
4. Name the electrode at which reduction takes place.
Ans: Cathode.
5. What is redox reaction?
Ans: Areaction inwhich both oxidation and reduction takesplace simultaneously is called redox reaction.
Zn(s) +Cu² (aq)Zn (aq) + Cu(s)
6. What is an electrode? Give an example.
Ans: A metal rod dipped in its own ion solution is called electrode.
Example: ) Zinc roddipped in Zn* ion (ZnSO) solution is called zinc electrode.
(ii) Copper rod dipped in Cu ion (CuSO.) solution is called copper electrode.
7. What is electrode potential or single electrode potential?
Ans: The potential developed between a metal rod (electrode) and its own ions in a solution (electrolytic solution)
at equilibrium is called electrode potential or single electrode potential.
It is denoted by E and expressed involts.
8. Name the unit to measure electrode potential.
Ans: Volt (V)
9. What are the factors that electrode potential depends on?
Ans: (i) Nature of electrode (ii) concentration of ions in this solution
(iii) temperature (iv) nature of ions in this solution
10. What is standard electrode potential?
a own ion in a solution at 298 K and 1
M concentration
Ans: Thepotential developed between metal rod and its
E°.
and at equilibrium is called standard electrode potential. It is denoted by
as standard reduction potential (SRP).
Note: According to IUPAC standard electrode potential E° also called
11. How does electrode potential changes with
concentration of metal ions?
ions increases.
Ans: Electrode potential increases concentration of metal
as

12. What is cell potential (voltage)?

(SRP values) of two electrodes of the galvanic cell is called
Ans: The difference between the electrode potentials
emf of a cell or céll potential.
which affects emf of the cell.
13. What is emf of the cell? Mention the factors cell
when no current is drawn through the cell. Emf of the
The cell potential is the electromotive force
depends on
) concentration of ions in electrodes
(i) temperature
<br>

(i) nature of ions in this solution

(i) nature of clectrode
Or
Prducticm
-E'oxidation

valuc is anode
in the galvanic cell,

Note: Among cathbode andless

the given two SRP valucs, more valuc is V arc
rcspcctivcly.
V and+0.34
Amye: The E° values of Zn and CuI are -0. 76
Zn is anode and Cu is cathodc.
14 Give DiMerence potential difference (voltage) Voltage (cell potential)
between Emf and
SLNo. difference of the clectrode potentia
Emf It is the
1.
Is thc potential diflerence
betwecn thc two two clectrodes when the cell
flowing in the the is utc
clectrodes when no current is
operation.
circuit. less than the maximum va
can It is always
2. tlhat tlhc cell can deliver
It is the maximum voltage of voltage which the cell
deliver.
It is not responsible for the steady flow
3 the steady flow of current
It is responsible for current in the cell.
in the cell.
It is measured using voltmeter
4. It is measured using potentiometer
a Galvanic cell the following cell reaction takes place
Cu(S) +
2Ag (aq)Cu"(ag)+2Aoe
15.
n
Write the symbolic notation of the cell.
Ans: Cu(s) | Cu(aq) | Ag(aq) |Ags)
or Normal Hydrogen Electrode (NHE),
16. Explain Standard Hydrogen Electrode (SHE) 2014,
March July 2014, July 2015, July 2017, July 2019)
Ans: SHE is a primary reference electrode because its SRP value
Copper wire
(E°) is assumed as zero V.
Glass jacket
The standard hydrogen electrode consists of a platinum foil
coated with finely divided platinum. The foil is connected
with platinum wire with mercury. A copper wire is Pure hydrogen
connected from mercury for external circuit. The platinum under 1 bar pressure
foilis dipped in IM HCI solution as shown in the figure. Narrow glasst

Working: Pass pure and dry hydrogen gas continuously at Mercury

1
bar pressure from inlet. The hydrogen gas gets adsorbed
on the surface of the Pt foil. The adsorbed hydrogen gas is -Platinum foil

in contact with the H

ions of 1 M
HCI solution, The
electrode reaction is 1MHCl acid

H(a4)
+eH,()
Symbolic notation of standard hydrogen electrode
is
P(s), H, (g lbar) | H“
(|M)
The standard hydrogen electrode (SHE)
potential is zero volts.

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s illuminator I| PU
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Jeevith Publications 55
Note: At 298K, the emf of the ccll, constructed by combining standard hydrogen electrode as
anode
(reference half cell) andthe other half cell as cathode, gives the standard reduction potential other half cell
of
by assuming SRPof SHEis ZERO volts.
17. What is the value assigned tothe clectrodc potential of SHE at 300K?
Ans: Zero volts.
18. Platinised platinum is used for the construction of SHE. Give reason.
Ans: Platinised platinum provides moresurface area for adsorption of hydrogen gas.
19. How to determine the SRP of copper electrode using SHE?
Ans: The standard hydrogen electrode (SHE) is the reference clectrode.
The given copper electrode is coupled with SHE using salt bridge.
Theemf of the cell formed is measured using a potentiometer and it is found to be 0.34V.
In this cell, copper electrode is positive relative to the hydrogen electrode. The potential of the copper
electrode is calculated as given below.
E
=Eeathode -Eanode

Enner
'copper
Ereference

FEell -BsHE
Ecopper

=0.34V -0.00V=+0.34V
Anode half-cell reaction: H, (g) 2H* (aq) + 2e
Cathode half-cell reaction: Cu (aq)+2e Cu(s)
Overall cell reaction: H,(g) +Cu*(aq) 2H* (aq)+Cu(s)

Cell notation: Pt(s) | H,(g,l bar) | H (aq,1 M) || Cu (aq, IM) |Cus)

20. How todetermine the SRP of zinc electrode using SHE?
Ans: The standard hydrogen electrode (SHE) isthe reference electrode.
The given zinc electrode is coupled with SHE using salt bridge.
The measured emf of the cell by using potentiometer is 0.76 V. The Standard Reduction Potential
(SRP) of Zn"/Zn is calculated by
= or ER-E?
E
E-E
Eel -Ez*/Za

0.76 = 0-Ez/Z

E1Zn =-0.76V
Therefore, SRP of Zn|Zn electrode is -0.76 V.
Half cell reactions: Atcathode: 2H (aq) + 2e H,(g)
At anode: Zn(s) Zn**(aq) +2e
-
Net cell reaction 2H* (aq)+Zn(s) H,(g) + Zn*(ag)
:

Cell notation: Zn |Zn (aq, 1M) || H" (a4, IM)|H, (g, l bar) |Pt(s)
What is
21. A galvanic cell is constructed using SHE and silver electrode. [Ag]=
IM and E°... =+0.8V.
thecell potential?
Ans: E,cell = E°'Agt/Ag -Eyn =0.8-0= 0.8 V
II PUChemistry
Student's Illuminator
<br>

22. What are inert clectrodes? Give an example.

Ans: Thc clectrodcs which do not participate in the reaction but provide their surface for oxidation or
reduct
rcactions and for the conduction of the clectrons are called incrt clcctrodes.
Platinum or gold arc uscd as inert clectrodes.
23, Whatis the role of platinum inthe hydrogen electrode Pt(s) |H:(g) |H"(aq)?
Ans: Platinum provides surface for the adsorption of hydrogen gas and the following half reaction
0ccurs On
surface. t
H (aq) + c
24. Whatis the role of platinum in the bromine electrode Pt(s) |Br;(aq) | Br (aq)?
Ans: In this electrode, platinum provides surface for the following
half reaction
1
Br, (aq)
2 +eBr (aq)

25. Differentiate between reactive and inert electrodes.

Ans:
Reactive electrodes
(1) | They participate in the reaction.
Inert Electrodes
They do not participate in the reaction.
(2)| Themselves undergo oxidation and
reduction.They provides surface for oxidation and
What are the importance SRP reduction reactiom
of values?
Ans: () Standard electrode potential
(E) value can be used to predict the ability
agent ora reducing agent.
Higher the standard electrode
of the species as an oxidisig
lesser is the reducing ability. potential, greater is the oxidising ability at
For example,
The standard electrode potential
for fluorine has the highest
(F) has the maximum tendency to get reduced value indicating that fluorine g
to fluoride ions (F) and therefore
the strongest oxidising agent and fluoride fluorine gsi
ion is the weakest reducing agent.
Lithium has the lowest electrode
potential indicating that lithium
agent while lithium metal ion is the weakest oxidis
is the most powerful reducing
(ii) If the standard electrode agent.
potential of an element is greater
hydrogen. If the standard electrode than zero, then its ion is reduced
potential of an element is negative
the metal to hydrogen gas. then hydrogen ion is reduced:
26. Give uses of electrochemical
cells.
Ans: Electrochemical cells are
extensively used for determining
() pH of solutions
(ii)Solubility product
(iii) Equilibrium constant
(iv) Thermodynamic properties and potentiometric titrations

Chemist
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Jeevith Publications 57

StandardReduction Potential (SRP) of different electrodes at 298 K

Reactions (oxidised form +ne) Reduced form EV
B(g) +2e
2F 2.87
Co+e 1.81
H,0, +2H* +2e 2H,0 1.78
MnO, +8H* + 5e Mn* +4H,0 1.51
Au +3e Au(s) 1.40
Cl,(g)+ 2e 2CI 1.36
Cr,0; +14H* +6e 2Cr* +7H,0 1.33
O,(g) +4H* +4e 2H,0 1.23
MnO,(s) +4H* +2e Mn* +2H,0 1.23
Br, + 2e 2Br: 1.09
NO; +4H* +3e NO(g)+ 2H,0 0.97
2Hg?* +2e Hg,* 0.92
Ag*+e Ag(s) agent
0.80
agent

Fe
+e +
Fe2+ reducing 0.77
2e
oxidising

0,(g) +2H* H,0, 0.68

I,+ 2e 2I
0.54
of
of Cut +e Cu(s) strength 0.52
strength

Cu2 +2e Cu(s) 0.34

AgCl(s) +e Ag(s)+CI -Increasing 0.22
AgBr(s) +e Br
-Increasing

Ag(s)+ 0.10
2H* +2e H,(g) 0.00
Pb2*+2e Pb(s) -0.13
Sn* +2e Sn(s) -0.14
Ni* +2e Ni(s) u
0.25
Fet +2e Fe(s)0 -0.44
Cr +3e Cr(s). -0.74
Zn²* +2e Zn(s) -0.76
2H,0+2e H,(g)+20H"(aq) -0.83
AP* +3e Al(s) 1.66
Mg +2e Mg(s) -2.36
Na" +e Na(s) -2.71
Ca+2e Ca(s) -2.87
Kt +e K(s) -2.93
Li +e Li(s) 3.05
1. A negative E
that the redox couple is a stronger reducing agent than the H´/H, couple.
means
2. A positive E means that the redox couple is a weaker reducing agent than the HH, couple.
Note: If E° (SRP) values are expressed in increasing order in the table then it is called electrochemical series.
Student's lluminator I PUChemistry
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Electroche
58

27. Following are the Values of E, valucs of certain clements. Arrange them in the descending order
their oxidising power
E-2.36 V, E0.25 V,Ees =0.77V, Ehe +0.8 V, Pr 2.87V
>E.
Ans:
Oxidising power decreases
28. Mention an observation made when an ironrod is dipped into 0.1 M CuSO4 solution?
Ans: Blue colour of CuSO, solution will be discharged due to reduction of Cu* to Cu and green
appcarcd due to oxidation of Fe to colour W

29
Fe.
Given Ey<E, then between nickel and hydrogen which is more stable in reduced form?
Ans: H;
30. Which of the following is strongest reducing agent? Zn|Zn
Ag | Ag=0.80 V.
=-0.76 V, NI |Ni =-0.25 V

Ans: Zn is the good reducing agent since

Zn has low SRP value.

2.3 Nernst Equation

For the electrode reaction;
Mn(aq) + ne M(s) the electrode potential at any
calculated using Nernst equation. given concentration ea
Nernst equation is given by
RT-InM]
nF [M*]
But concentration of solid metal
M is taken as unity and we
have
1
EMM= E

nFIn [M*]
Where, = Standard potential
EyM of the electrode
R= Molar gas constant (8.314 JK
mol)
T=Temperature in Kelvin
F= Faraday constant (96487 C mol or 96500 C
n=Number of electrons involved
mol'y
in
electrode reaction
[M] = Concentration of metal ion.
[M] = Concentration pure
of solid metal (taken as
unity).
Nernst equation for Daniell cell:
In Daniel cell at any
given concentrations
Zn(s) + Cu2t(ag) of Cu2+ and Zn2t ions at 298 K for the net
Zn(aq) + Cu(s), Nernst equation cel
is given by,
E
= Ecel 2.303RT-log (Zn(aq)]
2F [Cu (aq)]

log Zn*1
Ece
=E 2.303x 8.314×298
2x96500 [Cu]
Ece = Ecel o.059|og [Zn]
t's illuminator
2 [Cu']
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Jeevith Publications 59
Relation between equilibrium constant K¢
and En
In galvanic cell involving the net cell rcaction of the typc,
aA + bB ne >cC+dD
Nernst equation can be written as:

Ecel = Eel RT [CI(Dy

nF [AJ(B]"
Ece = Ecell RLnQ
nF
=
where Q is the reaction quotient, O LC|Dr
[AJ[B]
=
At equilibrium, Ecell =0, the reaction quotient, Q Kewhere K, is the equilibrium constant.

El =
KLIn Ke or Ece =+ 2.303RTlog K,
nF nF
This equation gives a relationship between equilibrium constant of the reaction and standard cell potential of the
cell.
At temperatureT=298&K, F= 96500C, and RR=8.314JK mol", the above equation can be written as
0.0591ogKe
Ece =+
n
In Daniell cell, when the circuit is closed, the concentration of Zn keeps on increasing while the concentration of
Cu2t keeps on decreasing. At the same time voltage of the cell as read on the voltmeter keeps on decreasing. After
some time, we shall note that there is no change in the concentration of Cu and Zn ions and voltmeter gives zero
reading. This indicates that equilibrium has been attained at which Ecell 0. Therefore,
[Zn (a)]
=Ke
[Cu²* (aq)]
o.0591ogK,
Then from Nernst equation, cel
2

In Daniel cell, n
=2, E=1,1V then,

Ll003 log K,.

2

By usual calculations, K, =1.678× 10"at 298K

Relation between standard free energy change AG° and Eel
that
the potential difference (Ecell in volts) and the charge
The electrical work done (w, in joules) is the product of
flows (in coulombs).
Wmax =Eell X
Charge
energy (-AG°).
on the surroundings is equal to decrease in free
The maximum work done
Wmax =-AGo
-AG° = E°, x charge
But charge = nF

IIPU Chemistry
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Electoche
60

AG°-nFB cquilibrium constant

cncrgy change and
Rclation betwccn standard frcc 2.303RT
E -log K.
We knowv that, nF
AG°
But
cel
nF
AG° 2.303RTLlog
nF nF
K.
AG° =-2.303RT log K

Reaction paramcters at the standard state

AG° K Reaction at standard state conditions
<0 >0 Spontaneous
-1
0 At equilibrium
>0 <1 <0 Non-spontaneous
Write the relation between standard Gibbs
free energy change of the reaction and equilibrium consta.e
Ans: AG° =-RTIn K
or AG° =-2.303RTlog,, K

Multiple Choice Questions

1. In a Galvanic cell d) Copper goes on dissolving
a) Chemical reaction produces
energy electrical5. A Galvanic cell become electrolytic cell
b) Electrical energy produces
a) Eell =Eet b) El >Et
chemical c) Eent > Eçell
reaction d) Ecel =0
c) Reduction occurs at anode 6. The difference between the elec
Oxidation occurs at cathode
d)
potentials of twYo electrodes when no cu
2. Which one of the following statement
is is drawn through the cell is called
Wrong about galvanic cell? a) Cell electromotive force
a) Cathode is positive electrode
b) Standard electrode potential
b) Cathode is a negative electrode
c) Potential difference
c) Electrons flows from
anode: to cathode d) Current
through external circuit
d) Reduction occurs at cathode 7. While representing the galvanic cell we
3. The two electrodes present in the
Daniell cell are
a) Ag* |Ag and Cu |Cu a) Anode on the left and cathode on th

b) of salt bridge
Zn* |Zn and Ag" |Ag b) Cathode on the right and Anode the
on

c) Zn |Zn and Cu*|Cu of salt bridge

Cathode and anode on any side of
tr
d) Zn
|Zn and Mg* | Mg c)
bridge
hen the Daniel cell is in use No specific convention tó
represent
Zn* are reduced to Zn d)
galvanic cell
Zn is oxidized to Zn*
Cu is oxidized to Cu*
 I.09
<br>

K
-log cell
()

= 0.34 x6
log Ke
0.0591 =-1.09-.0.0591
2
=34.5177
=-1.09- 0.0591
Ke= Anti log(34.5177)
2
Ke =3.294 x 104 0.0591
=-109 -log
(iii)) AG°=-nFEeell 2
=-6x96487x 0.34 =-l.09- 0.0591,-[log
2
=-196833.5 J nmol
0.0591,
=-L.09-
=-196.8335 kJ molr! 2
0.0
9. Write the Nernst equation and calculate 0.0591
emf =-1.09 x7.0
of the following cell. 2
Pt(s)| Br (0.010M) | Br,()|| H
(0.030M)|H,(1 bar) | Pt(s) =-1.09 -0.2082=-1.2
(NCERT Exercise) •. This cell is not feasible.

2.4 Conductance of Electrolytic Solutions

1. What are conductors?
Ans: Thesubstances which allow the passage
of electric current through them are called conductor
2. Name the types of conductors.
Ans: There are two types of conductors, (i) Metallic conductors (ii)
Electrolytic conductors

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<br>

Jeevith Publications
3. What are metallic conductors?
Ans: The conductors which allow the movement of clectric current due to the movement of electrons are called
metallic conductors. Examples: Al, C, etc.
4. What are super conductors? Name the typc of materials which shows super conducting property at
high temperatures as high as 150K.
Ans: Materials have zero resistivity or infinite conductivity are called super conductors.
Ceramic materials and mixed oxides.
5. What are electrolyticconductors?
are called
Ans: The conductors which allow the movement of electric current due to the movement of ions
etc.
electrolytic conductors. Examples: Aqueous solutions of NaCl, KCI,
6. On what factors the electronic conductance or metallic conductance depends?
Ans: (i) Nature and structure of the metal
(ii) Number of valence electrons per atom
(iii) Temperature
7. How does metallic conductance changes by increasing the temperature?
Ans: Metallic conductance decreases by increasing temperature.
(ionic conductance) depends.
8. Name the factors on which the conductivity of electrolytic conductance [March 2017|
or On what factors the conductance of a solution depends?
Ans: (i) Nature of the electrolyte.
temperature)
(ii) Temperature (It increases with increase of
(iii)Nature of the solvent and its viscosity.
(iv) Concentration of ions in the solution
solvation.
(v) The size of the ions and their
electrolytic conductors.
9. Give any twodifferences between metallic and
Ans: Electrolytic conductor
Metallic conductor
SI. No. movement of ions.
due to movement of electrons. The conductivity is due to the
i The conductivity is state or solution
They conduct electricity in fused
state.
ii. They conduct electricity in solid state.
Chemical change takes place.
No chemical change takes place.
ii.
in Conductivity increases with increase in
Conductivity decreases with increase
temperature.
iv. temperature.
Electrolytes decomposes into ions.
V. Metals do not decompose. Transfer of matter takes place.
matter takes place.
No transfer of Examples: HCI, NaOH, etc.
vi. Examples: Cu, Al, Pt, etc.
are called insulators
10. What are insulators? passage of electric current through them
which do not allow the
Ans: The substances wax, etc.,
Example: Rubber, wood, plastic, aqueous
are electrolytes? fused (molten) state or in the
11. What electricity either in the
electrolyte is a substance which conducts
Ans: An decomposes on passing
electricity.
solution state and it
etc.
Examples: HCI, NaOH, NaCI,
non electrolytes? or aqueous solution state ar
12. What are in molten state in the
conduct electricity either
Ans: The substances
which do not
alcohol, benzene, glucose, urea, sugar et.,
Example: Ethyl
called non electrolytes. ic
<br>

66

13. Name the types of electrolytes.

Ans: Elecctrolytes ate of two types.
() Strong clectrolytes
(ii) Wcak clcctrolytcs.
14. What are strong clectrolytes? Give examples. in
aqueous solution at mode
ionisation
undergoes complete NaOH. KOH, etc
Ans: A
strong clectrolyte is onc which ctc. Strong bases like
H,SO,
HCI, HNO,
concentration. Exanmples: Strong acids like
salts solutions likc NaCI, KCI, etc.
15. What areweak clectrolytes? Give examples. aqueous solution at moderate Concentrati
ionisation in
Ans: A weak electrolyte is one which undergoes partial (HBO,), phost
acid. formic acid, citric acid, lactic acid, Boric acid
ramples: Weak acids like acetic NH,OH, Zn(OH)2, CoHsNH,
(aniline), etc.
etc. Weak bases like
dcid, carbonic acid,
16. What is conductance? electric current is called conductance (G). or
a that allows the movement of
Ans: 1 he property of material
reciprocal of resistance is called conductance.
1
G= where R=resistance.
R
The unit of conductance is ohm
or mho or siemen (S).
17. What is the unit of resistance in SI units?
Ans: kg m² /s³A?
area of cross.section of the object?
18. How is electricalresistance related length and
to
to its a
Electrical resistance of any object is directly proportional to length () and inversely proportional
Ans:
of cross section (A).
Raor R=pA where p is resistivity or specific resistance
A
19. Define resistivity. What is the SI unit of resistivity?
it is one metre long and its a
Ans: Resistivity for a substance is defined as the resistance of the substance when
of cross section is one m.
The SI unit of resistivity is ohm m.
1Qm= 100 2em or 1 Qem=0.01 2m.
20. What is conductance (G)? Give its SI unit.
Ans: Reciprocal of resistance gives conductance.
The SI unit of conductance ohm or siemen (S) or mho.
21. What is specificconductance or conductivity (*)?
Ans: It is the conductance of electrolytic solution placed between two electrodes of length 1 m apart and ai

cross section m. 1
or
The conductance of Im' of electrolytic solution is called conductivity.
The reciprocalof resistivity gives conductivity.
The unit of specific conductance or conductivityis S m-' (in SI system) and S cm (in
Cs Sysicy
1S cm=100
1Sm 0,01 S cm
or S m

Mention thefactorson which conductivity depends.

Ans: (i) Nature of the electrolyte
(ii) Temperature (iii) Pressure. Chemis
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Jeevith Publications 67

23. What is cell constant?

Ans: It is the ratio of the distance between two clectrodes () and the area of cross section 'A'.

i.e., cell constant =G*:

A
24. Direct measurement of conductivity of ionic solutions by Wheatstone bridge is not possible. Give
reasons.
Ans: (i) Direct current (DC) will change the conmposition of the ionic mixture due to electrolysis.
(ii) Solutions cannot be connected to the bridge like other solid conductor.
25. How do you solve the problems arised in the measurement of conductivity of ionic solutions by using
Wheatstone bridge?
Ans: (i) Instead of direct current (DC), alternating current (AC) should be passed.
(ii) Electrolytic solution is connected to Wheatstone bridge by using conductivity cell.
26. Explain the construction of two simple designs of conductivity cell.
Ans: Conductivity cell consists of two platinum electrodes coated with platinum black. These two electrodes have
area of cross section equal to A and are separated by distance P. The solution is placed between these two
electrodes of length I and area of cross section 'A'. The resistance of this electrolytic solution is given by
R=p

R=y!
K A

The ratio is called cell constant (G*). The cell constant is usually determined by measuring the resistance
A
of the cell containing a solution whose conductivity is already known (more commonly KCl solution is used
for this purpose).
G* = RK
Connecting
Connecting wires
wires

Plantinized Pt
electrodes

Plantinized Pt electrode Plantinized Pt electrode

Fig. Two different types of conductivity cells

solution by using Wheatstone
27. Explain the experimental determination of conductance of electrolytic
bridge.
steps.
Ans: The determination involves the following two
Step 1: Determination of cell constant of conductivity
cell
known specific conductance (K). It is
Conductivity cell of suitable design is filled with KCl solution of
is a variable resistance, R, be the resistance of
connected to Wheatstone bridge as shown in the figure. R, an A.C.
P is the detector. The bridge is connected to
conductivity cell, Ry and Ry are two fixed resistances.
source of power as shown in figure. bridge is
that the detector shows no current in the circuit and the
The variable resistance adjusted such
cell is given by,
balanced. At this condition the resistance of the conductivity
R_R
R, R4
II PUChemistry
Student's Illuminator
<br>

68 Electroche

.:. R,= R,R, Conductivity ccll

R,
The ccllconstant of the conductivity ccll is calculatcd using De
the relation
G*=R,K (K is knovwn) P
Step 2: Determination of specific conductance of the
given clectrolyte solution
R
The conductivity ccll is now fillcd with given clectrolytic
solution. It is conncctcd to the Whcatstone bridge and the
Cxperimcnt is repcated. The resistance Ry of the clectrolytic
solution is determined. Specific conductance of the
clectrolytic solution is calculated using the relation, Fig. Arrangement for
G*
measurement of resistance of a
or conductivity = cell constant G
K= solution of an electrolyte
R, resistance R
28. What is molar conductance or molar conductivity? How is it related to concentration and
conductivity? [March 2014]
Ans: It is the conductance of allthe ions produced the entire solution which contains
in one mole of an elect
OR
It is the conductance of the yolume of solution containing one mole of electrolyte kept between
electrodes with area of cross section A and distance of unit length.
It is denoted by Am
Molar conductivity is related to specific conductance (conductivity) and concentration(c) of the solution is
K
(where c' is in mol/m)
Molar conductivity is related to specific conductance (conductivity) and volume (V) of the solution is

An =KV c=

29. Write the relation between molar conductivity and molarity of solution in both SI (S mol) m
and
CGS (S cm' mol) units.
[July 2014]
Ans: A(S m² mol) = K
A (S cm² mol')= KX1000
1000× M M
Note: m² 1S
mol= 10° S cm' mol-!
1S cm² mol =
10S m mol-!
30. What is the unit of molar conductivity?
Ans: S m² (SIsystem) and S cm mol (CGS system).
mol

31. What is the effect of dilution on conductivity? [July 2018, July 2020)
Ans: Specífic conductance decreases with dilution because as the dilution
a m increases, the total number o to
of solution decreases.
32. What is the effect of dilution on molar conductance?
July 2020)
Ans: Molar conductance increases with increase
in dilution.
fiv
$3. to
What happens to molar conductivity when one mole of KCI dissolved in one litre is diluted
litres? [March 2015)
Ans: Increases
Chemistr
Sdonto ill
<br>

69
Jeevith Publications
34. Explain the variation of molar conductivity with concentration. |March 2015)
an clcctrolyle incrcascs with dilution. This is bccausc the total volume (V) of
Ans: The molar conductance of on
found that decrease in conductivity
solution containing onc mole of clcctrolytc incrcascs. has becn
It

dilution of a solution is more than compensated by increase in its volume.

At low concentrations, the molar conductancc of strong clcctrolyte obeys the Debye
a - Huckel -Onsager
cquation.
OR A
=
A-AVe
A
= molar conductance at any concentration. 400
where CH,COOH
A = molar conductance at dilution, A = constant,
infinite

c= concentration
when c 0,
A
=A KCI
concentration Vc is
For strong electrolytes the variation of A, with
small (between 4 to 10%) as shown in the figure. 0.2 0.40

(moUL)"
The plots can be extrapolated to
zero concentration and the intercept cI
when concentration
gives limiting value of molar conductance (A)
at infinite dilution. The value of A in the above equation
depends
approaches zero, called molar conductance
on the cation and anion produced by the dissociation of the
on the type of electrolyte iie., the charges
electrolyte in the solution.
near lower
electrolysis, molar conductivity increases steeply (sudden rise) on dilution especially
For weak in the
to increase in the degree of dissociation and consequently the number of ions
concentrations due
For weak electrolytes the variation of A
with yc and limiting
solution containing one mole of electrolyte.
electrolyte by using
cannot be obtained by extrapolation. So we can obtain A for weak
molar conductivity
Kohlrasch's law.
[March 2018, March 2020]
35. Define limiting molar conductivity. conductivity.
electrolytic solution at infinite dilution is called limiting molar
Ans: The conductivity of
2019, March 2020]
law. (July 20I5, March 2015, March 2018, July
36. State Kohlrausch an electrolyte at infinite dilution is equal
to the sum of the ionic
molar conductance of
Ans: It states that the
anions of electrolyte.
conductances of respective cations and
ORt sairm
can be represented as the sum of the individu=
It states that the limiting molar
conductivity of an electrolyte
electrolyte.
contributions of the anion and cation of the th
, 2 are limiting molar conductivities of sodium and chloride ions respectively
Example: 1. If 2° and
of sodium chloride is A Naci) = +cr
the limiting molar conductivity
v_ anions then its limiting molar
conductivi
on dissociation gives V, cations and
In general if an electrolyte
is given by,

Example: For CaCl;

Am(CaCh,) =e +2r
For Na,SO4 m(Na,SO,)
= 24
tso
I| PU Chem
<br>

37. Giveany two applications of Kohlrausch Iaw. [April

Ans:
() It is uscd to determinc the limiting molar conductivity of a weak clcctrolyte which cannot be deterrineA
cxperimentally.
Evample 1: The molar conductance of weak clectrolyte acctic acid at infinite dilution weak
electroky
be calculated
3strong electrolytes namcly sodium acetate (CH;CO0Na), HCl and NaCl i.c.,

Am(CHC0OH) =Am
m(CH,-coONa) +A
m(01CI) -Am(NaC)

According Kohlrausch law, theR.H.S. is

=ACH,coo +A tA +er -(a +
er)
=AeH,coo +
tag. +2er -,. -

=CH.co0- +y =m(CH,COOH)
.. According
Kohlraush law LHS= RHS.
Example 2: The nolar conductance
weak electrolyte of NH,OH at
strong electrolytes namely NH,CI, infinite dilution can be calculated
NaOH and NaCi. i.e.,
A°
m(NH,CI) +Am(NaOH)
m(NH,OH)
m(NaCl)
According Kohlrausch law, the R.H.S. is

+cr + +or (a tar)

+cr++or-
NH; m(NH,OH)

According Kohlraush law LHS =

RHS.
(i) Kohlraush law is used to determine
the degree of dissociation
weak electrolyte (weak acid like
aceic acid)
c' and the dissociation constant 'Ki

OC= mm where oc = degree of

dissociation.

Am= molar conductance at any

concentration 'c', A = limiting
at infinite dilution, m molar conductivity or molar cond

We know that for weak

acids the ionization or dissociation
constant 'K,' is given
by the equation
K,= m C
m
(1– c)
A(A-^m)

Multiple Choice Questions

1 SI base units of resistance
is equal to 2.
a) kg m² sA-2 The SI unit of resistivity is
b) kg m²
a) ohm b) Ohm/metre
c) kg m² s² A3 d) kg m S
c) metrelohm d) Ohm
metre
<br>

dissociation constant if A, for acetic acid Ca2

is K,
390.5 S cm mol'. (NCERT (|-o)
Solved
problem) (0-025 mol L')(0-114
KX1000
Ans: A,, = (|-0-114)
M
x
3.67%10mol L!
4.95 10x1000V 8. The conductivity of 0.20 M solution
0.001028 at 298 K is 0.0248 S of KC
= 48,15 S cm² cm'. Calculate its
mo! molar conductivity. (NCERT Exercise)
Am Ans: Molar conductivity, = Kx1000
M
48.15 S cm² mol 0-0248x1000
390.5 S cm² mol-!
=0.1233 0-2
=124 S cm moll
= ca?
K, 9. Conductivity of 0.00241 M acetic acid is
(1-a) 7.896 x 105 S em-!. Calculate
its molar
0.001028 molLx (0.1233) conductivity and if A for acetic acid
is
1-0.1233 390.5 S cm² mo!, what is its dissociation
K, =1.78x 10 mol L-! constant? (NCERT Exercise)
.
The molar conductivity of 0.025 mol L1 Ans: Molar conductivity, Am= Kx1000
methanoic acid is 46.1 S cm mor'. M
Calculate its degree of dissociation and 7-896x10S cm 1000 cm
dissociation constant. 0-00241 molL L
Given
u) =349.6 S cm² mol-! =32.76S cm mol!
and Hcoo
=54.6 S cm' mol1 Now, a= 1m
(NCERT Intext question)
Ans: Am(HCOOH) = 32.76 S cm moll
u) +HCOO) 390.5 S cm molr!
=0.084
-349.6+54.6 ca?
= 404.2 S cm mol Dissociation constant, K,
(1-a)
Degree of dissociation; .oa=. m(HCOOH) (0.00241mol L')(0.084)
m(HCOOH) (1-0.084)
=1.86 x
46.1 10 mol L

=0.114
404-2

2.5 Electrolytic Cells and Electrolysis

1. What is an electrolytic cel1?
Ans: The cells in which electrical energy causes chemical reaction (electrolysis) are called
electrolytic cells. OR
The cells used to carryout electrolysis are called electrolytic cells. Example: Copper electrolytic cell.
What is electrolysis?
2.
Ans: The process of decomposition of an electrolyte by passing electricity through it is called electrolysis.

Student's lIluminator
II PU Chemistr
<br>

Electe
3. State Faraday's
I Iaw of clectrolysis. Write its mathematical form by using
1July 2015, March 2016, July 2018,
Ans: It states ,July
that,the anmount of
is dircctly proportional substance deposited or liberated at any clectrode during electrolysis
by
e
to the quantity of electricity passed through the electrolyte (solution or melt
i.C., wcO
where W mass ofthesubstance depositcd or liberated, Q - 4uantity of electricity passed.
But
Q-It whcre I curent in amperes, t timc in scconds.
W]t
of a material.
4. whereZ-
Definc elcctrochcmical cquivalent
clectrochemical cquivalent (e.c.c)
Ans: (c.C.e).
It is the mass of a 1 ampere of current is passed through an electroly
substance deposited when
second.
$.
What is the charge of one mole of electrons?
Ans: Charge off one molc of clcctrons =
96487 C mol 96500C mol!
Note: 96500 C = charge of x vogadro's
6.
le A
number.
Define a Faraday. What is the value of one
Faraday'?
Ans: The charge of one mole of electron is
called a Faraday ().
1F=96500 C
mol

7. State Faraday's 2nd law of electrolysis. July 2014, March 2019, July 20207
Ans: It states that, when same amount of electricity passed
is
the substances deposited or liberated at the electrodes is
through different electrolytic solutions the m

directly proportional to their equivalent masse

Mathematically it can be expressed as WL=PL
W, E,
8. What are the factors that determine the products of
Ans: (i) Nature of the electrolyte electrolysis?
(ii) Type of the electrode used.
(iii) Standard electrode potential competing
of ions.
(iv) Concentration of electrolytic solution.
(v) Over voltage or over potential.
9. What are the products of electrolysis of molten and aqueous
sodium chloride?
Ans: Molten NaCl: Na at cathode, Cl, gas at anode.
Aqueous NaCl : H gas at cathode and Cl, gas at the
anode and NaOH in the solution.
10.
What are the products formed during the electrolysis of agueous
solution of sodium chloride?
Ans: Cl2 gas at anode, H, gas at
cathode and NaOH in the solution.
1. During electrolysis of aqueous solution of NaCl, hydrogen gas
is liberated in preference sodius
cathode. Explain with suitable electrode
reactions.
ns:
The SRP value of hydrogen is greater than sodium, So, hydrogen gas
is liberated at cathode. This can bs
explained as follows;
At the cathode there is competition between
the following reduction reactions:
Na" (aq) +e Na (s) E
=-2.71V
H (aq) +e ½ H2 (g) E
=0.00V
At
cathode, the reaction with
cathode duct
higher value ofE' is preferred and, therefore, the reaction at the
electrolysis is:
Chem
ent's illuminator IIPU
<br>

Jeevith Publications 75
H
(aq) +e½H,(aq)
H (aq) isproduced by the dissociation of H;0,
H,O () H (ag) + OH (aq)
Therefore, the net reaction at the cathode may be written as the sum of above cquations and we have
H,O() +e ½ H;(g) +
OH"
aqueous solution of sodium chloride.
12. Explain the anodic reactions during the clectrolysis of
are possible:
Ans: At the anode the following oxidation reactions
NaCl (aq) Na + CI
Eee = 1.36 V
CI (aq) ½ Clh (g) + e
O;
(g) + 4H(aq) 4e;
+
=1.23 V
E

2H,0 () get oxidised in

value of E° is preferred and therefore, water should
The reaction at anode with lower
of over potential of
oxygen, the following reaction is preferred.
However, on account
preference to CI (aq).
½ Cl, (g)+e; E, =1.36 V
CI (aq)
13. What is over voltage? electrode potential required to discharge
an ion is called
excess potential over the standard
Ans: The minimum NaCl.
over potential. during electrolysis of aqueous solution of
cathode [March 2016]
Write the net reactions occur at anode and
14.

NaCl (aq) Na + CI + OH (ag)

Ans: +e 2 H,(g)
Cathode: H,0()
CI (ag) ½ Cl(g) +e
Ci(g)
Anode:
Na (ag) + OH(aq) + ½ H,(g) + ½
Net reaction: NaCI(aq) + H,O() electrolysis of dilute
sulphuric acid.
Write the anodicreaction in the
15. + 4e E=+1.23V concentrations.
Oz(g) + 4H(aq) sulphuric acid in higher
Ans: 2H,O() reaction in the electrolysis of
16. Write the anodic + 2e E,cell, =1.96
V

concentrated sulphuric acid.

(aq)
S,0 electrolysis of dilute and
Ans: 2sO (ag) anode during
the gas liberated at liberated at anode.
17. Name electrolysed, O, is at anode. lt itg ste
is liberated
dilute H,SO, electrolysed, S,0; is acid.
Ans: (a) When sulphuric acid is
and
concentrated sulphuric
concentrated electrolysis of dilute
(b)When cathode during
the gas liberated at
18. Name gas liberated at cathode.
cases H, is following
Ans: In both electrolysis for the electrodes
the products of graphite
19. Predict NaClwith electrodes
aqueous solution of CuSO4 with platinum electrodes
i) aqueous solution of AgNO, with silver
i) aqueous solution ofgas at cathode. at the
cathode.
anode.
ii) anode and H, copper is
deposited electrode to Ag" at
gas at and oxidationof silver
Ans: () Clz ted at anode
 C
deposits
<br>

58./g 1295-6 xg
2 x 96500 C depoists
Ni 6000 C deposits 63-5×1295-6
=0·4263 g
2×96500
$8-7x 6000 1.8248 g Zn + 2e
Zn
2x96500 2F Imole
2x96500 C 65-3g
B and C
8. Three clectrolytic cells A, AgNO, and
containing clectrolytes ZnS04, 2x96500 C
deposits
in 65-3gZ
CuSO, respectively were connccted was
scrics. A steady current of 1.5 A passed 1295-6 C deposits
1.45 g of Ag were
through them until
depositcd at the cathode of cell B. Howlong 65-3×1 295-6
=0-4383g
mass of copper X=
did the current flow? What mass of 2x96500
and zinc were deposited. (Atomic
Cu 63.5, Zn = 65.3, Ag= 108)
=
9. An electric current of 100ampere
(NCERT Exercise) through molten sodium chloride is a
Calculate the volume for5ta
Ans: Ag +le Ag of chlorine
Imole mole
1 Jiberated at the electrode at STP.
1F 108 g Ans: Q=Ix t =100 x 5x 60 x6ir
= 1800000C
Ix96500 C
deposits 108 Ag 96500 C liberates... 11.2L of CI, at S
1800000 liberates
C

QC deposits 1.45 g Ag .....VL of CL

.y l1-2x1800000
96500x 1·45 .:V=. =208-91L
..Q= =1295.6C 96500
108 Volume of CI, liberated at STP = 208.91
Q=It

2.6 Batteries
1. What are batteries Or Commercial cells?
Ans: The electrochemicalcells used to generate electricity are called batteries.
2. Name the types of batteries or commercial cells.
Ans: Batteries or commercial cells are of 2 types.
(i) Primary batteries or primary cells.
(i) Secondary batteries or secondary cells.
Note: (i) A primary battery acts as a galvanic cell.
(i1) A
secondary battery acts as a galvanic cell during discharging and acts as a electrolytic
t5 charging.

Student's illuminator IIPU C

<br>

Jeevith Publications 79
3. What areprimary batteries or primary cclls? Give exaples.
Ans: The batteries whiclh cannot
berecharged and reuscd are called primary batteries.
Examples: (i) Dry ccll (known as Leclanche cell after its discover)
(ii) Mercury cell

4. Explain dry cell or Leclanche cell.

Ans: Dry cell consists of a zinc container which acts as anode and a graphite (carbon)
rod surrounded by
powdered MnO, and carbon acts as cathode. The space between the electrodes is filled by a moist paste
ammonium chloride (NH,CI) andzinc chloride (ZnCl,)which acts as an electrolyte. of
The clectrode reactions indry cell are as shown below:
Anode: Zn(s)Zn² (aq)+2e
Cathode: MnO, + NH, + €"
MnO(OH) + NH,
The overall cell reaction is represented by Zn+2MnO, + 2NH;
a
Zn* +2MnO(OH) + 2NH,
The cell has potential of nearly 1.5 V.
Note: In the reaction at cathode, Mn is reduced from + 4 oxidation state to + 3 oxidation state.
NH, produced in the reaction forms a complex with Zn to give (ZnNH3),12*,
5. Give uses of dry cell.
Ans: (i) It is used in transistors;
(ii) It is used in clocks
(ii) It is used in portable radios,
(iv) It is used in tape recorders.
6. Explain mercury cell. (July 2019)
Ans: Mercury cell consists of zinc -
mercury as a
amalgam which acts anode and paste of HgO and carbon act as
the cathode. The electrolyte is a paste of KOH and Zn0. The electrode reactions for the cell are given below.

Anode: Zn(Hg) + 20H ZnO(s) + H,0+ 2e

Cathode: HgO + H,0 + 2e Hg()+ 20H
The overall reaction is represented by
Zn(Hg) + HgO(s) ZnO(s)+ Hg()
as the overall reaction does
The cell potential is approximately 1.35 V and remains constant during its life
notinvolve any ion in solution whose concentration can change during its life time.

7. Give uses of mercury cell.

portable radios, toys,
Ans: It is suitable for low and stable electricity devices like hearing aids, watches,
flashlights.
What are secondary cells or secondary batteries? [March 2014, July 2016, March 2020]
or
cells which can be recharged by passing current in opposite direction are called secondary cells
Ans: The
rechargeable cells are called secondary cells.
or Lead - H,SO, battery.
Example: (i) Lead storage battery or Lead-acid battery
-
(ii) Nickel cadmium cell.
A secondary cell can undergo large number of
discharging and charging cycles.
- 1July 20l6, March 2019]
Explain lead storage battery or Lead-acid battery. a packed with lead dioxide (PbO;) as
of lead as anode and grid of lead
Ans: It is a secondary cell. It consists
(H,SO4) as electrolyte.
cathode. A 38% aqueous solution of sulphuric acid
I PUChemistry
<br>

Elect
arc [discharging]
battery is in usc
The ccll reactions when
Anode: Pb(s)+SO (nq)
PbSO,(s) + 2e*
+ 4H“ (aq) + 2e PbSO, (s) + 2H,O)
Cathode: PbO, (s) +SO (aq)
+ PbO, (s) +2H,S0, (aq) >2PbSO, (s) +
The overall cell reaction is, Pb(s) 2H,0(0)
On charging the battery the reaction isreversed. Chemical reaction occurs during
recharging
+ PbO, (s) + 2H,SO, (aq)
2PbSO,(s) +
2H,0)- Pb(s) is

9. Give the uses oflead- storage battery.

Ans: () It is used in automobiles (i) It is used in invertors.
(ii)It is used in trains (iv) It used in emergency
power supplies
10. Explain Nickel-cadmium cell. (ups)
Ans: Nickel-cadmium cell consists of solid cadmium as
anode and
is oxidized and Ni(0H),Ni(OH);(s) as cathode.
KOH(aq). During operation, cadmium
is reduced. .Theelectrolytei
Oxidation (anode): Cd (s) + 20H (aq)
Reduction (cathode): CdO(s) +H,0(0)
2 Ni(OH), (s) + + 2e
Overall reaction cell: 2e
Ca(s) + 2 Ni(OH),(s) 2 Ni(OH), (S) +
The overall reaction 2 Ni(OH),(s)+
20H (aq)
produces about 1.30
V. Cdo (s) + Ho
2,7 Fuel Cells
1. What are fuel
cells? Give example.
Ans: The cells
prouce electrical energy
(CH,OH), etc., are by
called fuel cells. the combustion of fuels like
Example: Hydrogen- hydrogen (H,),
methane (CH) mA
oxygen
Note: (i) In fuel cell.
the fuel cells,
the reactants are
(ii) Fuel cells are continuously
used in space supplied to the
electrodes to generate
(iii) In rockets crafts (rockets) electricit.
liquid H, and
2, Explain hydrogen- liquid O, is used
oxygen as propellant.
fuel cell (H,
Ans: In March 2017, July -0, fuel cell).
H-0, fuel cell electrical energy 2017, March
2018, July 2018]
Construction: produced by the
combustion of hydrogen
through a pairsIn
this cell hydrogen as a fuel.
carbon electrode and oxygen are bubbled
KOH (aq)..
Catalyst like finely into conc. NaOH
are incorporated divided platinum (aq) or conc. H,0
or Anode tCathode
to the electrodes palladium metal
reactions. Hydrogen for increasing rate Aqued
Oxidised and oxygen
is passed into anode compartmentof electrode clecto'
is passed into where
it is reduced. the cathode compartment it is
where H,
The electrode
reactions are as
shown below.
Anode: 2H,(g) + 40H
(aq)4H,0() +4e
Cathode:
0,(g)+ 2H,0()
+4e 40H(aq)
tudent's illuminator PUChe
<br>

The overall cell reaction is 2H,(g) +O,(g)2H,0(1)

The cell runs continuously as long as the rcactants are supplicd.

Fuel cells produce electricity with an efficiency of about 709% compared to the thermal plants whose
efficiency is about 40%.
3. How does concentration of sulphuric acid change in lead storage battery when current is drawn from
it?
Ans: Concentration of sulphuric acid decreases.
4. Name the cellwhich is used in Apollo space programme.
-
Ans: Hydrogen oxygen fuel cell.

2.8 Corrosion
5. What is corrosion? Give an example.
or
Ans: The process of deterioration of a metal as a result of its reaction with air water in its surroundings is called

corrosion. Example: Rusting of iron.

5. What is rust? Give its formula.
Ans: Hydrated ferric oxide is called rust. The chemical composition of rust is Fe,O3.xH,0
or Explain the
7. Explain corrosion of metals or explain corrosion is an electrochemical phenomenon.
mechanism of rusting of iron. [July 2016]
Ans: Corrosion takes place by the transfer of electrons. So it is called electrochemical
phenomenon.
oxygen present in the air to
Example: when iron is exposed to moist air, it reacts with moisture, CO,, and
form rust.
Mechanism of corrosion:
or can be explained in terms of electrochemical theory which involves
The mechanism of rusting corrosion
Oxidation and reduction reactions:
undergoes oxidation and acts as anode. Released
When iron object is exposed to atmospheric air, iron
on the metal and reduce oxygen in the presence of H which
electrons move from anodic spot to another spot
acts as cathodic spot.
At anode: 2Fe(s)2Fe (aq) + 4e
Atcathode: 4H°(aq) +0,(g) +4e 2H,O(0)

The overall cell reaction is 2Fe+O, +4H12Fe +2H,0.

come out as rust in the form
The ferrous ions are further
oxidised.by'átmospheric oxygen to ferric ions which
of hydrated ferric oxide (Fez03 xH,0) and with
further production of hydrogen ions.

Fe,O,(s) + 4H“ (aq)

2Fe* (aq) +-0,+2H,0()
2
Fe,0, + xH,0 Fe,0, rustxH,0
Explain the methods used to prevent corrosion? coating
In this method, a barrier is placed between iron and atmospheric air by
Ans: (1) Barrier protection:
oil or grease or electroplating.
the surface with paint or by applying more active metal
In this method, iron is protected by covering with a layer of
(ii) Sacrificial protection:
like zinc, tin etc.
is called galvanization.
The covering of iron with zinc
are called galvanised iron pipes (G.I. pipes)
Zinccoated iron pipes connected with more active metal like
magnesium.
(111) Electrical protection: In this method, the iron is
II PUChemistry
Student's Illuminator
<br>

Electrocha
82
Jeevith
chromat
(iv) Using antirust solution: Antinust solution likebisphenol, alkaline phosphates, alkalne Fil
uscd to rctard the corrosion of iron.
9. Name any two methods to prevent corrosion.
Ans: (i) Painting
(ii) Galvanizing (coating iron with zinc)
(iii) Applying oil or grease 1.
(iv) Electroplating
to nrevent rusting of iron
10. Name onemetal which can be used as sacrificial electrode
Ans: Mg or Zn. Ans:
Multiple Choice Questions 2.
during dischara
The overall reaction
1. The anodic reaction occurs during the 6.
Nickel-cadmium battery is
working of Laclanche cell (dry cell) is Ans:
a) Zn, Zn* +2e a)
+ 2Ni(OH)3(9) CdO +2Ni(OH)
Cd,
b) MnO, + NH, +e MnO(OH) +
NH,
b) Cd²* +2e
Cd-
c) Zn(Hg) + 20H ZnO+H,0+2e Ni
c) Ni +2e
Hg,n +20H Cd²* + Ni
+
d) HgO H,0+2e d) Cd+ Ni*
drycell, formed ammonia forms a complex Which one of the following is a secnni 1.
2. In 7
with Zn to give battery
a) [Zn(NH,). b) [Zn(NH,).I a) Dry cell b) Mercury cell Ans:
c) Leclanche cell d) Lead storage cell 2.
c) [Zn(NH,)," ) [Zn(NH,). When lead storage cell is in use
8.
3. Anodic reaction occurs in mercury cell is a) At anode, Pb is converted into Pbso, Ans:
+
a) Zn(Hg) + 20HZnO,+H,0 2e b) Atcathode, Pb is converted into PbS0, 3.
b) HgO + H,0+ 2e Hgn + 20H" c) At anode, PbO, is converted into PbSO,
d) At anode, Pb is converted to PbO;
-
+
2e
c) ZnZn
+Hgo 9. In H, 0, fuel cell H, and O: gas
d) Zn(Hg) + HgO(s) ZnO
passed into the electrolyte of
4. The reducing agent and oxidizing agent used a) Aq NaOH b)Molten NaOH
in mercury cell are
1.
c) Aq NaCl d) Molten NaCl
a) Znand Hg b) Zn and HgClh
10. During rusting of iron anode reaction
c) Zn and HgO d) Zn and Hg,0 An
The electrolytic solution used in lead storage place is 2.
5.
battery is a) Fe+2
aq +2e Fes) An
a) 38% sulphuric acid +4e 3.
b) 20% sulphuric acid
b) 2Fes) 2Fe)
c) PbSO, c) O, +4H* +4e2H,0 An
d) PbO;
d) 2H,00,
+
4H* +4e

Answer Keys 1.

123
1
4
56 789
7 10
<br>

UNIT
ChemicalKinetics 3
1, What is chemical kinetics?
Ans: The study of reaction rates, the conditions by which the reaction rates can be altered and mechanism of
reaction is called chemical kinetics.

3.1 Rate of a Chemical Reaction

2. What is rate or velocity of a reaction?
Ans: Decrease in concentration of reactants in unit time is called rate of a reaction.
= A[R]
i.e., Rate or
At
Increase in concentration of products in unit time is called rate of a reaction.
A[P]
ie.. Rate =+
At
So, change in molar concentration of the reactants or products in unit time is called rate of a reaction.
de
and- sign in rate =t dt
+
3. Explain the significance of

Ans: The positive sign indicates the concentration of the product increases with time.
The negative sign indicates the concentration of reactant decreases with time.
4. What is average rate?
Ans: The rate of a reaction is measured over a long interval of time is called average rate of a reaction.
5 How do you calculate the average rate of rèaction with respect reactants and products? Explain b;

taking graphical representation.

(a) Caleulation of average rate of reaction with respect to reactants.
Consider a reaction, R P
where R is the reactant and P is the product. During the
reaction, concentration of reactant decreases with time.
reactants
[R],< [RJ,

Let R]i and [R, be the concentrations of the reactant R at time

t and t, respectively. of Concentration
ARJ
[R]2-[Rl
Rate of disappearance of R= t2 -ti [R],

Rate ...(1)
At At

The negative sign indicates the decrease in the concentration of t t

reactant with tme. Time
<br>

96
Chemie

(b) Calculation of average rate of reaction with respect to products: During

the reaçc
concentration of product increases with time.

products (P,> P],

[P].
of
Concentration
AP]
[P],

At

Time
Let [P] and [P]; be the concentrations of the product P at time t and t; respectively.
Rate of appearance of
[P})-[P]
P= t2ti

Rate ...(2)
At
The positive sign indicates the increases in the concentration of product with time.
6. What
is instantaneous rate?
Ans: The rate of a reaction measüred at any instant of time or a reactants

very small interval of time is called instantaneous rate.

Rate at the instant
Calculation of instantaneous rate of reaction: The is equal to the slope
instantaneous rate of a reaction is determined graphically of of the tangent drawn t=

by measuring the slope of the tangent drawn at a point

dRI)P
concentration

curve at the point P=

that corresponds to the given instant of time to the curve
idt
of concentration of reactant versus time as shown in the
figure:
Average rate = Instantaneous rate as At approaches zero. t time
Instantaneous Rate = d[R] d[P]
dt dt
7. What is the unit of concentration used in chemical kinetics?
Ans: mol L.
8. What is the unit of rate or velocity of a reaction?
Ans: mol L s [In case of gaseous phase reactions
unit of rate is atm.s]
Numerical Problems
1. The decomposition of N,0; in CCl, at 318 K
has been studied by monitoring the Calculate the average rate of this reac
concentration of NOs in the solution. terms of hours, minutes and seconds
Initially the concentration of N,Os is 2.33 s the rate of production of NO, durpro
mol L and after 184 minutes, it is reduced period? (NCERT Solved
to 2.08 mol L. The reaction takes place Ans: Average Rate
according to the equation
|(2-08-2.3)m
2N,0,(g)4N0,(g)+0,(g) 184 min

=6-79x10 mol
L'/ min
<br>

Jeevith Publications
97
= (6-79x10 mol
L'min') (60 min/ lh) x
(i) aA + bB cC + dD
=4-07x 10*mol L'/h
(ii) H; (g) + I; (g) 2HI (g)
=6-79x10 molL'xl min/ 60s
=1·13x10mol L's-! (iii) 5Br (aq) + Br0; (aq) + 6H*
3Br:(aq) + 3H,0)
=NOl
Rate
Ans:
A(NO,] (i) Rate =
=6-79x10x4mol L' min-!
At 1
A[A]1 A(B] 1 A[C]_
=+
1 A[D]
c
=2-72>x10mol L'minl a At b At At d At

(ii) = A(H,] 1 A[HI]

For the reaction R P, the Rate
At At At
concentration of a reactant changes from
0.03 M to 0.02 M in 25 minutes. Calculate (ii) Rate
the average rate of reaction using units of 1 A(Br ] A(BrO,] 1 A[H°]
time both in minutes and seconds. At At 6 At.
(NCERT Intext Question) 1 A[Br,] 1 A[H,0]
=+ 3
A[R] At3 At
Ans: Average rate of reaction
At Note: In case of gaseous reactions, the rate can be
[R],-[RI 0-02-0-03 expressed in terms of partial pressures of reactants
t, -t, 25
M min-! and products (since partial pressures are proportional
to the concentrations).
For example, N, +3H, 2NH
M min=4x10 M min-! 1APH 1 APNH,
APN
Rate = 3
At At
2 At
4x104 = 6.667 x Ms 5. Hydrogen gas has a nonpolluting
=
-Ms 10 combustion product (water vapour). It is
60
used as a fuel abord the space shuttle and in
In a reaction 2A products, the
earthbound cars with prototype engines:
concentration of decreases from 0.5 mol
A
2H2(g) + O:(g) 2H,O (g)
L' to 0.4 mol L in 10 minutes. Calculate
the rate during this interval? (a) Express the rate in terms of changes in
July 20I] (NCERT Intext Question) H,], (O,21, and [H,O] with time.
1A[A]
(b) When [O,] is decreasing at 0.23 mol
L
ns: Average rate
2 At
s', at what rate is [H,0] increasing?
I A[H,]_A(O,]_ 1 A(H,O]
Ans: (a) Rate =
2 At At 2At
-- -0-1 =0-005 mol L-l min-!
10 1 A[H,0]_ AO,]
(b)
=5x10 M min-! 2 At At

Express the rate for the following reactions At At

reactants and
in terms of concentrations of =2[-(-0-23 mol L's))=0.46 mol L's!
products
<br>

98 Che

3.2 Factors Influencing Rate of Reaction

the factors affecting the rate of reaction. or On which factors does the rate
a
1. Name
depends? [July 2019, March 2020, o
Ans: () Nature of the reactants (ii) Temperature
(iii) Concentration of the reactants (iv) Catalyst
(v) Presence of light photochemical reactions.
2. What is rate law or rate exprcssion?
Ans: Consider a reaction aA +
bBcC+dD
Rate a [AJ[b]'
a
where exponents X and y may or may not be equal to the stoichiometric coefficients and b.
Rate =k [AJb]" where k is called rate constant.
The equation which relates the rate of reaction to concentration of reactants is named as rate lawe
expression.
Thus, "the rate law is the expression in which reaction rate is given in terms of molar concens.
reactants with each term raised to some power, which may or may not be same as the stoiek:
coefficient of the reacting species in a balanced chemical equation".
d[R]
dt
This form of equation is known as differential rate equation.
3. Define rate constant or velocity constant or specific reaction rate.
Ans: Rate constant of reaction is equal to the rate of a reaction when the molar concentration of exch
reactant is taken as unity.
Example: Consider a reaction, A+B Products
Reactants
According to Law of mass action
Rate oc [AJ[B] or Rate = k[A][B]
wherek=rate constant or velocity constant
When [A]= [B]= 1 then
=
Rate k () (1) or Rate =k
4. a
Define molecularity of reaction. [March 2014]
Ans: The number of reactant molecules taking part in an elementary reaction, which must collide simultan
in order to bring about a chemical reaction is called molecularity
ofa reaction.
Example:
(1) NH,NO, N, +2H,0
Reactants
Molecularity = 1 or unimolecular reaction.
(ii) 2HI H, +1,
Reactants
Molecularity = 2 or bimolecular reaction.
(iii) 2NO +O, 2NO,
Reactants
=3 or termolecular
=
Molecularity (2+ 1) reaction
Note: Molecularity is more than 3 is not possible. Termolecular reactions are very rare.
5. What is an elementary reaction?
Ans: The reactions taking place in one step are called elementary reactions.
Student's illuminator IIPU Che
<br>

eevith Publications 99
What is a complex renction?
ns: The reactiontaking place in more than onc step
is called complex rcaction.
Define order of a renction.
Ans: It is the sunm of thepOwers of the concentration terms
of reactants appcarcd in the experimentally determined
rate cquation for the reaction.
For a reaction, xA + yB products. Rate= k[A][B]"
. order m.
=|+ where land m are determined experimentally.
. What the slovest step in a complex reaction also called?
is
Ans: Rate determining step
). Which step of reaction mechanism decides the order of reaction?
Ans: Slowest step
10. For what type of renctions is nmolecularity and order the same?
Ans: Order and molecularity are same in slowest step of complex reactions.
11. What is zero order reaction? Give an example. (July 2014, July 2020)
Ans: The rate of the reaction is independent of concentration of the reactant is called zero order reaction.
Example: (i) Decomposition of ammonia (NH,) on the hot surface of platinum (Pt) or molybdenum (Mo) at
high pressure.
2NH,(g) Pt catalyst N, (g) + 3H,(e)
Rate c[NH,1°
1130K
order =0. .
Example: (ii) Thermal decomposition of bydrogen iodide (HI) on the surface of gold (Au)
Au
2HI(g) H,(g) + I, (g)
Rate c [HI Order =)
on the surface of water.
Example: (iii)Photo chemical combination of hydrogen (H) and chlorine (Cl)
H,(g) + Cl, (g). sunlight (hv) 2HC1(g)
water surface

Rate [H,][CI,1' Order =0

12. What is first order reaction? Give an example.
power of the concentration of the reactant is called first
Ans: The rate of the reaction is proportional to the first
order reaction.
Rate oc [R]'
.. 1.
order=
Example: (i) Radio active decay
88Ra
226 Rn222 He
=
86
order=1 ..
Rate c [Ra] or Rate k[Ra]
(nitrogen pentoxide)
Example: (ii) Decomposition of N,0,

2N,0,4NO, +0,
Rate c (N,0,] order = 1

hydrogen peroxide (H,0,)

Example: (ii) Decomposition of
2H,0, 2H,0 +O,
.. order=1,
Rate c [H,0,]
I| PUChemistr
<br>

Ans: Rate =
102
affected on
increasing k [acctaldehyde Cherri
is the rate times?
ii) Howconcentration of Y thrce constant. [From units
the rate of rate
the SI unit for the order = 21 constant
i) Wrte
Ans: (i) Rate k[X][Y} Rate
times =(6-73x10M
k/X]x = 9k[X]=9
(i1) Rate
3

(Thírd order unit)

Rate = 2-06x10 sy-75x
(iüi) molL's' 17. Ms!
In which of the order the unit of rate Identify
15
constant is mol'L's-? followingthe reaction order
(concentration)-n
rateconstants. from
Unit of
.
k=
(i) k=2.3 ×
Ans: time 10-5L mol-1
(ii) k=3 × s1
(mol L'y-n Ans: 104 s-1
S
July
when n = 2, (i) The unit
k= mol!Ls-! of second
.:Order of reaction =+ 2, L mol-l order rate cor
s, therefore
represents k = 23
16. What is the rate
of the mol-! s
lacetaldehyde] = 1.75 reaction when the reaction. a second
*
constant is 6.73 x 10-6 10 M and the rate (ii)
M-1-l9 The unit
of a first order
s-,therefore rate con
3.3 Integrated a first order k=3 x 104 sl er
1. Derive an Rate Equations
expression
reaction.

rate constant or for integrated

velocity constant rate equation
[July 2015, of a zero for a zero
Ans: Consider a zero March 2016. order reaction. order reaction or Derive an express
order reaction July 2016, March
2017, July
2018, July
2020, April 2020
Zero order reaction
RP
is one in which
According to rate rate is proportional
law for zero order to zeroth power
reaction, Rate a of reactant concentration.
Rate = k[R] R]0
But R] =1
Rate k
Where kis rate constant .(1)
or velocity
constant for a zero order reaction.
But, Rate _[R]
dt
-d[R]
=k:
dt ..(2)
Rearranging the equation
(2), we get
d[R]=-kdt ..(3)
Integrate equation (3)

Where I is called integration constant.

[R]=-kt+I...(4)
Student's illuminator
II PUCher
<br>

Jeevith Publications 103

To get l, put t 0, (R] =
[R], the initial conccntration of the reactant.
[R), =-k x 0+I
I=[R],
Substitute Ivaluc in cquation (4), wc get
(R]= -kt + [R],
kt=[R],-[R]
[RJ, -[R
k=
t
This is the expression of rate constant of zero order reaction.
-[R],

[R]
Note: Slope =-*
On rearranging, [R]=-kt [R], +

Thisequation is in y=mx+c form and suggests that,

A plot [R]versus t gives a straight line with a slope =-k
of
Time
and y - intercept = [R],
2. For a reaction, the graph of rate of the reaction against molar concentration of the reactant is as
shown. What is the order of the reaction?

Rate

Concentration

Ans: Zero order reaction

of a reaction.
3. Define half-life period of a reaction or time for half change
a reactant is reduced to half of its initial concentration is called
Ans: The time during which the concentration of
half life period of a reaction. or.
denoted by
is called half life period. The- half life period is
The time taken to complete the reaction by 50%

a zero order reaction or Show that for a

zero order reaction
Derive an expression of half life period of reactants.
4. to the initial concentration of the
half life period is directly proportional
(RI, -[R] ...(1)
of zero order reaction is, k=
Ans: We know that the rate constant t
= =
concentration at any time, t time.
constant, [R], = initial concentration, [R]
where, k= rate
when t= t,, then R]=Ko
2
we get
Substitute these values in equation (1),
[R].
[R].
k= 2
_
2[R], -[R]. (RJ.
k= 2ty2
2ty2 IL PUChemistr
ont's illuminat
<br>

of
a zero order reactions becausc 2k is
constant
This shows t, [R, for
the time taken to rcduce the concentration
a zero order reaction, of reactant
5. In to reduce the concentration
40 minntes. What is the time rcquircd of reactant from10%
from
t,, [RI,
2
Ans: In zero orde reaction,
20 min 10 min
.100%
40 min
>50% > 25% >12-5%
Henes time required to reduce the concentration from 25% to 12.5% is 10
min
By how many times does the t, of zero order reaction increase
6.
2 if the initial concentr
reactant is doubled.
Ans: Two times
7. Derive integrated rate cquation for a first
or velocity constant of a first order reaction.order reaction or Derive an expression
[March 2015, July 2017, forthe r:
March 2018, March 2019,
Ans: Consider a first order reaction, .July 2019. Mov.

RP
A first order reaction
is one in which the rate
concentration. is directly proportional to
first power of ,
Therefore, according to rate
law,
Rate a [R]'
Rate k{R]
Wherekis rate constant or velocity constant ..(1)

But, Rate = d[R]

dt
d[R] -k[R]
d ..(2)
Rearrange the equation
(2), we get
d[R]
=-kdt
R] rl .3)
Integrate equation (3)
1

JRR)=-*fdt
In[R]= -kt +I
Where I is called integration constant ...(4)
When t=0, [R]=[R], where [R], is the initial concentration
of reactant R.
In[R], =-kx0+I
I=In[R].
Substituting the value of I in cquation
(4) we get,

Student's illuminator | PU
<br>

Jeevith Publications 105

In[R]= -t +
In[R]. ...(5)
kt In (R], - In[R]
R],
kt In
[R]
kt =2.303 log0 [RI,
[R]
2-303 [RJ,|
J0g10
t [R]
expression for the rate constant of a first order reaction.
This is the
Note: To create another form of rate law, rearrange equation (5) to get,
In[R]-ln[R], =-kt
[R]
In -=-kt
[RJ,
[R]= [R], e Intercept =n[RJ,
Equation (5) In[R]=-kt + ln[R], is in the form of y = mx +c
This suggests that a plot of ln [R] versus t' gives straight line with In [R]
Slope =-k
=
negative slope (-k) and y intercept In[RJo
positive]
[Note that the slope is negative but that the rate constant is always
The first order equation
[March 2017] Time

[RJ, k
-xt
logo 2-303
[R]

(R1. versus time gives the following graph with

The plot of log,o
[R]
Slope =
2-303
a slope of
2-303
Time
concentration of the
a order reaction, half life period isindependent of initial
8. Show that for first
reactants. OR
reaction.
life period of first order
a

Derive an expression for the half [March 2014, July 2014)

Ans: We know that

[R]o ...(1)
2-303
k= log0
t [R] concentration, [R]= concentration at any timne.
[R]o = initial
Where k= rate constant, t = time
(RJD
When t=ty2 then [R]= 2
(1l), we get
Substitute these values in equation
II PÜChemistry

Student's illuminator
<br>

2-303 RI

2-30 1o 2

0-693
2-303,0. 3010 =
0-6931

shows, the life

period ofa first order reaction
The above relation isindependent of initial concentratic
happens to half life time
of a first order reaction when temperature
What is increased?
9. Give re
temperature increase. Because
Ans: t, decreases as
kcT and
2
What happens to the half life period for a first
10.
reactants is increased?
order reaction, if the
initial concentratio
Ans: No change or remains constant. [March 2015]
le e frst order
11. reaction, the time
40 minutes. What is taken to
the time required to reduce the concentration of reactant
Ane Since,
in a first, order reduce the concentration from 1009% to
reaction,
tn 1S lndependent
on the initial of reactant from 25% to 12.5
the concentration concentration of reactant,
from 25% to 12.5%
is also 40 minutes. time taken t
12. Derive
integrated rate
equation for first
Ans: For the given gas order gas phase reaction,
phase reaction A(g)B(g)+C(g)
A(g)B(g) +C(g)
Att=0 P

At time t,
Where x' is
P; X -x X
the decrease in pressure
is the initial pressure of reactant A at time
After timet,
a
at
timet=0. t and increase in pressure
total pressure p, (P; of products B ar
-x) + x+ x
P, =P,+x

But at a time t, X=P,-Pi

PA =P,-x
PA
=P,-(P, -P)
PA
=P-P, +P,
PA=2p, -P,
In gas phase reactions,
pressures gaseous first order rate
of reactants as equation can
be written by
follows: replacing concentration
k=303 log P te
t PA
k 2-303-log Pi
2p,
dent's illuminator
-P
<br>

Publications
leevith
relation between half-life 107
Givethe
period and
13. order of a reaction.
Ans: [RJ
Half-lifc period,
where ti= [R],= initial concentration, n =
order of a rcaction.
Note:
For zero order reaction (n=0) ty2 c [Rlo
For first order reaction (n=1) ty, al So, tin is independent on
the initial concentration of reactant.
second order reaction
For
(n=2)= ty2
[RJ,
For third order reaction (n 1

=3)ty2 c or and so on.

[RJ'
What is pseudo first order reaction?
14. Give an
example. [March 2014, March 2019, July 2019)
Ans: The reactions in which higher order reactions can
be converted into first order by changing
conditions are regarded as pseudo first order reactions. the experimental
Example: (i) Acid hydrolysis of methyl acetate.
CH,COOCH, + H,0
or
dil- HCI

Methyl acetate H+ CH,COOH+ CH,OH

acetic acid Methyl alcohol
Order = 1 since Rate oc [CH,COOCH,]'

Inthis reaction water is taken as large excess and hence rate is independent on the concentration of water. So
rate depends only on the molar concentration of methyl acetate which is directly proportional to firstpower
of concentration of methyl acetate. Hence it is a pseudo first order reaction.
Example: (ii) Inversion of sucrose or cane sugar

C,H,,O H:
+ H,0C,H,0,+CH,,0,
sucrose (cane sugar) glu cose fructose

Rate oc [C2H,,O,,] Order = 1: (H,0]

=
constant

15. Mention any one condition under which a second order reaction of rate law: rate kA] |B]' can be

made å pseudo first order reaction.

Ans: By taking any one of the reactants (A or B) in excess.

Multiple Choice Questions (MCQs)

a
3. In reaction Hg, + Cle) HgCl9) the
l. Rate of reaction is defined as rate of disappearance of Hg is equal to
a) Increase in concentration of reactants with a) rate of disappearance of CI,
time rate of appearance of HgCl;
b)
0) Decrease in concentration of reactants with c) rate of appearance of Cl,
time d) both (a) and (b)
products with
) Decrease in concentration of In a
reaction,
time 4.
reactants or
SBr(a1) + BrOsaq) + 6Hag) 3Brz(aq) + 3H,Oe
in concentration of
d) Decrease
increase in concentration products with time the rate of consumption of Br0j is
2.
The unit of
rate of reaction is expressed in 2x10-3 mol L's. The rate. of formation of
a) mol
b) molL's-!
mo' Ls! Br, is
d)
I| PUChemistry
<br>

2-303, 0-55 half reduction

k, = 30 log 0-31
-=|·9||x10s!
100% 10 min 50% 10 min
25%
For t= 60 sec, 10min, 12.5 10 min
6.25
10.min
3.125
2·303, 0:351.957x10s
60
log
0-17
.:.After 50 min, 3.125 % is unreacted.
The rcaction SO,Cl;(g) SO:(g) +
sec, 18.
For t90 a rate constant of
Clh(g) is first order with
6,=303 log 0-5S =2-075x10s! 2.90 x 10 s at a given set
of conditions.
90 0-085
Find the (SO,CI,] at 865s when
Then, average rate constant, [S0;Cl;linitial 0.0225 M.
logR,
2·303
3
Ans: t-
t=
[RJ
[so,CI,J,
(1-911x
x
10)+(1·9571x 10)+(2-075 10-²) t303 -log
[So,CI,]
3
[So,CI, ], kt
k=1·98x10s-! log
[SO,CI,] 2-303
16. 70% of a first order reaction is completed in log
0-0225 2-9x10×865
23 min. Calculate the rate constant of the [So,Ci,] 2-303
reaction. [July 2016]
0-0225 =0-10892
2-303 [R], log
Ans: k= lo10 (So,CI,]
t [R]
0-0225 = Antilog [0-1089]
2-303 -log10 100 [SO,C1,]
k=
23 30 0-0225
=1-285
(: [R]=100-70 =30%) [SO,CI,]

k=
2-303.
-log,, 3-333 [SO,Ci,]= 0-0225 = 0.01751 M
23 1·285
2-303
19. Time required to decompose SO,Cl, to half
k= -x0-5228 of its initial. amount in 55 minutes. If the
23 decomposition is a first order reaction,
k=0-05235 min calculate the rate constant of the reaction.
(NCERT Intext Problem)
17. t,, of a reaction is 10 minutes, for a first
0.693 0.693 =0.0126
order reaction. What percent of the reactant Ans: k= min!
t2 55
remains unreacted at the end of 50 minutes?

3.4 Temperature Dependence of the Rate of Reaction

1. What is the effect of temperature on the rate of a reaction?
Ans: The rate of a reaction generally increases with increase in temperature due to the increase in number of

activated molecules.
Note: In general, for most of the chemical reactions, rate of reaction doubles for every 10° rise in temperature.
2. Define temperature co-efficient ofa reaction.
Ans: Temperature co-eficient KT0 2 or 3
k,

Student's illuminator I| PU Chemistry

<br>

114 a Chen
of ratc constant
of
reaction
defincd as thc ratio at particula:.
Temperature co-cficient ofa rcaction is tempcrature.
lower
to the rate constant atten degrec (10°) many times the rate of
reaction
a rcaction is 2. How
3 The temperature cocfficicnt of is iner
temperature is increascd from 30OK to 35OK?
Change in temperature
Ans: Rcaction rate = (T.C) 10

30
Reaction rate = (2)1o =
=32 times 2

as to what the symbols stand for?

(March 2017,
4. wteArrhenius equation. State Julyh
Ans: k=Ae RT

Where, k= Rate constant. A= Freauency factor or Arrhenius constant,

exponential, E, = energy of activation,
R=Universal gas constant (R= 8.314 JK mol),
T=Absolute temperature.
5. In the Arrhenius equation k = AeE, 'RT. What does e* represent?
E
Ans: e represents the fraction of molecules having energy equal to or greater
R
than E,.
6. x 10!" e28000rT
Ihe decomposition ofa hydrocarbon follows the equation: k= 4.5
Calculate E,. Given R=8.314 J
Kmol.
Ans: k=A-e-E,/RT

Given k=4.5x10!'e28000T
-ii)
On comparing two equations

=28000J
R
.". E, = 28000× 8.314 = 232792 J
=232.79 kJ molrl
7. Explain Arrhenius theory
of activated complex by
using potential energy
level diagram.
Ans: According to Arrhenius,
the reaction can take place [March 2016, March
activated complex. It exists only when reactant molecules
for a very short time and collide to ti
r example, formation HI the breaks up to form products.
of from H, and I, is as follows.
H Activated
H...|
HI cOmplex
+Thresbold
energy
H cne
H*1 H-1 Poteaital
Actvation
Reactants Intermediate Products
complex Most probable
(Activated complex) egy of reactants

2:1T
8. What is energy of activation or activation energy?
Ans: The minimum excess energy coordinate Rection
acquired by the reactants
energy of activation. It is denoted by E,. upon
collision to conmp

form activated
<br>

Jeevith Publications 115

Oxygen is available in air, yet fuels donot burn
9. spontancously at room temperature. Why*
Ans: The activation energy lor combustion reactions
not burn by themselves,
of fucls is very high at room temperature. Theretore, they co
10. What is threshold energy?
Ans: The minimum energy that the reacting
molecules should possess in order to form products upon
called threshold energy. It is denoted collision i5
by Eh:
Threshold energy =Average kinctic energy
possessed by reactants + Activation energy.
11. Using energy distribution curve showing temperature dependence of the rate
the effect of temperature on the rate of of the reaction, explain
reaction.
(July 2016]
Ans: The peak of the curve corresponds to
the most probable
kinetic energy. When the temperature is
raised, the
maxima of the curve moves to the energy
higher side T+0
and broadens out such that there is greater
proportion of
molecules with much higher energies.
Increasing the
temperature of the substance increases
the fraction of B'
molecules which collide with energies greater B
than E.
It is clear from the diagram
that in the area AA'BB' at E,
(T + 10), showing the fraction Energy
of molecules having
energy equal or greater than
activation energy gets doubled leading to doubling
the rate of reaction. In
Arrhenius equation, the factor e E RT
corresponds to the fraction of molecules that have kinetic energy
than E. greater

ote: x: E=eE,'RT where N = number of molecules with energy E and

N, N,= Total number of molecules.
Ng-= Fraction
N
of molecules.

What is most probable kinetic enmergy?

s: The kinetic energy
of maximum fraction of molecules is called most probable kinetic energy.
What are activated molecules?
s: The molecules
which have sufficient energy to form products upon
collision are called activated molecules.
What are effective collisions?
: The collisions between activated molecules are called effective collisions.
Give the relation between threshold energy
and energy of activation.
: E,= Eth-Eaverage. i.e., Energy of activation =
threshold energy - average energy of reactants.
where, E,= Energy of activation,
Eh = Threshold energy,
Average energy or normal energy.
Eaverage

How doyou calculate activation energy

from Arrhenius equation by Graphical
:We know that method
<br>

116
Chemic

Ink = In A -- Aog A

nlope
log,, k = log A log k
2-303R
The plot of log & vs 1/T gives straight
line with a slope = -E,
2-303 R
By calculating the slope from the graph, encrgy
activation can be calculated by E, = -2-303xR.
of
17. The graph of log k vs. 1/T for a reaction is
linear with intercept of 10 and slope of - 5.1x 10.c.
the frequency factor and E, of the reaction.
R=8.314 JK mor.
Ans: (a) Slope E,
2.303R
-$.1x10 =
E

2.303 x 8.314
E, =2.303 × 8.314x5.1x 10
97650 J =97.65 kJ mol
(b) Intercept = log A
10=logA
A= Antilog(10)
A=100
18. Calculation of energy of activation
from Arrhenius equation at two
Ans: We know that different temperatures.
RT
k=Ae
By taking log on both sides

In k = In

At two different temperatures,

At temperature Ti, In k, = In A -
-..(1)
At temperature T2,
In k, = In A -
...(2)
(2)- (1) gives In = In A -
k- In k,

In

logk2 E.
ki 2.303R
Using this equation,
we can
solve for
E.
nt's illuminator
<br>

Jeevith Publications 117

.0 Eplain the cffect of catalyst on the rate ofa reaction.
Ans: A July 2018J
catalyst incrcases the ratc of a reaction by decreasing energy activation
of (E). Acatalyst provides a rew
rcaction path for the reaction. Because a catalyst forms an unstable
intermediate with the reactants and
decomposcs to give products and the catalyst is
regencratcd.
t
Reaction path
Reaction without catalyst
path with
catalyst Energy of
activation
Energy of without
actívation catalyst
with
Keactants katalyst

Products

Reaction coordinate

20. What is the effect of catalyst on Gibbs energy (AG) of a reaction?

Ans: The catalyst does not alter the Gibbs energy of reaction.
21. Among spontaneous and non spontaneous reaction, which one is affected by catalyst?
Ans: Catalyst catalyses only spontaneous reaction. Catalyst does not catalyses non spontaneous reactions.

22. What is the effect of catalyst on the equilibrium state and equilibrium constant in a reversibie
reaction?
Ans: Catalyst does not change the equilibrium constant and does not disturb the position of equilibrium. helps
It in
reactions to the same
attaining the equilibrium fast by increasing the rates of both forward and backward
extent.

3.5 Collision Theory of Chemical Reactions

[March 2014, March 2017]
23. What is collision frequency?
sec per unit volume of a reaction mixture is called collision frequency.
Ans: The number of collisions per
rates. [March 2015, July 2017, March 2020)
24. Explain simple collision theory of reaction
collisions between the reactant molecules. For this two
Ans: Chemical reaction occurs as result of effective
a

factors are important.

(i) Energy of activation
(ii) Proper orientation of reacting molecules.
amount of energy to react.
The reacting molecule should possess certain minimum
(iii)
reactant molecules are considered as hard spheres. The collisions in which
According to this theory, the facilitate
with sufficient kinetic energy (equal to threshold energy)and a proper orientation
molecules collide new bondsto form products.
species and formation of
breaking of bonds between reacting
reaction is given by
From collision theory, the rate of the
E,
RT
k=pZane
where k= rate constant,
1
PUChemistry
<br>

Chernical

factor or
probability factor or oricntation steric factor for reaction collision.
ZAR Collision frequcncy
Cve the importance of proper and improper orientations of reactant
25. molecules according to sim
collision theory.
Ans: The proper orientation of reactant molecules lead to bond formation where as improper orientation
them sinnply bounce back and no products are formed.

Improper

Hs -5 |Orientation H-C-Br
H
OH- No
products
H-C-Br + OH
H H
+
Methyl bromide
Proper.
Orientation HOBr H –-H
H
Br
H H
Intermediate Methylalcohol
26.
What are the main criteria for effective collisions according to simple collision theory?
Ans: 1) Activation energy
(i) Proper orientation of
the molecules.
7. For many reactions, it is found that a large number of colliding molecules have energy more than
threshold value, yet the rate of the reaction is slow. What might be the reason?
Ans: This is because colliding reactants also need to have favourable orientation between themselves ta

activated complex.
8. Give a drawback of simple collision theory.
Ans: This theory considers reactants as hard spheres and ignores their
structural aspects.
Multiple Choice Questions (MCQs)
. For chemical reaction with rise in
temperature by 10°C, the rate constant is
4. In Arrhenius equation k=AeR
factor e-E/RT
nearly corresponds to
a) Tripled b) halved a) the fraction of molecules that have kit
c) four times d) doubled energy greater than energy of activati
2. Arrhenius equation is given by b) the fraction of molecules that have
a) k=AeE,/RT energy less than activation energy
c) the fraction of molecules that have
b) Ink=B
RT
+ In A
energy greater than threshold energy
E, d) the fraction of molecules that have
c) log
2.303R energy less than threshold energy
k TT S.
d) All of these Threshold energy is equal to
a) Activation energy
1 plot between In k and b) Activation energy- energy of molecu
the slope is c) Activation energy + energy
Ofmolecu
equal tò d) None of these
E, 6. Th
<br>

UNIT
d- and f-Block Elements
d-Block Elements
4
or Transition elements
1. What arcd-block
Ans: clements?
The clemcnts
2.
in which the added electron enters
What are transition into (n- 1)d orbitals are called d-block elements.
Ans: The elements which clements?
possess partially filled
called transition d-subshell either in
elements. the atomic state or
in the oxidation
statea
4.1 Position in
1.
the Periodic Table
What is the position
Ans: d-Block elements are of d-block elements in the
placed in the middle periodic table?
2. Give reason: of the periodic table i.e.. between
Ans: Because their d-block elements are called transition the s- and p-block elements
properties are intermediate elements.
3. Givethe group between s and p-block
Ans: Groups 3-12. numbersof d-block elements.
elements in the periodic
table.
4.2 Electronic Configurations
Write the general of the d-Block
Ans: [Noble gas] electronic configuration Elements
of d-block elements.
(n- 1)d'-0 ng!-2
Write the valence
ns: (n - 1)d-1ns-2 shell electronic configuration
of d-block elements.
Write the general electronic
s: [Ar] 3d-10 48-2 configuration of 3d
series of elements.
How many series
s: 4 series of d-block elements are
(namely. 3d, 4d, Sd and 6d
known?
series).
3d series or first transition
series; 2,Sc to
4d series or second transition Zn (3d-°4s)
series; Y to 4Cd
5d series or third transition 39 (4d-°ss)
series; 57La, Hf Hg (5d'-°6s-2)
6d series or fourth
transition series;
89 Ac, 103Rb-u, Rg (6d-0 7s-2)
<br>

Publications
wth clectronic configuration 133
Writethe of clements
Name of clements
Symbol of 3d series.
Scandium Atomic number
Sc Elcctronícconfiguration
Titanium 21
T [Ar|3d'4s'
Vanadium 22 [Ar]3d'4s'
23 [Ar]3d'4s?
*Chromium
Cr 24
Mangancse [Ar]3d'4s!
Mn 25 [Ar]3d'4s?
Iron Fe 26 [Ar]3d4s?
Cobalt Co 27 [Arj3d'4s
Nickel Ni 28 [Ar]3d°4s?
*Copper Cu 29 [Ar]34°4s'
Zinc Zn [Arj3a'°4s?
30
Explain the exceptional l electronic configuration of
d-block elements.
:Since cnergy difterence between ns and (n 1)d -
is less, some d-block elements show some exceptional
electronic configuration. This is due to extra stability of half filled and completely filled orbitals.
Example 1:The electronic configuration of Cr is [Ar] 3d 4s' instead of fAr]3d 4s'. This is due to the extra
stability of half- filled d orbitals than d orbitals.
Example 2: The electronic configuration of copper (Cu) is [Ar)3a"4s' instead of [Ar]3d'4s. This is because
completely filled d" orbitals are more stable than d orbitals.
Why Zn, Cd and Hg are not regarded as transition elements?
as well as in their common oxidation states. So
They contain completely filled d-orbitals in the ground state
they are not considered as transition elements.
even though they contain completely filled
Why Zn, Cd and Hg are included under transition elements
common oxidation state?
d-orbitals both in ground state and
some of their properties.
Because they resemble other transition elements in
elements even though they contain completely filled
Why Cu, Ag and Au are included under transition
orbitals in their ground state?
in the common oxidation states
Because they possess partially filled d-orbitals
Ag 4d, Au'*
(Cu2+ 3d,
you say that Sc (Scandium) (Z=21)
transition element but Zn is not
is a
On what ground can (NCERT Example)
(Z=30)? it is considered as transition element. Zn contains completely
(3d'). So
Sc contains partially filled d-orbitals is not considered as a
its ground state as well as in oxidation state. Hence
lled d-orbitals (3d'°) in
transition element.
in its ground state. How
can you say that it is a
Silver atom has completely filled
d-orbitals (4d)
(NCERT Intext question)
hence
transition element? it will have incompletely filled d-orbitals (4d)
Silver (Z= 47) can exhibit+2
oxidation state wherein
Ag is a transition element.
 Multiple Choice Quest
<br>

3. General clcctronic configuration

1. Transition metals are defincd as metals which
have
orbitals of d-block elements is
a) incomplcte d-subshellcithcr in ncutral atom a) (n -)d' ns? b) (n-l)d"ne
or in their ions c) (n -)d?-"ns-2
b) completcly filled d-subshells only in ncutral
4, and completely filled sets
Half filled
atom are relatively ot
c) partially filled d-subshclls only in neutral
a) less stable
atom
b) Imore stable
d) partially filled d-subshells only in their
c) stability cannot be predicted
ionic state
d) none of these
2. Which of the following clements are not
5. The electronic configuration of chromin:
regarded as transition metals?
a) Zn, Cd and V b) Zn, Mn and Co copper respectively are
c) Cd, Ti and Mn d) Zn, Cd and Hg a) [Ar3d4s' and [Ar3d°4s?
b) [Ar3d'4s' and [Ar]3d"4s'
c) [Arl3d'4s' and [Ar]34°4s'
d) [Arj3d'4s and [Ar]3d°4s!

Answer Keys
2 345
a b

1.3General Properties of the Transition Elements (d-Block)

Explain the metallic character of transition elements.
Ans: Transition metals can lose valence
electrons and form cations;
clements show metallic properties
such as high tensile strength, MM"*+
ne.
Therefore all trans
electrical conductivity and ductility, malleability, high thermal
metallic lusture.
They have simple cubic, hcp, ccp
and bcc lattice. Except Hg all
The melting and boiling transition elements are solids.
points of the transition
Why? metals are maximum at
Ans: Due to the presence more
the middle of each ser
of
between the atoms is very
number of unpaired electrons
in the middle
(n-1)d and ns in intermetallic
strong due the
involvement of more of each series, metallic bon
number
they have high melting of unpaired electrons from b
bonding. Therefore
Meltíng points of
Ans: This is
transition metals increases and boiling points.
because upto d upto d configuration
configuration, the and then decreases. Explain.
stronger and hence number of unpaired
melting point becomes electrons increases.
number of unpaired higher. After d So metallic bond be
electrons decreases. configuration, pairing
Mercury is the liquid Metallic bond of electrons takes pla
at room temperature, becomes weaker
Explain. and hence melting
1S: Due
Zn and Cd are soft metals point devie
to the absence of with low meltinB P
melting point are unpaired electrons
less. Hence Hg in Hg, Zn and Cd
exists as liquid metallic bond
at room temperature is very Thereforeweak.
and Zn and Cd are
dent's illuminator soft metals.
<br>

Publications
Jeevith 135
Melting points of 3d series are
less than 4d and 5d series. Explain.
5,Ans: This is due to high cnthalpy of
atomisation (heat rcquired to brcak the mctal lattice to get free atoms) of
4d and 5d serics than 3d scrics.
Note: Tungsten
(W) has highest melting point
(3410°C) and mercury has lowest m.p. (-38°C).
Why do transition clements exhibit
higher cnthalpics of atomisation? (NCERT Example)
Ans:
Because of large number of unpaired clectrons in their atoms, they have stronger interatomic interaction and
hence stronger bonding between atoms, resulting in higher cnthalpies atomisation.
of
Enthalpy of atomisation is nmaximum in the middle of cach transition series. Wny
to the more number of unpaircd clcctrons interaction is
Ans: Due in the middle cach scries, interatomic
of

stronger. Theretore, enthalpy of atomisation is maximum in the middle of each transition series
In the series Se (Z = 21) to Zn (Z = 30), the cnthalpy of atomisation of zinc is the lowest, i.e- 20 ho
S.
mol. Vhy? (NCERT Intext question)
more extensive the
Ans: The extent of metallic bonding of an element decides the enthalny of atomisation. The
In all transition metals (except
metallic bonding of an element, the more will be its enthalpy of atomisation.
are some unnaired electrons that account for their stronger
Zn, electronic configuration: 3a° 4s). there
electrons. the inter-atomic electronic bonding is the
metallic bonding. Due to the absence of these unpaired
weakest in Zn and as a result, it has the least enthalpy of atomisation.
series. Give reason.
9. Enthalpy of atomisation is more in 4d and 5d series than 3d metals (4d and 5d) than 3d series.
Ans: This is due to the strong metal-metal
bonding in heavy transition
unpaired electrons are present in Mn (3d series) Tc (4d series) and
10. Eventhough more number of
Re (5d series) their melting points
are less. Why? are
filled d5 electronic configuration. Therefore electrons
Re have stable half
Ans: This is because Mn, Tc and delocalisation of electrons is less and hence metallic bond
is weak.
So
held more tightly by the nucleus. metals. [March-2019)
and ionic sizes (radii) of transition
1L/Explain the variation of atomic decrease in atomic radi
with increase in atomic number but this
radii decreases
Ans: The atomic and ionic
becomes small after midway. due to increase in effective nuclear
charge.
radius decreases from Sc
to Cr
Example: In 3d series atomic effective nuclear charge
same. This is because the increase in
remains almost
From Cr – Cu atomic radius or screening effect. expansion due
compensated by shielding effect completely filled orbitals and electron cloud
copper due to
Zn has arger atomic
radius than
paired electrons. Co Ni Cu
Cr Mn Fe
Sc
T

128 128 137

Element 129 128 128
147 135 129
164 reason.
Atomic radius (pm) density increases. Give
series, effective nuclear charge.
the period of each transition to increase in
2. Along because decrease in metallic
radius due
d-block elements.
[March-2015]
increas
Ans: This ionisation enthalpies in across a period. This is due to the
of as we move ionisation ener
13.Explain the variations
enthalpy of 3d series
increase
inner d orbitals. The second
the filling of the and there
Ans: The ionisation which accompanies
number. But this trend is not regular
effective nuclear charge with the increase in atomic
also increases neighbours. This is d
of the 3d seriesvariations. sufficiently higher than their
some irregular Cr and Cu are
enthalpy of and d0 in Cu).
1. Second ionization configuration (d in Cr
stable electronic
their
I| PUChe
<br>

d- and The
ionisation enthalpy of chromium is lower bccause removal (-Block
2 The first of one electron
configurntion and that of zinc is higher because the removal
Eer
stable produces
of electron takes
filld 4s orbital. place
Cr=3 from
4s Crt=3aß
Zn =3d0 4ç2 Znt =3d104s!
3. The sccond ionization enthalpy of Zn is less than second
ionization
removal of second electron in Zn produces stable d1o
configuration enthalpy of Cu.
in Cu disrupts the d° configuration with a considerable while This
configuration.
loss in exchangethe removal of is becay
energy second
to form elect
Cu
(3d10)Cu't less stable
(3P)
Zn' (3d10 4s!
4. Secondionization (3a10)
enthalpy of Mn
second electron (Z= 25) is less than
in Mn produces half flled that of Fe
S.
Third ionisation
enthalpy
configuration(Z= 26). This
of Mn is more Fe but
produces is because
Mn disrupts
stable than that of Fe.
configuration
but in Fe This is (less stable removal of
6.
Third ionisation energy removal of because than
third removal of
third electron).
of copper, electron
state greater
than two for these nickel and Zzinc forms
elemnents. is very stable P
14. What
isthe reason high. Because configuration.from
for irregular it is difficult
(3d) of the
Ane Theiregular transition elements? variation of ionization to obtain
vaiation of enthalpies oxidation
15 Explain the variable ionizationenthalpies 1s (first and
Knc oxidation due second)
The variable
oxidation states state of transition
to varying egree (NCERT in the first series
The minimum elements. of stability Intext question)
oxidation stateoftransition metals of different
The maximum
oxidation is the loss ns are due to configurations
of electrons. the loSs of
The oxidation
Os in 5d series.
state
states increasesis the sum of
as the theloss
inner (n
1)d and
-
[July-20is]
outer ns
The oxidation Then it decreases atomic numberof both (n-1)d electrons.
states due to the increases unpaired
of3d-series pairing upto Mn electrons
elements are of electrons in 3d and ns electrons.
as shown below: in d-orbitals. series and Ru in
Tonu Sc T
Cr Mn [The most common 4d series and
+2 +1 Fe Co ones are
+2 Ni Cu in bold types
+2+2 +2 Zn
+2 +3 +2 +3
+3 +3 +4 +3 +1 +2
+3 +4 +3 +3
+4 +2
+4 +5 +4 +5 t4 +4
+5 +5
In 3d sernes +6
manganese +6
Cushows +6
+ 1 oxidation(Mn) showS a +7
Tne Oxidation state maximum
due to completely oxidation
ligands
(CO)are
Fe is more
states
of
capable
Ni and Fe state
filled d-orbitals.of t
in the complexes
.
stable ofhaving - Ni(CO)]
Cr than acceptor
Student's
1s more
stable Fe
than C2
Hence and
Fe2t acts character in addition |FeCOs are zero (0) because
illuminator Hence C as a reducing to the g-bonding. the
acts as agent
reducing
ag
<br>

Publications
Jeevilth
more stable than Mn". Hcncc
Mn is Mn
acts as oxidizing 137
Note: In 4d series Ruthcniunm agent.
(Ru) shows a maximum
series osmium oxidation statc of +
In Sd . (Os) shows a maximum
oxidation state of+ 8.
Jd-series transition metals exhilbit as (July-2014]
+2 the most common
16.
The Oxidation state arises fromthe loSs of two oxidation state (except Sc) why?
Ans: ne more stable than 4s clcctrons. This means
the S-orbital. Hencc 3d-scrics transition that after scandium d-orbitals
Oxidation state (except Sc). metals cxhibit +2 as the most common
Name the clement of 3d serics which
17. shows maximum or highest
oxidation state.
.nc Manganese (Mn). 0.S. =+7 [Marclt-2014, March-2017
transition element which does
not exhibit variable
=+3] oxidation states. [July-2022]
ns: Sc [0.S
Which of the 3d series of
9. the transition metals exhibits the largest
why? number of oxidation states and
Manganese (Mn). The OXIdation states of Mn are
+ 2,+3, + 4, + 5, + 6 and + 7. Mn
of oxidation states due to the presence of mnaximum exhibits largest number
number of unpaired 3d electrons and two
Why Cr* is reducing 4s electrons.
Mn and oxidizing when both have configuration?
C
is reducing because its configuration d
rom d to d, the later has half
changes
Oxidising because the configuration filled to level. Mn is
changes from Mn to Mn results in the
which has extra stability.
half filled (d) configuration
Why is the highest oxidation state a
of metal exhibited in its oxide or fluoride only?
ms:
Both oxygen and fluorine are highly electronegative (NCERT Intext question)
and have a very small size. Due to these properties, they
are able to oxidize the to metal its highest oxidation state.
Note: a) The ability of Fluorine to stabilize
the highest oxidation state is due to either higher lattice enthalpy
[Ex:CoF] or higher bond enthalpy (Ex: VFs and CrF:]
b) The ability of oxygen to stabilize high oxidation state exceeds that of fluorine, this is due to ability
of oxygen to form multiple bonds.
Ex: The highest Mn fluoride is MnF4 whereas the highest oxide is
Mn,0,.
c) In Mn,O7, each Mn is tetrahedrally led by O's including a Mn
–0-Mn bridge.

Mn. Mn=0

Which is a stronger reducing agent Cr²* or Fezt and why? NCERT Intext question)
The following reactions are involved when C and Fe?t act as reducing agents.
Cr2+ Cr3t Fe2tFe3t
The value is -
0.41 V and is + 0.77 V. This means that C* can be easily oxidised to Cr+, but Fe2+ does
hot get oxidised to Fest easily. Therefore, Crt is a better reducing agent that Fet,
Which is a stronger reducing agent between Cr or. Fe and why?
C
a stronger reducing agent than Fe". This is because the configuration of C changes from
and d is stable due to half filled tzg level.
d to d
<br>

d- and
The
Note: In higher otidation states, transition metal ions arc good oxidizing
agents.
Kh0. are good oNidizing agents. (In KMnO,, O.S. of Mn =+7 and In KCr;0,, 0.S.Example
24. How docs ioniccharacter of metaloxides vary with oxidation numbcr? of Ct
Ans: Lower theoxidation state of metal Oxide higher the ionic character. t6
25. Between MnO and Mn,0, which one of these has morc
covalcnt character?
Ans: Mn-0, (Higher oxidation state will show covalent character)
26. Whnt is meant by "disproportionation' of.
fan oxidation state? Give an
Ans: When a particular oxidation state
becomes less stable relative to example.
other
example, manganese oxidation states,
higher, it is said to undergo disproportionation. For
manganese (VI) and manganese (1V) in (VI) becomes one
acidic solution. lower
3Mn "o, unstable
+4H*2Mn "O, Mn "0, + 2H,0
+ relat
27. Arrange Cr;O3, CrO; CrOin increasing
Ans: Higher oxidation state shows mnore
order of their acidic
acidic character character.
Hence CrO< Cr,O,
CrO; <

28. The Eo{M*/M)

value for copper
is positve ( U.3
V). hat is
Ans: Copper has high energy the possible reaee
of
atomization and
Cu(ag) is not comnpensated low hydration energy. (NCERT
by hydration energy. The high energy Intext question)
29. Scandium has Hence E° value to transform
less E°(M*/M*) for copper Cu(s) to
Ans: This is due
to extra stability
value why? is + ve.
of Sc which has
30. Zinc has very
high E°(M*
noble gas configuration
/M*) value. Why? [Arll8
Ans: The highest
E° 30
Zn (Zn1Zn) value for
Zn is due to
the removal an
31. Vanadium has of electron from
relatively low stable dlo
configuration o
Ans: This is
due to the extra
E°(M'*/M*) value.
stability of Give reason.
32. E°(Mn
V* due to half filled
Ans: Due to
/Mn*)value of Mn" is comparatively
t. orbital.
d configuration
33. ofMn", it is very high. Why?
E°(Fe stable.
Ans: This
/Fe*)value of Fe* (NCERT example)
is due to extra is low. Why?
stability
34. How do
you explain of Fe* (d). i.e.,
low third ionisation
the relative enthalpPy.
Ans: The stability of ions
relative stabilities by using standard electrode
For example of cations potential values?
can be
explained onthe basis [July-2018]
Cu of their standard electrode potential
+eCu
Cu+2eCu' Pred
=0.52 V
values.

Thestability
ofion is E,red =0 34 V
Here inversely
Pcu' Cu
1Sless proportional to Eo
than value.
E.*/Cu Hence Cu is more Higher theCuE°ion.value lesser is the stability.
stable than
<br>

Jeevit
How would you account for
35. the increasing oxidizing power 139
in theseries VO" <
Cr,0 <
MnO,.
This is duc to thc inercasing
Ans:
is a
stability of the lower (NCERT example)
1Which strong reducing ngent spccics to which
they are
36. Cr" or Fe reduced.
is good roducing
Ans: Cr agent becausc of and why?
Many copper () compounds
its less standard reduction potential
37. arc unstable in
aqueous solution and
value than Fe.
Explain. the undergo disproportionation.
Thc stability
of Cu*
Ans: ion is morcthan Cu (NCERT Intext question)
vdration of Cu 1onthan ionin aqueous solutions.
Cu ion which more than the second ionisation dueto more negative enthalpy
This is of
Eplain the magnctic propertiesor enthalpy of Cu.
38. paramagnetic property of transition
elements.
Ans: Most of the transition metals and (March-2017, July-2017|
their compounds are paramagnetic
The paramagnetism is due to presence (slightly attracted by the magnet).
the of unpaired electrons in the d-orbitals.
The main causes of paramagnetism are orbital
angular momentum and spin momentum electron.
of
The magnetic moment is calculated by using -
spin onlyformula i.e., u=n(n +2) BM.
where u= Magnetic moment, B.M. = Bohr magneton (the unit of magnetic
moment) n= Number of
unpaired electrons.
Themagnetic moment increases as the number of unpaired electrons increases.
39. What are diamagnetic substances?
Ans: The substances, which are repelled or not attracted by an applied magnetic filled due to the absence of
unpaired electrons are called diamagnetic substances. Example: Zn, Zn, Sc, Ti", Cu etc are
diamagnetic due to the absence of unpaired electrons.
Zn2+ and Co which is not attracted by a magnet?
40. Among
Ans: Zn due to the absence of unpaired electrons.

41. Among zincsalts and cobalt salts which

is attracted by a magnet?
Ans: Cobalt salts due to the presence of unpaired electrons.
are not attracted
42. Cu is diamagnetic and
Cu is paramagnetic. Why? or Cu() compounds
magnet. Why?
magneticbut Cu() compounds areattracted by
contain unpaired electrons. So it is diamagnetic. So it is not attracted by magnet.
Ans: Cu or Cu () does not
by magnet.
Cu or Cu(I) contains unpaired d-electrons.
So it is paramagnetic. So it is attracted

43. Sc salts are diamagnetic. Why?

d-electrons. So they are diamagnetic.
Ans: Sc does not contain unpaired
calculate the number of unpaired electrons in 3d series.
to
Note: Formula state - Atomic number of
argon (18).
of an element- oxidation
n=At.number
Formula 1: Ifn to 5, all are unpaired electrons.
=l = 10 -n.
then number of unpaired electrons
Formula 2: Ifn >5,
Examples: number ofAr.
Sc-0.S-Atomic
() Sc: n=Atomic number of
n=21 -3- 18=0
(ii) Tt of Ti-0.5. - Atomic number
of Ar
n=Atomicnumber
ll PU Che
- 18 =1
<br>

(iii) Mn?+ or Mn in Tho

MnSO,.
n d- and
Atomicnunnber Mn b
of 0.S, -
Atomic number of Ar.
n-25--2-18$
(v) Cu

nAtomic number of
Cu–0.S, -Atomic number of Ar.
n29-|- 1810
.n=(10- 10)
=0
(vi) Cu or CuSO4
n=Atomic nunmber of
Cu-0.S, - Atomic number of Ar.
..n=29-2- 18=9
n=(10- n) (10- 9) =1 =

(vii) Zn*
n=Atomic number of -
Zn-0.S. Atomic number of Ar.
n=30 -2- 18= 10
. n=(10- 10) =0
44: Calculate the magnetic
moment of
Sc" (Z=21).
Ans: n=21-3- 18=0 [March-2
:: p=/n(n + 2)BM
=/0(0+2)BM
l=0BM
45. Calculate the magnetic moment
of Ti' (Z=22),
Ans: n=22 -3– 18 =] tse
. u=/n(n +2)BM [July-2019)

=/1(1+2) -(3) =3
=1.73 BM
A6, Calculate the magnetic moment
of a divalent ion in aqueous
solution if its atomic number is 25.
Ans: Given: At. number [July-205]
=25 (Mn) (NCERT Example)
Divalent ion = Mn2+

n=At. number ofMn – oxidation

state atomic number of Ar.
n=25-2- 18 =5
=n(n+2)BM
=/5(5+2) -/5(7)
=35
=5.92 BM
Calculate the 'spin
only' magnetic moment
of M
ion (Z=27).
:Z=27: [Ar] 3d 4s (NCERT Intext question)

t's illuminator
I| PUChets
<br>

Publications
Jeevith 141

; M2t=[Ar] 3': 3d-1na

i.c., 3 unpaired clectrons
n3
H=n(n+2)
=3(3+ 2) =V1s-3-87 BM
A8.
Exnlain the colour of transitionmetals ions.
of a
Ans: The colour transition metal ion is due to
The presence of unpaired electrons in the d-orbitals.
()
(ii) d-d transitions.
The unpaired d-electrons absorb colour from the visible region and undergo d - d transition and radiate
complementary colours.
Example: Cu absorbs red colour and emits blue colour. So the complementary colour to the fed is blue.
are colourless. Why? [March-2014, July- 2016]
49. Zn2* salts
Ance Due to the absence of unpaired electrons.

Cuz salts are coloured. Give reason. [March-2014, July-201 July-2019, April-2022]
50.
Ans: Due to the presence of unpaired d-electrons.
is coloured?
51. Among zincsalts and cobalt salts which
Ans: Cobalt salts.
[March-2016]
52. Which of the following ion is coloured? Se, Zn* and Cr.
Ans: Cr* ion is coloured due to the
presence of3 unpaired d-electrons.
are coloured. Why?
53. Cu(I) salts are colourless and Cu (I) salts
d-electrons. So they are colourless.
Ans: Cu(l) salts (Cu) do not contain unpaired
So they are coloured.
Cu (I) salts (Cu) contains unpaired d-electrons.
series which is colourless in both atomic state and oxidation state.
54. Name a transition element in 3d
are colourless).
Ans: Zinc (both Znand Zn reasons. [July-2014, July-2017]
metals form large number of complex compounds. Give
Transition
transition metal ions
Ans: This is due to (i) smaller size of ratio)
polarizing power i.e., high charge by size
(ii) larger ionic charges (Or high
(iii) the availability of
vacant d- orbitals for bond formation.
catalytic properties of transition metals. March-2019)
56. Explain the [March-2015, March-2018, July-2018,
compounds behaves as catalysts due
-to
elements and their
Ans: The transition
Variable oxidation states.
()
surface.area for adsorption of reactant molecules
(ii) Large filled d-orbitals.
presence of incompletely filled or partially
(iii) The
intermediate compounds.
(iv) Formation of
Examples: contactprocess (Manufacture of H,SO4)
pentoxide is used as catalyst in NH;)
(1) Vanadium Haber's process (Manufacture of
as a catalyst in the
(2) Iron oxide is used of oils Oils+ H, Fat)
the hydrogenation
(3) Nickel is used as a catalyst in

II PUChemistr
<br>

,-
The
and
57 Explain the formation of interstitinl compounds. [March
Ans: The compounds in which small atoms like Cor Narc trapped into the (cmpty space) cavities
H.

of
lattices of metals. Such compounds arc called interstitial compounds.
Erample: TiC, Mn,C, Fe,H, VHo56 and TiH,; ctc.
The physical and chemical propertics of interstitial compounds are:
collg (i) interstitial compounds are non-stoichiometric.
of pure
metals.
(ii) They have high melting points, higher than those
(ii) They are very hard, some borides are hard as diamond.
(iv) They are chemically inert.
) They retain metallic conductivity.
as or
ANOte: he empty space present in the crystal lattice is called interstitial site void.
Tl

58% Explain the formation of alloys of transition elements.

Ans: Transition elements have strong tendency to form alloys because their atomic sizes are very simila
the crystal lattice one metal can be readily replaced by another. Alloys have high melting point and hc:
Example:
() Stainless steel is an alloy of Fe, C, Cr and Ni.
(ü) Amalgam is an alloy of Hg with other metals.
(ii) Brass (Cu + Zn)
(iv) Bronze (Cu + Sn) [April-201)

Multiple Choice Questiòns (MCQs)

1. Which of the following d-block element has c) does not affect
highest melting point? ) exchange energy is not related to
t
a) w b
Mo of atom
c) Cr d) Mn 5
The lowest common oxidation state
2. The metals of the second and third transition series of element is
series have greater enthalpies of atomization e
a)+2 b) +3
than the corresponding element of the first +7
c) d)+4
series.This is because
metal-metal bonding is stronger in heavy
a)
6. Highest oxidation state shown in

transition metals than 3d-series compounds by

b) metal-metal bonding is weaker
a) Fe b) Cr
in heavy. be
c) Mn
transition metals than 3d-series d) Ni
c) metal-metal bonding is same in
heavy 7..The stability of Cu than Cu
is duet
transition metals than 3d-series a) more negative hydration enthalpy of
d) none of these C
b) less negative hydration enthalpy of Cu
The terms responsible for the value c) hydration enthalpies are same in both =
ionization enthalpy are of
d) none of these
a) attraction of each electron towards nucleus
b) repulsion between the electrons
8. Paramagnetic properties of d-block eleme
c) exchange energy are due to
d) all of these
a
the presence of unpaired electrons
b
4
The loss of exchange energy the absence of unpaired electrons
c
orbitals
in. degenerate the presence of lone pair of electrons
the stabilities of atom d) the.absence of lone pair of electrons
a) increases
b) decreases

Student's illuminator
<br>

Publications
Joevith 143
The magnctic moment of clements can
by be b) their high ionic charges
caleulated
+ c) availability of d-orbitals for bond formation
a) /n(n 2) b) n(n )
+
d) all of these
n(n - ) d)
c) n(n-2) 14. The transition metals and their compounds
arc known for their catalytic activity. This is
10. The units of magnetic mnoment is
magneton due to their
a) Bohr b) Kgm
c) Kg
m
a) variable oxidation states
d) Kg m
.. b) formation of complexes
The magnetic moment of nn clemcnt is 1.73 arca to form bonds
c) provide morc surface
BM. The number of unpaired electrons is d) all of thesc
a) 2 b)
c) 1
d)
15. Interstitial compounds are
a) having high mclting points
12. Zn* ion is colourless. It is due to b) very hard
a) the presence of unpaired elcctrons Dc) chemically inert
b) the absence of unpaired electrons d) all of these
c) the presence of lone pair of electrons
16. As the oxidation number of a metal in its
d) the absence of lone pair of electrons
compound increases,
13. Transition metals form a large number of a) ionic character increases
complex compounds. This is due to b) ionic character decreases
a) comparatively smaller sizes of the metal c) covalent character decreases
d) none of these
ions
Answer Keys

2 3 45 6 7 8 10 11 12 13 14 15 16

a a a C a a a a b d d d

.4 Some Important Compounds of Transition Elements

Give characteristics of oxides and oxoanions of transition metals.
ns: 1) Alltransition metals except Sc form metal oxides which are ionic and basic nature.
(ii) Higher oxidation state oxides like Mn,O, are covalent and acidic in nature.
(ii) Some metal oxides react with both acids and bases. Such oxides are called amphoteric oxides.
Examples: Cr-O3, V,0s,
Vanadium pentoxide (V,0,) is amphoteric oxide. Explain.
1s:
V,0, reacts with both alkalies as well as acids to give VO} and VO; respectively. Hence Vanadium
pentoxide (V,Os) is amphoteric oxide.
Give an example for amphoteric oxide.
S: Cr0,
Note:
a) As oxidation number of metal atom increases, (i) ionic and basic character decreaes (i) covalent and
acidic character increases.
b) In a transition series, across a period from left to right (i) ionic and basic character decreases
(i) covalent, acidic character increases.
Example: The acidic character of oxides is in the order of TiO< VO < CrO<MnO <.....

lenfe
I PUChemistrN
<br>

The d-
and
f-e
144 aqucous solution-
(permanganic acid) in that
c)Mn,0, is a covalent green oil andI it gives HMnO,
acidic clharacter.
acidic in naturc.
d) CrO, gives H;CO, and H;Cr;0, showing CrO, is and VO; (withacid
gives VO} (with alkalics)
c) V;0, is amphotcricthough mainly acidic andit
) Cro is basic and Cr,O, is amphotcric. dichromate(K,Cr;0)
4. Namethe important ore or chicf orc of potassium
- or
Ans: Chromite orc or chrome iron stone FeO.Cr,O, FeCr;04
5. Give three uses of potassium dichromate.
Ans: (i) It is uscd in leather industry
(ii) Used as an oxidizing agent.
(ii) In quantitative analysis as a primary standard.
iv) In qualitative analysis (test for CI ions) (March-2014, July-2014, Marc
How is potassium dichromate (K,Cr,O) manufactured:
July-2019, April-2022, Juy-20Z2J
March-2016, Jul'-2015. July-2018. Marcl-2019.
1s manufactured from chromite
ore or chromne iron stone. Fe0. Cr2O3 Or FecI204.
S2r2071-Chromnite ore is heated with sodium carbonate in excess of air to form SOdTum chromate
Sep
4 FeCr,O4 + 8 Na,CO, + 7O; 8Na,CrO4 + 2Fe,O; + 8CO,.
- acidified with sulphuric acid to oiv
Step Il The yellow solution of sodium chromate is filtered and
solution of sodium dichromate.
2Na,CrO, + 2H* Na,Cr,O, + 2Na* + H,0
The less soluble sodium sulphate is removed by filtration.
Step III: The solution of sodium dichromate is treated with KCl to form potassium dichromate.
Na,CrO, +2KCI-K,CH0, + 2NaCl
Solution on cooling gives orange red crystals of K,Cr;0,
Write, the structure of chromate ion and dichromate ion.
Ans: The structure of chromate ion [CrO;] is tetrahedral. The structure of dichromate ion consists
tetrahedra sharing one corner with Cr-O-Cr bond angle of 126°.

Chromate (CrO;)
Dichromate (Cr,0,)
How does KCr0, reacts with
() r
Ans: Potassium and sodium dichromates are(ii) Fe (iii) Sn* (iv) H,S.
can be written as powerful oxidising agents.
Cr,0 +14H" In the presence off acids, oxidisinE
+6e 2Cr*+7H,0 (E° = 1.33V)
i) Acidified K,Cr,0,oxidises
iodide to iodine
Cr,0 +14H* +6e
2Cr*+7H,0
61
31, + 6e
Cr,0+14H* +61
31,+2Cr*+7H,O
luminator
<br>

Publications
Jeevith
145
Acidificd K,Cr,0,oxidises
(i) Fe (II)salts to Fe (II) salts.(Ferrous to
Ferric)
Cr,0} +14H" + 6c
6Fe >6Fe" +6e
Cr,0 + 14H' +6Fe?* 6Fe'"+2Cr* +7H,0
(iüi) Itoxidises hydrogen sulphide to
pale yellow precipitate of sulphur.
C,0; +14H' +6c 2Cr* +7H,0
3H,S 6H* +3S 6e+

+
Cr,0 8H* +3H,S3S J+2Cr+7H,0
(iv) It oxidises Sn (I) salts to Sn (IV) salts (Stannous to
Stannic)
Cr,0 +14H* + 6e2Cr* +
7H,0
3Sn2+ 3Sn* +6e
Cr,0, +14H* + 3Sn2+ >3Sn* +2Cr* +7H,0
on pH.
Explain the interconversion of chromates and dichromate ions depending
9. in basic medium dichromate is converted into
Ans: In acidic medium, chromate is converted into dichromate and
chromate. Hence dichromate and chromate are interconvertible.
+ 2H*
Cr,0; + H,02Cr0?
(yellow)
(orange red)
permanganate (KMnO) manufactured? [July-20I6, March-2017, March-2018]
10 How is potassium
Ans: KMnO4 is manufactured from
pyrolusite (MnO,) an agent to form
fused with KOH in presence of KNO; as oxidizing
Step- :
Pyrolusite is powdered and
potassium manganate.
2MnO, +4KOH+0, 2K,MnO, +2H,0 dispropörtionation in acidic or neutral
manganate undergoes
green coloured potassium
Step II: The
medium to give permanganate.
+4H“2MnO;+
+
MnO, 2H,0
3Mn0? crystals of KMnO,.
so obtained is concentrated to get dark purple manganate ion in alkaline
The purple solution obtained by electrolytic oxidation of
permanganate ion is
Note: Commercially,
medium. Electrolytic oxidation in
Fused with KOH,oxidised alkaline medium MnO;
with airor KNO3 MnO Parmanganate ion
MnO, Manganate ion

preparation of potassium permanganate. oxidation of a manganese (I) ion salt by

Sive the laboratory permanganate is obtained by the
potassium
Ans: In the laboratory,
peroxodisulphate. + 8SO? +16H*

2Mn*+5S,0 +8H,O2MnO,
ions.
structure of Mn0 and Mn0;
12.
Write the
Ans: Both have tetrahedral structure.
II PUChemistry
<br>

and
Er,
Mn Mn

[manganate ion] Iparamanganate ion]

13. What is the action of heat on
Ans: KMnO, on hcating at S13 KMnO,?
K
undergo redox reaction to give potassiun manganate, MnO, and O,.
2KMnO, S13K K,MnO,+ MnO,
14.
+0,
How does KMnO, reacts with
I ,Fe*,C,0,H,S,
Ans: Potassium permanganate is a powerful oxidising agent
in acidic, basic and neutalmeuum.
In acidic solutions, oxidation of Mn0; ion can
be written as
Mn0, +
8H* +
5eMn* +4H,0
(a) MnO; oxidises iodide to iodine
[MnO, +8H* +5e Mn
+4H,0]x 2
I+2e]x5
2MnO, +101+16H+ >2Mn* +8H,0+51,
(b) It oxidises Fe2+ ion (green) to Fe+ (yellow).
MnO, +8H* +5eMn* +4H,0
[Fe2+
Fe* +e]x5
MnO, +SFe? +8H Mn 2+ +5Fe*+4H,0
(c) Oxalate ion or oxalic acid is oxidised to CO, at 333 K
by MnO, ion.
[MnO7+8H +5e >Mn* +4H,0]x2
[C,02CO, +2e]x5
2MnO, +5C,0 +16H* 2Mn+8H,0 +10CO,
(d) Hydrogen sulphide is oxidised to yellow precipitate
of sulphur by MnO; ion
(H,S2H*+S)
[MnO; +8H“ + 5e
Mn* +4H,0]x 2

[SS+2e]x5
Mn0, +
5S +16H* 2Mn* +5S +8H,0
Explain the oxidation of nitrite ion by
acidified
: Acidified KMnO4 oxidises nitrite ion. to nitrate ion.potassium permanganate. Give equation.
2MnO, + 5NO, + 6H* 2Mn* +5NO;+3H,0
<br>

Publications
Jeevith
147
Explain the oxidation of sulpurous
16. acid or sulphite
Acidificd permanganate oxidiscs ion by acidified potassium permanganate.
Ans: sulphurous acid (sulphate
2MnO, + 5SO; ion)to sulphuric acid or sulphate ion.
lHow docs
+6H'2Mn
KMnO,
+
5SO +311,0
oxidises thiosulphate
17.
KMnO, oxidises thiosulphate into sulphate
in neutral medium.
Ans: ion.
3S,0; +8MnO, + H,0- 8MnO, + 6S0 4+
201
How does KMnO4 reacts with
18. iodide in neutral medium?
Ans: KMnO4 oxidises iodide into iodate (I0,) in ncutral medium.
+
I+2Mn0, H,0 2MnO,
+ 20H" + 10,
How docs KMnO4 Oxidises manganous salt in
19. neutral or alkaline medium.
nct KMnO4 0Xidises manganous salt to MnO, in the presence of zinc sulphate or zinc oxide catalyst in neutral
medium.
2MnO, + 3Mn* + 2H,0SMnO, +4H*
Permanganate titrations in presence of hydrochloric acid' areunsatisfactory. Why?
Ans: Becausehydrochloric acid is oxidized to chlorine by permanganate ions.
21. Between KMn04and KCr207which one of these is used as primary standard in volumetricanalysiS?
Ans: KCr207
Multiple Choice Questions (MCQs)
1. Potassium dichromate can be manufactured 6. Oxidation of Mn* ion salt by
from peroxodisulphate gives
a) chromite ore b) calamine
a) MnO b) MnO,
c) malachite d) siderite
c), MnO, d) Mn0:
2. The structure of dichromate ion (Cr,0 ).is
7.Both Mn0; and Mn0, have
a) tetrahedral
a) tetrahedral structure
b two tetrahedral sharing one corner with Cr
-0-Cr bond angle of 126° *ib) square planar structure
c) square planar c) pyramidal structure
d) pyramidal d)none of these
3. Acidified potassium dichromate oxidizes 8. Acidified permanganate solution oxidizes
hydrogen sulphide to Oxalic acid to
-a) sulphur b) sulphur dioxide a) CO,i b) CO
c) sulphur trioxide d) all of these c) C
d) all of these
4. Fusion of MnO, with KOH and oxidizing 9. Dark purple crystalsof KMnO4 ar
agent KNO,produces isostructural with
a) potassium manganate b) K,MnO4
b) potassium permanganate c) MnO, d) both (a) and (b)
10. Neutral KMnO, oxidizes iodide to
c) both (a) and (b)
d) none of these a) , b) 0,
D. Electrolytic oxidation of Mn0 in alkaline c). both (à) and (b) d) none of these
solution gives 11. Neutral KMnO, solution oxidises Mn* in t
a) MnO; b) MnO, presence of Zn0 to
none of these a) Mn0; b) Mn;O,
c) Mn0 d)
) MnO? d) All of these
<br>

The d-
and
148 -Bos

Answer Keys
10 11
4 5 7 8

The Inner Transitional Elements (f Block)

1.
What are f-block clements?
s
he clements in wvhich the added clcctron
1
-
centers into (n 2) f orbitals or ann penultimate sL
Callcd t-block elements. There are two series in f- block cleménts, namely
(i) Lanthanides (4f series) (ü) Actinides (5f series)
2 Write the general clectronic configuration of f-block elements.
Ans: [Noble gas] (n- 2)f-14 (n- 1)d°'ns
3. Why f-block elements are called inner transition elements?
Ans: Because in these clements the added electrons are entered into antipenultimate, (n-2)f, sub - shel,

4.5 The Lanthanoids

1. What are lanthanoids? (or rare earths)
Ans: The elements from Cerium (Z = 58) to Lutetium (Z = 71) are called lanthanoids. In these elenments t%

electrons enters into 4f orbitals.

2. Write the general electronic configuration of lanthanoids.
Ans: [Xe]4f-14 5-! 6s
3. What is lanthanoid contraction? IMarch-2014, March-2017, Jul_
Ans: The gradual decrease in atomic and ionic radii from lanthanum to lutitium is called lanthanoid contrae
4. What is the cause for lanthanide contraction? March-2017, March-201
to
Ans: Due the imperfect shielding of one electron by another in the same set of orbitals. It is due to si
effect of4f electrons is less than 5d electrons with increase in nuclear charge along the series.
5. Give any twoconsequences of lanthanoid contraction. [March-2014, July-2016]
Ans: (i) Due to lanthanoid contraction the atomic radii of Zr (160 pm) and Hf (159 pm) is almost sa
they occur together. Hence it is difficult to separate them. [July-2014, March-2016, July-20
(ii) Covalent character of cations increases.
(iii) Electronegativity of trivalent ions increases slightly.
(iv) Basicity decreases from La to Lu
(v) Standard electrode potential (E°) values increases.
6. What is the common oxidation state of lanthanoides?
Ans: +3
7. Why Eu and Yb show +2 oxidation state?
Ans: Eushows +2 oxidation state to attain half filled orbitals
(4f')
Yb shows +2 oxidation state to attain completely
filled orbitals (4f*)
8. Why Ce shows +4 oxidation state?
Ans: Ce shows +4 oxidation state to attain [July-2015, March-2018]
noble gas configuration (Ce**
9. Name a member of the lanthanoid [Xe]4f)
series which is well known to exhibit +4 oxidatiol
Ans: Cerium (Z = 58) (NCERT Example)
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Publications
Jeevith
generalI characteristics of t49
Give
10. I anthanidcs ate silvery
lanthanides.
Ans: () white metals
Hardncss incrcases with increasing and tarnish rapidiy in ait.
(ü) atomic number.
(ii) They are goode conductors of heat
and clectricity.
All lanthanoid ions except La and Lu
(iv) ae coloured hoth in the solid state and in aqueous solutionis
duc the presence of clcctrons in f-orbitals.
(v) Lanthanide ions except f (La" andCet) and the type (YH and are all paramagnetic.
Give the chemical properties of lanthanoids.
' Lu)
1.
They burn with oxygen to form Ln,O,
Ans: 1.
4Ln +30, 2Ln,0,
2. Lanthanoids combine with hydrogen when they are gently heated forming hydrides.
3. Lanthanoids form corresponding carbides when thev are heated with carbon at 2773 K.
3Ln +CLn,C
2Ln +3CLn,C,
Ln + 2CLnC,
They liberate hydrogen from dilute acids. [July 2019)
4.
Ln+ dilute acids hydrogen gas
5. They burn in halogens to form halides.
2Ln +3X,2Lnx,
6. They react with water to form hydroxides with the liberation of hydrogen.
2Ln +6H,02Ln(OH), +3H,
-7. They form nitrides when they are heated with nitrogen.
2Ln +N,2LnN
sulphides.
They react with sulphur when they are heated to form corresponding
8.
2Ln +3SLn,S,
Give its use.
12. What is the composition of Mischmetall?
5%) + traces of S, C, Ca and Al.
Ans: Lanthanoid (95%)+ Iron (z to producebullets, shell and lighter
flint.
Mishchmetallis used in Mg– based alloy

4.6 The Actinoids

actinoids.
1. What are actinoids? to Lawarencium (Z= 103)
are called
thorium (Z=90)
Ans: The elements from
elements the added electrons enters into 5f orbitals.
Inthese configuration of actinoids.
Writethe general electronic
2.
Ans: [Rn]sr-16d-1 7s?
contraction? series is called actinoid contractio
3. What is actinoid atoms of actinoids across the actinoid
decrease in the size of [July-2014, July-2015S]
Ans: The gradual states. Why?
greater number of oxidation levels.
4. Actinoids show between 5f, 6d and 7s (July-2016, July-2018
comparable energies
Ans: Due to the actinoids?
common oxidation state of
5. What is the
Ans: + 3
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150

6. What are the oxidation states of actinoids?

The d-
and -.
Ans: +3, 44, +5, t6, +7.
7. What is
the highest oxidation state shown by actinoids? Or Name an element that shom
oxidation number among actinoids.
Ans: +7 (Np and Pu)
8. Giveany 4 general characteristics
Ans: (i) of actinoids.
Al actinides are radioactive.
(ii) They are silvery metals.
(iii) They are highly reactive in the finely
divided state.
(iv) They are paramagnetic nature.
in
(v) Actinides are slightly affected of
by conc. nitric acid owing to the formation protective
oie
(passivity) but highly affected by hydrochloric acid.
(Vi) They form OXocation in higher oxidation state
like Np0*, UO; etc.
9 Give any two differences between lanthanoids
and actinoids.
Ans:
SI. No.
1
Lanthanoids Actinoids
Electrons enters into 4f orbitals Electrons enters into 5f orbitals.
2. They are non radioactive except Pm Allare radioactive.
(promethium is radioactive).
3 Binding energies of 4f electrons are higher Binding energies
of 5f electrons are lesser
4 They are less basic. They are more basic.
5 Maximnum oxidation state is +4 They show maximum oxidation state upto +1
6 4f electrons have greater shielding effect
7
5f electrons have poor shielding effect.
Lanthanide contraction is lesser Actinide contraction is greater.
10. 5f electrons will be more effectively shielded from the
nuclear charge than the 4f electrons of the
corresponding lanthanides. Give reason.
Ans: Because in actinoids, the outer electrons are less firmly held
and are available for bonding.
11. Actinoid contraction is greater from element to
element than lanthanoid contraction. Why?
Ans: This is because 5f electrons will be less effectively [March-2018, March-201
shielded from the nuclear charge than the 4f electt
the corresponding lanthanides.
12. Study of actinide elemnents is
difficult. Give two reasons.
Ans: (1) Actinides are radioactive elements. [July-2017]
min - 24 hrs)
(2) Half life of actinides are very short (3
(3) They could be prepared in nanograms.
4.7 Applications of d and f-Block
1. Give somuses (applications) of d Elements
Ans: 1.
and f-block elements.
Iron and steel are used as construction
materials.
2. Some oxides of d-block elements
3. like TiO are used in pigment
MnO, is used in dry battery industry.
cells and Zn and Ni/Cd also
4. CuNialloy is used for making required in battery cells.
5.
coins (Silver and UK coins).
TiCl, with (CH))3Al (Ziegler-Natta
6. AgBr has special light sensitive catalyst) is used in the manufacture
properties in photography. of polythene.
7. d-block elements are used as
catalysts in many industrial productions.
udent's illuminator
II PU Che
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Publications
Jeevith
151
8.
PdCI, is used as the catalyst in the oxidation
of cthync to cthanal in Wacker process.
9. Nickclcomplexes are uscful in the polymerization
of alkyncs and other organic compounds like benzene.
10. UK copper coins are copper coatcd
stccl,

Multiple Choice Questions (MCQs)

The gradual decrease in atomic and ionic
1. 4. The common oxidation state of lanthanoids is
radiifrom Lanthanum to Lutetium is called a) +2 b) +4
a) Lanthanoid contraction d) +3
c) +1
b) Actinoid contraction 5. The composition of mischmetall is
c) Shielding effect a) Lanthanoid metal (-95%) + iron (-5%) and
d) Allof these
traces of S, C, Ca and Al
2. The almost identical radii of Zr and Hf is a b) Lanthanoid metal (-80%) + iron (-20%)
consequence of and traces of S, C,Ca and AI
a) Shielding effect
c) Lanthanoid metal (-60%) + iron (40%)
b) Actinoid contraction and traces of S, C, Ca and Al
c) Lanthanoid contraction d) Lanthanoid metal (~40%) + iron (-60%)
d) None of these and traces of S, C, Ca and Al
3. The cause of lanthanoid contraction is due to 6. Mischmetall is used in Mg-based alloy to
a) imperfect shielding of one electron by produce
another in the same shell a
bullets b) shell
b) imperfect shielding of one electron by c) lighter flint d) all of these
another in the different shell 7. Ziegler catalyst is
perfect shielding of one electron by another a) TiCI, + Al(CH,), b) TiCI, + Al(OH),
in the same shell c) TiCl, + AICI, d) TiCI, + AIBr,
d) perfect shielding of one electron by another
in the different shell
Answer Keys
45 67
a

Fillin the blanks by choosing the appropriate word from those

given in the brackets
Set -1
(variable oxidation states, Mn, Zinc, Cu, inner-d-orbitals, lanthanoid contraction)
The (n-1l) in [NGJ(n-1)d-"ns electronic
1. 3d series element has3.
completely filled .a configuration in its configuration stands for
ground state as well as in common oxidation Ans: Inner d-orbitals
state. 4. Transition metals show
Ans: Zinc Ans: variable oxidation states
2
has highest oxidation state in 5. The filling of 4f orbitals before 5d orbitals
its compounds results in a regular decrease in atomic radii
Ans: Mn called
Ans: lanthanoid contraction
<br>

Coordination UNI
Compounds 5
1,
What are co-ordination
Ans: Compounds compounds?
containing a central metal ion which is
co-ordinate bonds are surrounded by number of ligands linked
called co-ordination
Example: (i) K,[Fe(CN),1, compounds.
potassium ferrocyanide
2. What is adouble (i) K,[Fe(CN),], potassium ferricyanide.
salt?
Ans: Adouble salt one
is which is formed
all the constituent by two simple salts
ions present in when it is dissolved
Example: (i) Potash it. in water, it dissociatest
alum - K,SO,
Al,(SO,), 24H,0
(i) Ferrous ammonium
sulphate (Mohr's
3. Give any two
differences between salt) - FeS0, (NH,), SO,
Ans: double salt
and complex salts -6H,0
(co-ordination
SI. No. compounds).
Double salt
1
It loses its identity
in solution. Complex salt
2.
Itdoes not contain It retains its
co-ordinate identity in
3. bonds. solution.
It is stable It contains
in solid state. co-ordinate
4:
It shows normal
bonds.
It is stable
4. Name valency. in solid state
Ans: Haemoglobin thetransition and in aqueous
metals present It shows primary
Chlorophyll - Iron in the, complexes valency
solution.
Vitamin-By2 -Magnesium haemoglobin, and secondary
valency.
Addition -Cobalt chlorophyll
of excess
The conductivity of AgNO, and vitamin –
a toan aqueous
ofthis solution B2:
1:l electrolyte
correspondssolution
Ans: 1:2 electrolyte to of 1 mole
(c)
1:2electrolyte of PaCl,.4NH3
5.1 Werner's b
1:3 electrolyte gives-2
d) moles
1.
What are Theory 1:4 electrolyte of Agu
thepostulates of Coordination
Ans:
() Ametal ofWerner's
atom theory
Student's
(a)Primary incoordination
valences
Compounds
of co-ordination
illuminator compound compo
pOS IJul
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Publications
Jeovith
161
Secondary valenccs,
(b)
The prinary valences are ionisable
(i) and arc satisficd
The sccondary valences are non only by ncgative ions.
(ü) ionisable and are or negative ions
(called ligands) satisficd cither by neutral molecules
(ii) Primary valenccs correspond to the oxidation state valences
correspondto the co-ordination of the central metal atom and secondary
number.
(iv) Primary valence may be variable but secondary
valences are fixed.
(v) Primary Valence 1s non-directional. But secondary valences are directional. So comple
different geometrical shape. Coordination
number 4 gives tetrahedral geometry.
umber 6 oives octahedral geometry and coo
Which type of ions satisfics the primary
valency of the complex?
2. Negative ions or anions.
Ans:
On the basis of the following observations made with agueous solutions, assign secondary valences to
metals in the following compounds. (NCERT Example)

Formula Moles of AgCl precipitated per mole of the

compounds with excess AgNO,
() PdCI,4NH, 2
(ii) NiCI,.6H,0
(iii) PtCI,.2HCI 0

(iv) CoCl,.4NH, 1.

(v)PC,.2NH,
= (ii) Secondary 6
Ans: () Secondary 4 =
Secondary = 6 ige (iv) Secondary=6 () Secondary 4
(ii) are
with excess of AgNO; solution, three moles of CI ions
4. The complex CoCl,6NH, is treated and secondary valency of cobalt
in the
of AgCI. What is the primary
precipitated as three moles-
complex?
. 3AgCl
Ans: CoCI,6NH, +3AgNO,
(3 molCI ions) are
three primary valencies and 6 NH molecules
are ionically bound through
This indicates that 3CI ions
cobalt metal ion through six secondary valencies. secondary =6.
bound to the central valency =3and
as [Co(NH)6]Cl,. Primary is
The complex can be wrítten
in which no AgClppt is formed when it
PtCl,.2NH;
valence of the complex
5. What is the secondary
treated with AgNO, solution? complex of the type [Pt(NH;);CI;].
can form
AnS: 4 because PtC,.2NH,
Werner's theory.
secondary valences of central
of a
limitations or demerits primary and
6.
Give any two a ligand can satisfy
both
not explain how
Ans: () This theory does
formation of complex ions.
metal ion. interpretation of
offer electronic compounds.
This theory does not
optical properties of co-ordination
(") explain magnetic and
(iii)This theory does not

II PU Chemist
<br>

162

Multiple Choice COordinalion

1, In coordination
compounds metals Questions (MCQs)
show
types of linkages (valences) (a) oxidation number
(a) one
(b) two (b) coordination
(c) number
thrce (c) ions in the solution
2 (d) zerto
The primary
valences of (d) none of these
compounds are coordination
(a) ionisable and 4. The complex CoCI,·
satisfied by negative 4NH,
excess of AgNO,
solution, one is
ions treetes
(b) non ionisable and
satisficd by positive precipitated. mole
(c) non ionisable ions The primary
and satisficd by negative valence of this complex is
and
(d) ionisable and ions
satisficd by positive (a) 6 and I

ions (b) 6 and 2

3. Secondary (c) I and 6
valence of (d) 3and
compounds is equal to coordination

Answer Keys
123|4
|b a b

5.2 Definitions of Some

Important Terms Pertaining
Coordination Compounds to
1. What isco-ordinate bond or dative
Ans: It is a type of covalent bond?
bond in which one the
2. of atom/group donates lone
What is central metal atom or pair of electrons.
Ans: The metal atom or ion ion?
surrounded by number
called central metal atom or of neutral molecules or negative
ion, In a complex compound ions (ligands) in a compla
pair acceptor) central metal atom/ion acts as
Lewis acid (ele
3. What is co-ordination entity?
Ans: A central metal atom bonded
coordination entity. by fixed number of ligands
with a definite geometrical arrangement
is cak
Example: [CoCI,(NH,),] a
is co-ordination entity
ions. in which Co is surrounded
by 3 NH, molecules and3

What are ligands?

Ans: Ligands are
ions or molecules which can
through a co-ordinate bond. donate one or more lone
In a complex compound pairs of electrons to the central
ligands acts as meti
Name the types of ligands. Lewis base (electron
pair donar)
ns: i) Monodentate
ligands.
(ii) Bidentate ligands.
(ii) Polydentate ligands.
(iv) Ambidentate ligands.
What are monodentate ligands?
s: The ligands which can
donate only one lone
ligands. pair of electrons to the
central metal ion are called monou
Example: (a) Neutral
ligands: NH, (ammine),
H,0 (aqua), Co (Carbonyl),
NO (Nitrosyl).
lent's illuminator
 Jee
<br>

(b) Negativcly
charged ligands: 163
(Fluorido), SCN CN
(Cyanido),
(thiocyanato), CT
(Chlorido), Br (Bromido), I (lodido), F
(nitrato). ClH,CO0
(acctato),
SO (Sulphato), CO} (Carbonato), OH(hydroxo), O(oxo), NO; (nitro), NO,
Positively charged ligands: ONO (nitrito).
NO; (nitronium), NO*
(nitrosonium)
7.
What arebidentate
ligands or Didentate
The ligands which can
donate two lone ligands? Give examples.
Ans:

Example: pairs of electrons

to the central metal ion are called bidentate ligands.
(i) Oxalate ion (ox)
(ii) Ethane -1,2- diamine (en)
COO or
C,0,
H, N-CH, -CH, NH,
CO0
8. What are polydentate ligands?
Ans: The ligands which can donate many lone pairs
called polydentate ligands. of electrons to the central metal ion to form a
complex are
Example: EDTA (Ethylene
diamine tetra acetate ion)
EDTA is a hexadentate ligand.

:0:
:0:
-CH,
:N CH, CH, :
CH-ö:
:0-Ç-CH, CH, 0:

:0: :0:
9. What is chelating agent? Give an example.
Ans: A di or poly dentate ligand that uses two or more donar atoms to bind a single metal ion is called chelating
ligand. Example: EDTA
10. What is chelating complex?
Ans: A complex in which a di or poly dentate ligand is bonded-to a central metal atom or ion with two or more
coordinate bonds is called chelating complex.
11. What are ambidentate ligands? [March - 2018]
Ans: The ligands containing more than one donar atoms but which can ligate (link) through only one donar atom
are called ambidentate ligands.
CN group can ligate through C
or N atoms.
Example: (1)
M+CN M-NC"
. Isocyanido
Cyanido
atoms.
(i) NO; group can ligate through N orO
M-NO, M-0-N=0 Nitrito
Nitro
or nitrogen.
(ii) SCN can ligate through sulphur
M+SCN MNCS
Isothiocyanato
Thiocyanato s
I| PUChemist
Student's illuminator
<br>

164 Coordination

12, What is denticity?

Ans: The number of ligating groups present in a ligand is called denticity.
Example: i) The denticity of oxalate ion 2.
(ii) The denticity of ethanc-1, 2-diamine is 2.
(iii) Thc denticity of EDTA is 6.
13. What is co-ordination number?
Ans: The number of monodentate ligands or the number of coordinate bonds present in a complex
is
co-ordination number. Examples:
Metal ion Complex Co-ordination number
Ni [Ni(CO),J 4

Cu2+ [Cu(NH,),P* 4

Fet [Fe(CN), ] 6

Fe* [Fe(CN), 6

Co+ [(Co(C,0,), 3x2 = 6

14. What is co-ordination sphere?
Ans: The central metal atom and ligands which are enclosed in a square bracket is called coordination snber
Example: The co-ordination sphere in K,[Fe(CN),] is [Fe(CN),J
15. What are counter ions in coordination.compounds?
Ans: The ionisable groups of coordination compounds are present outside the coordination sphere are called
counter ions. The counter ion in K[Fe(CN),] is K* and [Co(NH)6]Cl, is CI.
16. What is co-ordination polyhedron?
Ans: The spatial arangement of ligands around central metal atom or
the geömetrical shape of the compler
called co-ordination polyhedron.
Example: [Ni(CO),]- Tetrahedral,
[Co(NH,),* -Octahedral, [Cu(NH,),* -squareplanar
17. What are homoleptic complexes? Give examples.
Ans: The complexes in which the central metal ion is [July-2016]
surrounded by only one type of ligands are called
homoleptic complexes. (i) [Ni(CO),] (ii) [Fe(CN),J
18. What are heterolepticcomplexes?
Give examples.
Ans: The complexes in which the central
metal ion is surrounded by more
heteroleptic complexes. than one type of ligands are cak
Example: [Pi(NH,),C1,],
[Co(NH, ),CI,I'
19. What is a complex ion?
Ans: It is a charged species contäining
central metal ion surrounded
Example: [Co(NH,),CI,J, by ligands.
[Fe(CN), J
20. What isprimary valency or
oxidation state of a
Ans: The charge on the central metal central metal atom?
atom in a complex is
number. called primary oxidatot
valency or
oxidation state Or
<br>

Publications
Joevith 165
Calculate the oxidation state of
21.
the central transition metalIion in the following complexes.
Ans: Iron in K,[Fc(CN),l
(i) (ii) Iron in K,[Fe(CN),] To find oxídation state,
K,[Fe(CN),]=0 For neutralcomplex =0
K,[Fe(CN),]=0
4K + Fc+ 6CN =0 Complcx ion =Charge
3K* + Fc + 6CN =0 = –1
4(+1) + Fe + 6(-1)=0 For CI, Br, F,CN, NO,
3(+1)+ Fe + 6(-1) =0 For SO4, CO, =-2
4+ Fe -6=0 3+ Fe-6=0 Na, K=+1
Fe-2=0 Fc -3=0
Fe= +2 Fe=+3
Fe (II) Fe (III)
Co in [Co(NH,),JCI, (iv) Niin [Ni(CO)|
(iii)
[Co(NH,).]C1, = 0 [Ni(CO),]=0
Ni+4x CO=0
Co +6x NH, +3CI =0
Ni+4(0) =0
Co + 6(0) +3(-1) =0
Ni=0
Co
-3=0 ..
Ni(0)
Co =+3
Co (II)
Give examples.
Name the types of complexes.
i2.
Complexes are of three types: (ii) Neutral
complexes
Ans: (ii) Anionic complexes
complexes
(i) Cationic
are cationic complexes? Give examples. cationic complex.
What it is called as
23. ve charge, hexaammine cobalt (III)
Ans: complex ion has +
Ifthe Cuprammonium ion, [Co(NH, ),“
Example: [Cu(NH,),1* examples.
are anionic complexes? Give as anionic complex. ferricyanide ion.
24. What
the complex ion
has ve -
charge, it is called
ion,
[Fe(CN),I
Ans: If Ferrocyanide
Example: [Fe(CN), J examples.
complexes? Give neutral complex. carbonyl.
What are neutral species, it is called
[Fe(CO),l iron penta
25. a neutral
the complex entity is tetracarbonyl
Ans: If Nickel
Example: [Ni(CO),] (MCQs)
Choice Questions to a metal is
ion
bound
Multiple When a ligand
is
donor atoms, the
ligand
3.
through its several
bound to the central be
or molecules entity are called said tomonodentate ligand
I. The ions coordination (a)
the
atom/ion in didentate ligand
(b)
(a) Ligands dentate ligand
Coordination entities (c) poly these
(b) none of more donor
Coordination spheres (d) uses its two or
(c) Polydentate ligand
to bind a single metal
(d) Lewis
acids central metal 4. atoms simultaneously
the
coordination entity, said to be ligand
ion isAmbidentate
In a as
atom or ionacts (a)
(b)-Chelate ligand Chemistry
(a) Lewis base ell PU
(b)
Arrhenius acid
acid
<br>

166
Coordination
(c) Didentate ligand Co
(d) All of these In thecomplex, [Fe(C,0,), the
is
5, Ligand which has two coordination number of Fe
different donor atoms (a) 3 (b) 4
and cither of the two ligates
in the complex is (c) 2 (d) 6
called
(a) Ambidentate ligand 7. The oxidation number of Cu in
(Cu(CN
(b) Chclate ligand (a) +1 (b) +4
(c) Didentate ligand (c) +2 (d) +3
(d) Monodentate ligand following is homg
Which of the
complex? (b) [Co(NH,),C,
(a) CoNH, ), JCI,
(c) [Co(NH,),CI, JCI, (d)
all of these

Answer Keys
2 3 4 5 6 7 8

a b a d a

5.3 Nomenclature in Coordination Compounas

1. Rules for IUPAC naming:
Ans: 1. no matter whether the complex ion is cation or anion, ah
10 name a coordination compound.
name the cation before.the anion.
2
In naming the complex ion:
or ion.
(a) Name the ligands first, in alphabetical order, then the metal atom
is replaced by '0' iie., "-ide
(b While naming anionic ligands, the terminal e' of the ligand
ido (e.g. chloride as chlorido), "-ate'" as "ato" (e.g. sulphate
as sulphato, nitrate as nitrato),
names
as ito' (e.g. nirite as nitrito). Neutral ligands are named with the special
-ite"
indicated in Table 3.
Anionic Ligands Names Neutral Ligands Names
Br bromido NH, Ammine
F fluorido H,0 Aqua
CI chlorido NO Nitrosyl
OH hydroxido CO Carbonyl
CN cyanido C,H,N Pyridine
C,0} Oxalato H,NCH,CH,NH, ethane-1,2-diamine

cO; carbonato PPh3 triphenyl phosphis

CH,CO0 acetato

NO; nitrito-N
ONO nitrito-O
SCN thiocyanato-S
NCS thiocyanato-N

dent's illuminator
|| PUChemis
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Publications
Jeevith 167
Greck prefixcs are uscd
3.
prefixes di-, tri- and to designate the numbcr
tctta- ctc., are of cach type of ligand in the complex ion.The
already contains a Greck prcfix uscd to indicate the number of monodentate ligands. If the ligand
(c.g, cthylenceliamine) or iC it is nolvdentate
tris-, tetrakis-, pentakis-, are ligand the prenke
uscd.
After naming nc ngands, name the
central metal 1C he connley ion is a cation, the
with normal name. For Cxample, Co metal 1s na
in a comnlex cation is named cobalt
the complex i0h is an anion, the name and P
is calleo p
of he metal ende uith the suffix -ate. For example, o m
complcx anion Is called cobaltate and P is
called nlatinoto Eor some metals, the Latin names
in the complex anions c.g. Fe is
called ferrate (not ironate).
Name of metals in anionic complexes
Name of Metal Name in an Anionic Complex
Iron Ferrate
Copper Cuprate
Lead Plumbate
Silver Argentate
Gold Aurate
Tin Stannate
5. Following the name of the metal, the oxidation state of the metal in the complex is given as a Roman
numeral in parentheses.
6. To name a neutral complex molecule, follow the rules of naming a complex cation.

2 Give the IUPAC names for the following complexes.

Ans: (a) Cationic complexes:
Oxidation state in name of simple anion out
Nameof ligands
Name of transition metal + Roman number side the complex
alphabetical order

i. [Co(NH,),JC1, hexaamminecobalt (II) chloride.

[Co(NH,), CIjCl, pentaamminechloridocobalt (III) chloride.

ii.
tetraamminediaquacobalt (III) chloride.
iii. [Co(NH,),(H,0),JC1,
chloride.
iv. [Co(en), JCI,tris (ethane -1, 2-diamine) cobalt (II)
pentaamminecarbonatocobalt (III) chloride.
V. [Co(NH,), (CO,)JCl
diamminechlorido(methylamine) platinum (II) chloride.
vi. [Pt(NH,), Cl(NH, -CH,)JCl
(b) Anionic complexes:
Latin name of Oxidation state in
Name of the simplecation Name of the
ligands(alpabeticalorder) transition metal Roman number
outside the complex
hexacyanidoferrate (I)
i. K,[Fe(CN),] potassium
(III)
ii.
potassium trioxalatoferrate
K,[Fe(C,0,),]>
tetrachloridopaladiate (I)
iii. K,[PdC1,] potassium
hexafluoridocobaltate (I)
iv. Na,[CoF] sodium
PU Chemist

Student's illuminator
<br>

Goordination
V. [NiCi, tctrachloridonickelate (11)
ion
vi. [Ni(CN),J tetracyanidonickelate(II)
ion
vi. Hg[Co(SCN),] mercury tctrathiocyanato-S-cobaltate
n. ()
PI(NH,)BrCl(NO,)T ammincbromidochloridonitrito -
N-platinate (
(c) Neutral complexes
Name of Oxidation statein
Common name of
ligand with alphabetical order roman letter
transition metal
i. [Ni(CO),] tetracarbonylnickel (0)
ii. (PBrCi(CaH,N)NH,] ammincbromidochloridopyridineplatinum(II)
i. [PICl,(NH3),] diamminedichloridoplatinum(I)
orACnames of doublecomplexes (both cation and anion arecomplexes)
[Ag(NH,)-1[Ag(CN),] diamminesilver(I) dicyanidoargentate()

PNH)][PtCl] tetraammineplatinum(I) tetrachloridoplatinate()

tetraamminedichloridocobalt(III)hexacynidochromate(III)
iii [CoCl,(NH;).],[Cr(CN)]
iv [PICI,(NH).1[PtCL] tetraamminedichloridoplatinum(IV) tetrachloridoplatinate(|1)
3. Rules to write the formulae of the complexes
Ans: The following rules are applied while writing the formulae:
1. The central atom is listed first.
2. The ligands are then listed in alphabetical order.
abbreviation is used to determine
3. In case of abbreviated ligand, the first letter of the
position of the ligand in the alphabetical order.
the entire coordination entity, whether charged or not, is enclosed in squs
The
4
formula for
brackets
sphere.
5. There should be no space between the ligands and the metal within the coordination
coun
6. When the formula of a charged coordination entity is to be written wvithout that of the
jon, the charge is indicated outside the square brackets as a right superscript with the numt
before the sign. For example, [Co(CN),J, [Cr(H,0),1+, etc.
7
The charge of the cation(s) is balanced by the charge of the anion(s).
4. Write the formulae of the complexes.
i.potassium hexacyanidoferrate (II) K,[Fe(CN),]
ii. potassium tetrahydroxidozincate (1) K,[Zn(OH),]
iii. potassium trioxalatoaluminate (III) K,[AI(C,0,),]
Ív. potassium trioxalatochromate (IIl) K,[Cr(C,0,),J
V
tris (ethane-1, 2-diamine)chromium (III) chloride
[Cr(en), jCl,
vi. triammine triaquachromium (IIl) chloride
[Cr(NH,), (H,0),]Ci,
dent's illuminator
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Publications 169
Jeevith
tris(cthane--1,2-dianminc)cobal(Ill) - NH,),),(SO),
vi. sulphate ->
[Co(H,N -CH, -CH,
or [Co(cn):]:(SO,),

viii.
dichloridobis(cthanc-1, 2-diaminc) cobalt
(II) ion [CoCI, (en), 1'
Aichloridobis(cthanc-1, 2-diaminc)
cobalt (III) chloride [CoCI, (en), ]CI
pentacarbonyliron (0) [Fe(CO),].

Multiple Choice Questions (MCQS)

Pe IUPAC name of [Co(NH,),(H,0)CIjCI, coordination compound
2. The formula of the (III) chloride is
1. tetramminediaquacobalt
is
tetrammineaquachloridocobaltate a) [Co(NH,), (H,0),JCI,
a) (II)
chloride b) [Co(NH,),2H,0]CI,
b tetrammineaquachloridocobalt (II) c) [Co(NH,),2H,O]Cl,
chloride [Co(NH,), (H,0),]Cl,
d)
aquatetraamminechloridocobaltate (II)
chloride
d) chloridoaquatetraammine cobaltate (II)
chloride
Answer Keys
1 2
b

5.4 Isomerism in Coordination Compounds

What are isomers? atoms a
1.
having the same chemical formula but differ in their arrangement of
Ans: Two or more complexes
called isomers.
2. Name the types of isomerism in complexes.
Ans: Isomerism is of 2 types:
isomerism
(i) Structural isomerism (ii) Stereo
isomerism.
3. Name the types of structural
Ans: Structural isomerism is of 4 types:
(i) Ionisation isomerism
(ii) Linkage isomerism
or hydrate isomerism
(ii) Solvate isomerism
(iv) Co-ordination isomerism [July-20167 (NCERT Intext quest
Give an example. wa
4. What is ionisation isomerism? but they give different ions when dissolyed in
same molecular formula
Ans: Complexes having the isomerism.
isomers and the phenomenon is called ionisation
called ionisation
and [Co(NH,),Br]SO,
Example 1: [Co(NH,),S0,]Br comple
the second complex gives SOf in water. The first
The first complex gives Br
in water and
second one gives white ppt with BaCl, solution.
solution and
pale yellow ppt with AgNO,
and [Co(NH,),SO,JCI
Example 2: [Co(NH,), CIIso,
I| PU
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Coordination Compe,
170
(March-2018,
5. What is linkage isomerism? Give an example. towards ,
donate clectrons
Ans: Complexes having the same molccular formula but differcnt ligating atoms to
isomerism.
metal ion arc callcd linkage isomers and the phenomenon is called linkage

[Co(NH,), NO,J" and [Co(NH, ), ONOJ*

(Co)
Inthe first complex nitrogen (N) donates electrons to the central metal ion (Co)
In the second complex OXygen (0) donates elcctrons to the central
metal ion

6. What type of ligand can give rise to linkage isomerism?

Ans: Ambidentate ligand
an exanmple molecules in the inne
7. What is solvate isomerism or hvdrate isomerism? Give of water
different umber and the phenomenoni
Ans: Complexeshaving same molecular formula but or hydrate isomers
solvate isomers
coordination sphere inside the complex are called
called solvate isomerism or hydrate isomerism.
Example:
() [Cr(H,0),JCI, and [Cr(H,0), CIjCI, ·H,0
(1) [Co(H, 0), JCI, and [Co(H,0),CIjCI, ·H,O
Give an example. cationic sr
8. What is co-ordination isomerism? ligands are interchanged between the
same molecular formula but the the phenomenon is call:
COmplexes having the isomers and
us: anionic entities of different
metal ions are called
co-ordination
[Cr(CN),1[Co(NH,)%]
isomerism. Example: [Cr(NH,), J[Co(CN),] and
co-ordination
ligands around
9. What is stereo isomerism? formula but differ in the spacial
arrangement of

having the same molecular

Ans: Compounds phenomenon called stereo isomerism.
atom are called stereo isomers and the
central metal
10. Name the types of stereo isomerism.
Ans: Stereo isomnerism is of 2 types:
() Geometrical isomerism
(ii) Optical isomerism
Write a note on geometrical isomerism. [March-2014, July-2015, July-2017, March-2019,July-2022]
ns: )) Thís type of isomerism arises in heteroleptic complexes due to ligands occupying different positions
around the central metal atom or ion.
(i) The ligands occupy positions either adjacent to one another or opposite to one another. This is also
called cis-trans isomerism. If similar ligands are adjacent to each other,
the resulting isomer is called
cis-isomer. If similar ligands are opposite to each other, the
reulting isomer is called trans isomer.
(iii) The complexes having the coordination numbers 4
(with square planar geometry) and 6 (octahedral
geometry) usually show geometrical isomerism.
(iv) Geometrical isomerism is exhibited
by complexes of the type MX,L
octahedral complexes of the type MX,Ly (square planar complexes) and
and MX;Lg.
Example l: (Pi(NH;)>Cl,]
C1 C1
NH, NH,

NH,
NH, CI
cis
Geometrical isomers (cis trans
and trans) [Pt(NH,),CL,]
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Publications
171
Jeevith
Example 2: [Co(NH,),CI,1.

T
C

CI CI
NH,
H,N NH,
Co
H,N
NH,
H,N NH,
NH,
cis C
trans
Geometrical isomers (cis and trans)
of [Co(NH),CIH)
(v) Square planar complex of the type MABXL (where A B L are unidentate liganas) S
X

isomers among them two cis and one trans isomers.

(vi) Geometrical isomerism is also possible in coordination compounds having bidentate ligands
type MX(L-L)2. Example: [CoClh(en)]*.
o
e
Cl
en
en en

C1
en
cis trans
Geometrical isomers (cis and trans) of [CoC1,(en),]
isomerism called fac and mer isomerism which occurs in octahedral
(vii) Another type of geometrical at
type If three donar atoms of the same ligands occupy adjacent positions
complexes of the Mab;]. the
corners octahedral face, the resulting isomer is called facial isomer (fac isomer). lf
the of the resulting isomer is called
are around the meridian of the octahedron, the
positions of the ligands
meridional (mer) isomer.
Example: [Co(NH,), (NO,), *
3+

NH,
NH, NO,
O,NZNH, HN
Co

SNH, O,N NO,

NO,
NH,
mer

fac-.
isomers of [Fe(NH)2(CN)|.
Draw the geometrical

NH,
NH,
NH, NC CN
NC,
Fe
Fe
CN NC CN
NC
NH,
CN trans
ciS
 Why geometrical
<br>

ligands coordinatedisomerism is not possible Coordination Comp

with the central in tetrahedral
Ans: Tetrahedral metal complexes
complexes do ion? having two different unidenta
ligands attached not show geometrical
to the central isomerism because (NCERT Example)
14. What metal atom arc the same the relative positions of the unident
is optical isomerism? with respect to
Ans: The isomers cach other.
which are mirror
(enatiomers) and images that cannot
the phenomenon is be supcrimposed on one optical isomes
called optical isomerism. another are callcd
15, What is chiral mnolecule?
Ans: The molecules or
ions that cannot be superimposed are
16. What type of molecules rotates called chiral molecule.
Ans: Chiral molecules the plane polarized light
and optically activei
17. What is laevorotatory substance?
Ans: A chiral nolecule which rotates
the plane polarized light to the left is called laevorotatory substance.
18. What is dextrorotatory substance?
Ans: A chiral molecule which rotates the plane dextrorotatory substance.
polarized light to the right is called
19. In which type of coordination compounds the ontical isomerism is common.
Ans: Octabedral complexes involving didentate ligands or bidentate ligands
20. Write the optical isomers of [Co(en)3]
Ans:
3+
3+

en

en en

en
en

dextro mirror laevo

cis [PtCI,(en),].
Write the optical isomers of
ns: +2 +2
Cl
Cl
Cl Cl

Pt Pt en

en en
dextro
mirror laevo
Note: Only cis isomer shows optical isomerism.
ich isomer of (CoCIh (en)2] cannot show optical isomerism? and why ?
Trans isomer because in trans isonmer mirror images are or trans
Superimposable isomer does not have mim
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Publications
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173
Out ofthe following two coordinntion
entitics which is
(a) cis - |CrCl,(ox),) (b) trans - chiral t(optically active) [April-2022]
|CrCl(ox):'
Ans:

OX CT

OX Cr 0X

C1
OX

(a) cis - [CrCl,(ox),]

-
(b) trans - [CrCl(ox),
is [CrCl;(0x)2] 1s optically active because it has mirror image. Trans isomer does
-nge Hence it does not show optical isomerism. n0t nave

24.
Indicate the types of,1somerism exhibited by the following comnlexes and draw the structures oI these
isomers:
) K{Cr(H;0).(C;0.)2l (i) [Co(en),|Cl, (ii) [Co(NH), (NO)](NO)2 (iv) [Pt(NH)(H,0)Cl3]
Solation: (1) [Cr(H,0),(C,0,)aT ion shows both geometrical and optical isomerism.
(a) Geometrical isomers

OH,
17OH OH,
OX
OX ox

OX
OH,
ci trans
(b) Optical isomers (d- and ) of cis

OH,
OH,
Cr Ct OX

OX Ox
Mirror
d
in text page number 175)
(ii1) Shows optical isomerism (Discussed
(NO3)2, [Co(NH)(NO,)] (NO,) (NO,)
(ii) Ionization isomers: [Co(NH;)s(NO:)]
(NO3)2, [Co(NH:)5(ONO)] (NO,)2
Linkage isomers: [Co(NH3)5(NO:)]
(iv) Geometrical isomers (cis and trans) H,N
CI
NH, Cl

H,0
CI C OH,
trans
cis
<br>

Coordination
1, Geometrical Multiple Choice Questions
isomerism
a) Homoleptic arises in (MCas)
complexes d) all of these
b) Cationic complexes a
coordinat
6.
Linkage isomerism arises in
c) Anionic complexcs compound containing
d) Heteroleptic a) monodentate ligand
complexes
2. b) didentate ligand
Geometrical isomers
coordination numbers generally found with c) polydentate ligand
d) ambidentate
ligand
a) 4 and 6
when
c) 3 and 6 b) 2 and 4
7. Coordination isomerism arises
between cationie.
d) 2and 6 a) interchange of ligands
3. different metal
Square planar complex anionic entities of i
(where A, B, X, L are of the type MABXL present in a comnplex
three isomers. Among unidentates) shows ligands between two
Catic

them b) interchange of
a) twWo
cis and one trans complexes two anis
b) one cis and two trans c) interchange of ligands between
all three are cis only complexes
catios.
d) all three are trans only d) interchange of ligands between
present
complex and anionic complex
4. Geometrical isomerism is not possible
(a) Square planar complexes
for different complexes.
(b) Octahedral complexes 8
The isomers an
(c) Tetrahedral complexes [Co(NH, ),S0,]Br and [Co(NH,),Br]So,
(d) All of these example for
5. In facial (fac) isomer of the octahedral a) coordination isomerism
complex of the type [Mabs], b
linkage isomerism
a) three donor atoms of the same ligands c) ionisation isomerism
occupy adjacent positions at the corners of
d) solvate isomerism
an octahedral face.
Number of stereoisomers exhibited br
b) three donor atoms of the same ligands 9.
Occupy opposite positions at the corners of [Co(en),CI,]" is
an octahedral face, a) 2 b) 5
c) three donor atoms of the same ligands c) 3 d) 4
occupy meridian of the octahedran.
Answer Keys
1 2 7
6
a C d a C C

5.5 Bonding in Coordination Compounds

10. What
are the salient features of valence
bond theory?
Ans: According to VBT,
() The metal atom or ion under
hybridisation to yielda set of
the influence of ligands can use
equivalent hybrid orbitals
its (n -
1)d, ns, np nd orbitals
(ii) The geometrical of definite geometry.
shape of the complex ion depends on
the type hybridisation the
sp- hybridisation -
Linear of metal orbitals.
sp- Trigonal planar or planar triangular
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Publications
Jneith 175
sp'hybridisation -tetrahcdral
dsp-square planar
d'sp or sp'd- octahcdral
dsp- trigonal bypyramidal
a'sp' or sp'd- pentagonal bypyramidal.
The hybrid orbitals of the metal
(ii) honds ion overlap axially with orbitals of the ligands to form co-ordinate

.
Note:
(i)
(sigma)

if (n -
bctween metal and ligands.

orbitals are used for hybridisation, the comnleyes are called

1)d
inner orbital compleXes.
(i) If nd orbitals are used for hybridisation, the complexes are called outer orbital complexes
Gii) If a complex contains one or more unpaired electrons it
unpaired electrons, it is diamagnetic.
is naramagnetic. If it does notcoe
iv) Strong ligands ikeCO, NH3, CN etc causes pairing ofelectrons a9ainst Hund's rule in
metal ion. Sothey form inner orbital the Central
complexes.
(v) Weak ligands like F,Ci,Br,I etc do not cause nairing ofelectrons against Hund's rule. So they
form outer orbital complexes.
11.
On the basis of valence bond theory (VBT) explain the hybridisation, geometrical shape and magnetic
nroperty of [Co(NH,), , hexaammine cobalt (|II) ion. [July-2016, March-2019]
Ans: In[Co(NH),1*, the cobalt ion is in +3 oxidation state and has the electronic configuration [Ar]34s".
Orbitals of Co* ion are represented as

3d 4s 4p
When strong ligand, NH, is approaching towards central metal ion, rearrangement of electrons takesplace
against the Hund's.rule.

3d 4s 4p!
undergo hybridisation to form six sp³ hybridised orbitals
Two d orbitals, one s orbital and three p orbitals
corners of an octahedron.
of cobalt pointing towards the six

six 'sp hybrid orbitals

Co+ overlapswith orbitals of six ammonia ligands and six pairs of electrons
These six hybridised orbitals of
donated by six ammonia ligands to form six coordinate bonds.

six dsp' hybrid orbitals

NH,
with six pairs of electrons of
ligands
unpaired
geometry and is diamagnetic because of the absence of
Thus, the complex has octahedral hybridisation, the complex
complex, since the inner d orbital (3d) is used in
electron. In the formation of this
an orbitalcomplex or low spin complex or spin paired complex.
(Co(NH,)13+ is called inner II PUChemist
<br>

Jeevith,

Four
dsp' hybrid orbitals with 4
complex
pairs of electrons ofligands diamagnetic complex
undergocs dsp'
the geometry is square planar. is
It
Since the hybridisation,
abscnce of unpaircd clectrons. During inner 3d-orbitals is
due tothe the formation of the complex, since the
complex or Iow
used in the hybridisation [Ni(CN),12 is called inner orbital complex or spin paired
spin or hyper ligand complex, or
On the basisVBT explain the hybridisation, geometry and magnetic property of [NiCLJ
of
14.
tetrachlorido nickelante(ll) ion. (March-2018]
The ONidation state of nickel in [NiCI,j2 is+ 2. The outer clectronic configuration of nickel(+2) 3440.
is
Ans:

3d 4s 4p'
When weak ligand, Cl
central metal ion, one 4s and three 4p orbitals
hybridised to
w
is approaching towards
yield four sp' hybrid orbitals pointing towards the four cormers of tetrahedron.

3d 4s 4p

Four sp hybrid orbitals

a
Each CI ion donates pair of electrons to four sp³ hybrid orbitals to form tetrahedral complex.

Since the complex undergo sp hybridisation, the complex is tetrahedral. It is paramagnetic complex due
tothe presence of two unpaired electrons in 3d orbitals.
The spin magneticmoment of (MnBr4 is 5.9 BM. Predict the geometry of the complex ion.
According tothe spin only formula, if magnetic moment is 5.9, the number of unpaired electrons is 5. It is an
outer orbital complex with coordination number 4. Br is a weak ligand. The electrons in 3d orbitals of Mn
are not paired up. Therefore the shape of the complex is tetrahedral with sp hybridisation.
A six coordinated high spin complex is bonded to weak ligands. What would be the hybridisation of
the central metal?
sp'a
Can hybrid orbitals actually exist? If not, what is the real meaning?
Hybrid orbitals do not actually exist. But hybridisation is a mathematical manipulation of wave equation for
he atomic orbitals involved.
NiCIJ is paramagnetic while [Ni(CO)| is diamagnetic though both are tetrahedral. Why?
n[NiCIJ, Ni is +2 oxidation state with the configuration 4s". CI is weak ligand. It cannot pair up the
3
lectrons in 3d orbitals. Hence, it is paramagnetic. In [Ni(CO)A), Ni is in zero oxidation state with the
onfiguration 3d' 4s'. In the presence of CO strong ligand, the 4s electrons shift to 3d to pair up 3d electrons.
hus, there is no unpaired electron present. Hence, it is diamagnetic. In both complexes Ni undergo sp
ybridisation.
<br>

Coordination
176 Compound

property
12, On
the basis VBT explain the hybridisation, geometrical shape
of and magnetic
April-2022/
hexafluorido cobaltate (III) April-2016, July-2015, July-20I7, +3
ion. of cobalt in oxidation
Ans: In
this complex,the oxidation statc oof Co is +3. The clectronic configuration state
i
[Ar]3^46,
Orbitals of Cot ion are represented as

4p 4d
3d 4s hybridised to yieldsix
Since F
ion provides a weak ligand field, one 4s, three 4p andtwo outer 4d-orbitals
sp° hybrid orbitals pointing towards the six corners of an octahedron.

4s 4p 4d

six sp' hybrid orbitals

These six hybridised orbitals of Co3t overlaps with orbitals of six F- 1igands and six pairs of electrons
donated by six F to form six coordinate bonds.

six sp° hybrid orbitals with six pairs of electrons from ligands.
Thus, the complex has octahedral geometry. This complex is paramagnetic because of the presence of
unpaired electrons. In the formation of this complex, since the outer d orbital (4d) is used in hybridisation,
the complex, [CoF] is called an outer orbital complex or high spin complex or spin
free
complex.
13. On the basis of VBT explain the hybridisation, geometrical shape and magnetic property
of
[Ni(CN)4], tetracyanido nickelate (II).
[March-2014, July-2014, March-2015, March-2017, March-2019,
July-2022/
Ans: In this complex, the oxidation state of nickel +2 and has an electronic
is configuration of [Ar]3®.

3d 4s 4p
In this case, the two unpaired electrons the
of 3d-orbitals are forced to pair in the presence of a strong ligand
CN-ion. Since four ligands are to be accommodated, nickel(Il) ion
undergoes dsp hybridisation forming
four equivalent dsp² hybrid orbitals.

dsp

Four dsp hybrid orbitals

rhece four hybrid orbitals overlap with the orbitals of ligands and ligands donate
four pairs of electrons to
form four coordinate bonds.

Student's iiluminator I PUChemistry

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Publications
leyith 177

Four
dsp hybrid orbitals with 4
complex undergocs pairs of clectrons of ligands
Since the dsp" hybridisation,
the geometry square planar. It is diamagnetic complex
due to the
absence of unpaired clectrons. is
During the formation of
used in the hybridisation [Ni(CN),1- is called
the complex, since the inner 3d-orbitals is
inner orbital complex or spin paired complex or low
spin orhyper ligand complex.
On the basis of VBT explain the hybridisation, or
geometry and magnetic property of [NÍCIJ"
totrachlorido nickelate(II) ion.
|March-2018]
Ans: The oxidation state of nickel in [NiCI,j?- is + 2. The outer electronic configuration of nickel(+2) is 34sº.
N": [Arj 3d4s
ttt
3d 4s 4p°
When weak ligand, CF is approaching towards central metal jon, one 4s and three 4p orbitals hybridised to
vield four sp³ hybrid orbitals pointing towards the four corners of tetrahedron.

3d 4s 4p

Four sp hybrid orbitals

to form tetrahedral complex.
Each Cl ion donates a pair of electrons to four sp² hybrid orbitals

complex due
undergo sp' hybridisation, the complex is tetrahedral. It is paramagnetic
Since the complex
orbitals.
to the presence of two unpaired electrons in 3d
MnBr4] is5.9 BM. Predict the
geometry of the complex ion.
The spin magnetic moment of is 5. It is an
is 5.9, the number of unpaired electrons
15.
magnetic moment
Ans: According to the spin only formula, if electrons in 3d orbitals of Mn
coordination number 4. Br is a weak ligand. The
outer orbital complex with sp hybridisation.
the complex is tetrahedral with
are not paired up. Therefore the shape of of
to weak ligands. What would be the hybridisation
16. A six coordinated high spin complex is bonded
the central metal?
Ans: sp'd meaning?
orbitals actually exist? If not, what is the real
a mathematical manipulation of
wave equation for.
17. Can hybrid But hybridisation is
exist.
Ans: Hybrid orbitals do not actually
the atomic orbitals involved. are tetrahedral., Why?
diamagnetic though both
while [Ni(CO)J is It cannot pair up the
1e. INiCI,] isparamagnetic state with the configuration 4s. CI is weak ligand.
3d state with the
Ans: In [NiCI.1, Ni is +2 oxidation In [Ni(CO)4}, Ni is in zero oxidation
it is paramagnetic. up 3d electrOns.
electrons in 3d orbitals. Hence, strong ligand, the 4s electrons shift to 3d to pair
presence of CO complexes Ni undergo sp
configuration 3d 4s. In the present. Hence, it is diamagnetic. In both
Thus, there isno unpaired electron
hybridisation.
|Fe(CN)6 is weakly paramagnetic. Explain.
paramagnetic whereas
19, (Fe(H,0)a* is strongly
I| PUChemistry
<br>

\lon
Comy
a
configuration 3d.
CN- is strongligand.
178
oxidation state with thc hybirdisation is 'sp' formingja
clectron. The
Ans: In both the complexes,
Fe
isupin +3 only one
unpaircd
not pair up. The hybridisation ing
clectrons pair
lcaving prescncc, 3d clectrons do isg
Presence, 3d its Hence, it is strongly paramagnetic,
a wcak ligand. In unpaired clectrons.
orbital complex. H,0 is containing five
an outer orbital complex whereas [Ni(NH,)6* is an outer orbita] complex,
toming complex presence of NH,. 3/ clectrons
an inner orbital In the
20. Explain |Co(NH)J
is
state with the configuration 3a. an inner orbital
pair
Co is in +3 hybridisation is sp' forming complex,
Ans: In [CoNH)., Hence, the
d-orbitals empty. 3do, In presence of NH3, the 3d electrons do not
lcaving two with the
configuration
Ni is in +2 state
NiNH), forming an outer orbital complex.
involved is sp'a
up. The hybridisation
clectrons in the square planar [Pt(CN),J jon.
Predict the number of
unpaired
5ad 6s'. Hence, Pt has the configuration d
21. group 10 with the configuration
Ans: zPt lies in
Pt*
5d 6s óp
is dsp*. Hence, the unpaired electrons in 5d
pair up to mala
For square planar shape, the hybridisation
orbitalempty for dsp hybridisation. Thus, there is no unpaired electron.
VBT.
22. Give any 2 limitations (demerits) of
Ans: () involves a number of assumptions.
It

(ii) It does not give quantitative interpretation of magnetic data.

(ii) It does not explain the relative stability of complexes.
(iv) It does not explain colour exhibited by coordination compounds
(V) It does not give exact predictions regarding the tetralhedral and square planar structures of coordinati;
number 4 compounds.
(vi) It does not distinguish between weak and strong ligands.
23.
Give the main points of CFT.
Ans: Crystal field theory (CFT) is an electrostatic model that describes the breaking of orbital degencras
in transition metal complexes due to static electric field produced by ligands.
According to crystal field theory,
the bonding between a central metal ion and a ligand is purely electrostatic (ionic).
ligands are treated as point charges in case of anions and dipoles in case
of neutral molecules.
the interaction between a transition metal and ligands arises from the attraction
between the positivel
charged metal cation and negative charge or negative pole
of the ligand.
Due to this interaction, the degeneracy of d-orbitals
is lifted and causes the spliting ofd orbitals.
The splitting of five degenerate d-orbitals of metal ion into two sets
of d - orbitals with ditter
energies under the influence of approaching ligands is
called crystal field splitting. The exte
which energies of these two sets of orbitals are split
is called crystal field splitting energy. It denv
by A, This is also measured in terms of parameter
called Dg. The magnitude of splitting is arblu
fixed as 10Dq so that A= 10Dq.
The five degenerate d orbitals split
into two sets of different energies,
t, and e,.
(a) The three d-orbitals, d,,
d and d,, which are oriented in between the co-ordinate 2
called t,o- orbitals.
(b) The other two d-orbitals,
da -d, and d, oriented along the axes are called e, orbitas
dent's illuminator
I DU Ches
<br>

The ligands which cause nature of the

greater crystal crystal field.
those causing lesser crystal field splitting
ficld splitting are termed as strong field ligands while
are calledweak field
The arrangement of
the ligands in ligands.
spectrochemical series. the increasing order of
It is an experimentally the field strength is called
complexes with different ligands. determined series based on the absorption of light by
The increasing
are: order of field strength among some of the ligands
|-< Br < SCN
<CF<s<F< OH-< C.0- <HOSNCs-<EDTA4 <NH, < en <
Weak field ligands CN<CO
H
What is crystal field splitting? strong field ligands
The splitting
of d-orbitals into lower energy to Set and higher energy e.
set in presence
definite geometry is called as
crystal field splitting.
of ligands n a

% What is spectrochemical series?

inct The arrangement of ligands a series
in in the order of increasing field strength (splitting
energy) is called
spectrochemical series.
Spectrochemical series is an show below:
[<Br< SCN <
Cr<S?<F<0H < C,O? <H,0< NCS- <
EDTA+<NH, < NO, < en < CN<CO
weak ligands (upto NCS) Strong ligands (from EDTA)
Iisthe weakest ligand and CO is the strongest ligand.
Stronger the ligand, greater is the crystal field splitting energy.
26. Explain crystal field splitting in octahedral complexes using energy level diagram.
Ans:

Energy
Z

A,
Barycentre
A

Metal
d orbitals
Average energy Splitting of d orbitals
of the d orbitals in in octahedral
spherical crystal field crystal field
Free metal ion
surrounded by ligands. There is repulsion between the
6
In octahedral complexes the central metal ion is of the ligands. The repulsion is more when the
central metal and electrons , and
electrons of
the d-orbitals of the 1s away trom the ligands. So d, d.
the ligand and less when t
ietal d-orbitals directed towards raised in energy. So they
experience more repulsion and
will be
orbitals are towards the ligand. Hence they
form e, set.
<br>

Com
and will move
expericncec lcss repulsion
they
away from ligands. So
do

otbitals are 2 scts namely (a) tg set conta

d,. d,, and d,, orbitals splits into
octahedral complexes the 5d
chetgy. Hence in y and d,, orbitals.
containing d,,
orbitals. (b) c, set crystal ficld splitting cnergy
y d,, and d,,
and c, orbital is
known as
(a)
cncrgy bctween ty, orbitalsoctahcdral.
The difference in
denotcd by A, where 0" indicates
octahedral complexes itis 3
,
For orbitals (d,: and d,, ) the incrcase in energy is 0-6A,

2
energy willdecrcase by =A,.
and d,, ), the 5
For t, orbitals (d,,.d,,

27. What is pairing

encrgy (P)? energy.
Thec energy required for clectron pairing in a single orbital is called pairing
Ans:
28. Give the
significancc of d' ions in octahedral ficld.
Ans:
() If A < P.,
the 4h electron enters into one of the e, orbitals giving the configuration t.e!. fi
from which A, <P are called weak field ligands. So they form high spin complexes.

(i) If A, >
electron enters into tzg orbitals giving the configuration
P,
the 4
te. Ligands #

produce this effect are called strong field ligands. So they form low spin complexes.
29. Explain crystal field splitting in tetrahedral complexes.
Ans: In tetrahedral complexes, the central metal ion is surrounded by 4 ligands. In presence of ligands
-
d-orbitals splits into 2 sets namely lower energy 'e' orbitals containing d, and d,, and higher ener;
orbitals containing d,,, d,g, d, orbitals.

Energy

4
Metal
d orbitals

dda
Free
d, dd,
Average energy
metal ion
of the d orbitals in Splitting of d orbitals
spherical crystal field in tetrahedral
In tetrahedral field, the crystal field
crystal field splitting energy
is inverted when compared to is A,. In tetrahedral
the octahedral complexes. complexes, the splitting of
d0
For t; orbitals, the increase
in energy is
and for 'e' orbitals
Relation between
the decrease in energy 3
A, and A,
is
for the complexes
distances is having same metal, metal-Iigad
the same ligand and
<br>
PUbid
ih
181

The eubscript 'g is

Note: used for the octahedral and square
symmetry. Since tetrahedral complex
havelack of symmtry. planar complexes which have centre of

Many tetrahedral complexes are high spin "g' subscript is not used with energy levels.
rare for the A, of tetrahedral complexes. Why?
Itis complexes
An:
the higher energy orbitals ratherthan pair. to exceed the pairing energy. Usually, clectrons will move up to
Because of
Explainthe colour of complexes this, most tetrahedral complexes are
!. using CFT. high spin.
light is passed through a
When white
rs: solution of transition
wavelengths of white light and mixture metal complex,
of remaining the solution absorbs certain
wavelengths are
Example: (i) [Cu(H,0, P* absorbs red transmitted as complementary colours.
light(600nm) and emits
blue colour. So the complementary colour
to the red is blue. (ii) [Ti(H,0),* absorbs
blue green light (498 nm) and emits violet colour. So the
complementary colour tothe blue – green
is violet.
According to CFT Ti(H,0)% has one unpaired electron in 3d orbitals,
(T* is 3d'). The 3d' electron
excite from tzg level to eg level
-
by absorbing blue green wavelength (498 nm)
and emits violet colour due to
d-d transitions.
Give
three limitations of crystal field theory.
Ans: (i) It cannot explain the colour
of substances with full or emptyd orbitals.
) It assumes ligands as point charges so, the anionic ligands should exert greatest splitting effect, but
actually the anionic ligands are found at the lower end the spectrochemical
of series.
ii) It does not involveand accounts for the covalent bonding between the ligand and the central atom.

Multiple Choice Questions (McQs)

1.
According to VBT, c)coordinate d) all of these
sp°d hybridisation found
in 5. In CFT, ligands are treated as
a) point charges in anionic ligands
a) [CoF, J b) [Co(NH,),I* b) point dipoles in neutral ligands
c) [Ni(CN), d) [NiCI, c) both (a) and (b)
2. The geometry and magnetic property d) none of these
[Ni(CO).] is
of 6. In octahedral complexes, tz, Set orbitals have
a) tetrahedral and diamagnetic a) lesser energy than e, set orbitals
b) tetrahedral and paramagnetic b) more energy than e, set orbitals
c) square planar and diamagnetic c) same energy than e, set orbitals
d) all of these
) square planar and paranagnetic
Valence bond
theory is limited due to 7
In octahedral complexes, if A, <P (pairing
2) it does not give quantitative interpretation
energy), the fourth electron enters into
of magnetic data e orbital
t does not explain the colour exhibited by'
a) togive t,e, configuration
coordination compounds b) tag orbital to give tie configuration
weak and
does not distinguish between
c) both (a) and (b)
strong ligands d) none of these
d) all of these
4, The electrostatic 8. Ligands for which A,>P are
crystal field - theory is an bond a) weak field ligands and forms high spin
model
which considers the metal ligand
to be complexes
a) ionic b) ovalent
<br>

artl
complexes
ligands and forms 12.
Which according to spectrochemical
field ligand
c) weak spin b) NH,
complexes ligands and form high
strong ficld a) CN d)en
a) complexcs CO
complcxes, t, orbitals
have c)
the following sequence
tetrahedral comparcd to c orbitals Which of of ligands
13. strength
9. In encrgy
a) Sameenergy than e orbitals
regarding field series?
sepectrochemical
b) less
encrgy than c orbitals <CN <CO
c) more SCN <F
none of these in
octahedral a) <CN <CO
d) d-orbitals F<SCN
splitting of b)
10. During
the
energy of t orbitals CN <CO<SCN <F
complexes, c) <F<CN
3 , b) increased by A, SCN < CO
decreased by d)
a)
2 increased by
decreased by A, d)

Answer Keys 11 12 13
910
1 23
4 5 678 b C C a C

a a
a a d

Bonding in Metal Carbonyls

5.6 examples. monoxide (CO)acts as ligand.
What are metal carbonyls? Give compounds in which carbon
1. organometallic
carbonyls are
Ans: Metal andCo,(CO)l
Fe(CO)s. (iv) [Mn,(CO)1o]
Examples: Ni(CO)4,
[Ni(CO)] () (Fe(CO):|(ii) [Cr(CO)|
2, Write the structure uf ()
ÇO
Ans:
CO
OC OCco
Ni FeCO CO
OC
OCCo
CO
CO
CO
Cr(CO).
Fe(CO),
Ni(CO). Trigonal bipyramidal Octahedral
Tetrahedral

CO CO
OC

OC Mn
Mn -CO
oC Co 0C CO
OC
CO CO

(Mn,(CO),] [Co,(CO).]

3. Write a note on bonding in metal carbonyls.

o character. The formation of bonds bet
Ans: The metal-carbon bonds in carbonyls have both and I
metaland carbon atom of carbon monoxide is explained below.

PUC
I|
Student's illuminator
<br>

Publications
nyth
bond is formed when
M-C o 183
The the carbonyl carbon
of electrons to the vacant donates a
pair orbital ofthe mctal.
lone is formed by
The
M-C n bond thc donation a
of pair of clectrons
d
metal orbital
pi fiomthe filled intothe vacant antibonding
monoxide This is called back bonding orbital of
carbon of the carbonyl
eflect of bond formation strengthens group.
The
called SYnergic effect. Thus as a the bond and vice-versa. Synergic bonding
This is result of synergic effect,
strengthened. the bond between CO and metal is

Multiple Choice Questions (MCQs)

The
state of metal in
oxidation metal 6. Cr-C bond in the compound [Cr(CO)%] shows
carbonyl complexes is
1. T -character due to
1 b) a) covalent bonding b) coordinate bonding
a)
d) 0 c) synergic bonding d) ionic bonding
c) 3
Metal-carbon bond in metal carbonyls 7. The correct structure of Fe(CO), is (Z= 26 for
2
possesses Fe)
a) octahedral
a) g character
b) tetrahedral
b) Character square pyramidal
c)
c) both gand character d) trigonal bipyramidal
d) neither o or I character 8. Select the true statement from the following for
1 The bond between CO and the metal in metal metal carbonyls.
T back bonding strengthens M-C bond
carbonyls is stronger due to a)
a) synergic effect b) ligand effect order as well as CO bond order.
weakens M-C bond order
G bond character d)
none of these b) T back bonding
c) as well as CO bond order.
The terminal and bridged CO
ligands in the bond order
back bonding weakens M-C
4.

compound [Co,(CO)s] are respectively

c)
order.
1 but strengthens CO bond
a) 0,2 b) 6, bonding strengthens M-C bond
d) 6, 2 d) I back
order.
c) 5,2
order and weakens CO bond
[Ni(CO)4] is
3.
The geometry possessed by
a) tetrahedral b) square planar
c) linear d) octahedral
Answer Keys
1
2 344567 d

C
Coordination
a Compounds
of
Applications compounds.
5.7
Importance and of coordination
present in the minerals,
compounds are widely
applications
5,
Give the important great importance. These functions in the area of analytical chemistry,
are of
many important
Ans:
The coordination Compounds to play
are known systems.
plant and animal World and important role in biological
medicine.
industry and play an
metallurgy, biological systems, Coordination compounds
systems: compound of
1, In biological photosynthesis is a cOordination
are
Some important examples responsible for
chlorophyll
(a) The pigment I| PUChemistry
magnesium.
<br>

Coordination
184 Corme.
oxygen carrier is a
Hacmoglobin, the red pigment of blood which acts as coordination
(b)
of iron. factor, is a
coordination co
(c) Vitamin B,, cyanocobalaminc, the anti-pernicious anacmia

of cobalt.
of biological importance with coordinated metal:
(d) Among the other compounds
enzymes like, carboxypeptidase and carbonic anhydrase (catalysts biological systerns).
of
A

use in many qualitative and

I
2. In qualitative analysis: Coordination compounds find quantit
of complex substances by using suitable reagents very
chemical analysis. The formation is effect
separation of cations in qualitative analysis. The familiar coolour
used in thedetection and rea

given by metal ions with number of ligands (especially chelating ligands), as a result offorrmator
a

coordination entities, form the basis for their detection and estimation by classical and in
methods of analysis. Examples of such reagents include EDTA, DMG (dimethylglyoxime),,a-nito

a-naphthol, cupron, etc.

3. in metallurgy: Formation of coordinate compounds during metallurgical extractions plae.
importance in metallurgy. Extraction processes of metals, like silver and gold, make use of co
formation. Gold combines with cyanide in the presence of oxygen and water to form the coori
entity [Au(CN),] in aqueous solution in hydrometallurgy. Gold can be separated in metallic
from this solution by the addition of zinc.
Refining of metal can also be achieved by the formation of complexes and then subsg
decomposition of that complex. For example, impure nickel is converted to [Ni(CO)land s
decomposed to give pure Ni (Mond's process).
Estimation of hardness of water: Hardness of water can be estimated by the titration
s

4.
Na,EDTA. The Ca* and Mg?* ions present in hard water will form stable complexes with EDTA)
selective estimation of Cat and Mg ions can be done due to difference in the stability constants
calcium and magnesium complexes.
5. Ascatalysts: In many industrialprocess, coordination compounds are used as catalysts. For exarg
Wilkinson catalyst (a complex of rhodium with the fornmula [(Ph,P),RhCI)] is used for
hydrogenation of alkenes.
6. In electroplating: Articles can be electroplated with silver or gold much more smoothly and erd
from the solutions of the complexes [Ag(CN),I and [Au(CN),I than from the solutions of sim
metal ions.
7
In photography: The developed film is fixed by washing with hypo solution. which issolves
undecomposed AgBr to form a complex.
AgBr+ 2Na,S,O, Na,[Ag(S,0,),]+ NaBr
Sodium thiosulphate Sodium dithiosulphato argentate(1)
8. The presence of metals in toxic proportions in plant or animal systems can be removed 0y
therapy in medicinal chemistry. For example, excess of copper and iron are removed by c
agents D-penicillamine and desferrioxime B via the forimation
of coordination compounds. E
used in the treatment of lead poisoning(Antidote). Cis-platin inhibit the growth tumours (Ca
of
<br>

Publications 185

s2h Multiple Choice Questions

incorrect match (Mcas) II and mark
Mark the 3. Matchthe column I with the column
Insulin -
zinc
) Hacmogiobin iron - the appropriate choice
Column II
-Cobalt ColumnI
Vitamin B12 Analytical chemistry i) EDTA
Chlorophyll - Chromium
A)
with B) Volumetric ii) Silver
column I column II and mark the
Matchthe estimation
choice Ni
sppropriate C) Catalyst ii) Cu, Fe.
Column I Column II D) Electroplating iv) (PhP);RhCi
Estimation of i) cis-platin a) A-ii, B-iii, C-I, D-iv
A) water
hardness of b) A-I, B-iii, C-ii, D-iv
Detection and i) EDTA c) A-ii, B-1,C-iv, D-ii
B)
estimation of nickel d) A-I, B-iv, c-ii, D-iii
Electroplating ii) Dimethylglyoxime Which of the following statements is
incorrect
C) 4.
cancer iv) Potassium regarding the. importance of
coordination
D) Treatment of
dicyanoargentate compounds in biological systems?
prevent anaemia is a
a) A-i, B-iv, C-ii, D-iii a) Vitamain B12 used to
complex compound of zinc
b) A-ii, B-ii, C-iv, D-i pigment of blood
b) Haemoglobin is the red
c) A-iv, B-ii, C-iii, D-ii
and contains iron.
d) A-iv, B-ii, C-iii, D-i green pigment of plants
c) Chlorophyll is the
and contains magnesium
d All are correct

Answer keys
1 2 3 4

d b C

word from those

Fillin the blanks by choosing the appropriate
given in the brackets
Set - 1
ionisable, homoleptic, Ambidentate)
(heteroleptic, facial, coordination, same ligands
coordination 4. If three donor- atoms of the corner
Occupy adjacent positions at the
of the
l The primary valences of metals in is named
Compounds are normally octahedral face, the resulting isomer
Ans: ionisable as isomer

SCN is an example for Ans: facial

interchange of
Ans:
ambidentate 5. The isomerism arises from the entities
more
ligands between cationic and
anionic
Complexes in which metal is bound to
3.
are called present in a complex is
than one kind of donor groups of different metal ions
called isòmerism.

Ans: coordination
Ans:
heteroleptic
<br>

Haloalkanes and 6
Haloarenes,
1. What are haloalkanes?
Ans: Halogen derivatives of alkanes are called haloalkanes.
CH,CI,
CHCI,
Examples: CH, -CI
Methyl chloride Methylene chloride Chloroform
(dichloromethane) (Trichloromethane)
(Chloromethane)
2
Write the general formula of monohaloalkanes.
Ans: C,Hn+1X where X=F,C1, Br or I.
3. What are haloarenes?
Ans: Aromatic hydrocarbons in which halogen atom is directly attached to the benzene ring are called haloaren
Examples:
Br

H,C

Chlorobenzene. p-bromotoluene
6.1 Classification
1. Give the classification of haloalkanes and
haloarenes on the basis of number of halogen atoms?
Ans: Depending on the number of halogen atoms
in their structure, haloalkanes and
three types. haloarenes are classified i
(i) Monohalgen compounds: They contain
only one halogen atom in their structure.
Examples: C,H,-Br
Ethyl bromide CH,-CI
(bromoethane) Chlorobenzene
(ii) Dihalogen compounds: They
contain two halogen atoms in
their structure.
Examples: CH, -CHBr, Br
Ethylidine bromide
(1,1-dibromoethane)

Br
1,2-dibromobenzene

(iii)Polyhalogen compounds: They contain more

thantwo halogen atoms
Examples: CHCI, -( Chloroform, in their structure.
CCl,-Carbon tetrachloride,
2. Howdo youclassify Tribromobenzene, etc.
monohalocompounds on
the basis of sp
Ans: On the basis of sp hybridised carbon
to which CX bond2
halogen is attached, classif
into three types. monohalogen compouns are
() Alkyl halides
Student's illuininator
<br>

Publications

Gi) Allylic halides 195

Benzylic halides
(ii)
Alkyl halides: In
this typc of compounds,
Monohalogen derivatives the halogen atom is
of alkanes
are called attached to alkyl group or
Thegeneral formula alkyl halides alkyl halides.
is C,H2nl
Example: C,H, Br - -X where X F, CI, Br, .
Ethyl bromide CH, -CI
(bromocthane)
Methylchloride
(ii) Allylichalides: In allylic
halides, the halogen
the carbon - carbon double atom is bonded sp
bond to hybridised carbon atom next to
General formula
Examples:
Br

Allyl chloride 3-bromo cyclohexene

(IUPAC:3-chloro propene)
Gi) Benzylic halides: In benzylic halides,
the halogen atom is bonded to
(adjacent) next to the benzene ring. sp³ hybridised carbon atom
General formula
Example:
CH, X CH,CI

Benzyl halide Benzyl chloride

(Primary alkyl halide)
Name the types of alkyl halides?
s: There are three types of alkyl halides:
Primary alkyl halides or 1° alkyl halides
() Secondary alkyl halides or 2° alkyl halides
(1) Tertiary alkyl halides or 3° alkyl halides
What are primary alkyl halides? Give an example.
compounds, the halogen atom is attached to the primary carbon atom.
s
In these

is
Ine general formula of primary alkyl halides
H

R--x

- Br
Examples: (ii) CH, -CH,
(i) CH, -CH, -Cl, Ethyl Bromide
Ethyl chloride (Bromoethane)
(Chloroethane)

Pert's I| PU Chemistry
llurnin
 What is the hybridisation
<br>

of halogen containing 197

Alkyl halides carbonin
() halides
(ii) Aryl halides the following?
(i) Vinylic (iv) Allylic
Alkyl halides - sp halides
(ii) (v) Benzylic halides
(üü) Vinylic halides
(iv)
- sp? Aryl halides - sp
Allylic halides –-sp
are alkylidenes or alkylene
Benzylic halides - sp
What
dihalides? Give (v)
aihaloalkanes their classification with examples.
Ans:
The havingthe same type
of halogen
atoms are called
They are classified into twvo types: alkylidenes or alkylene dihalides.
Geminal halides (Gem = same),
(ii) Vicinal
halides (Vic = adjacent)
Geminal halides (gem-dihalides):
called geminal halides.
Iftwo halogen atoms are
bonded to the same carbon atom, they are
Exanple:

H H
H-C-C-X H-(-Ç- Br

H X
H Br
geminal dihalide 1, 1-Dibromoethane (Ethyldene
bromide)
(ii) Vicinal halides (vic-dihalides): If two halogen atoms are
are called vicinal halides.
bonded to the adjacent carbon atoms, they

Example:
H H H H
H-C-Ç-Xt H-¢-¢- Br

X H Br H
vicinal halide 1,2-dibromoethane

6.2
Nomenclature
) The common names of alkyl halides are derived by naming the alkyl group followed by the halide
In
iUPAC system, alkyl halides are named as haloalkanes.
) Haloarene is the common as well IUPAC name of aryl halides.
arenes, the prefixes o-, p-,
ror dihalogen or m- are used in common names and (1, 2)5(1,3, (1,4)-are
used in IUPACsystem.
y
bhni 2010/
Ans:
Write the IUPACnames of following:*kilotiti

Common name IUPAC name

SI. No. Structure
CH,CH,CH(CI)CH, sec- Butyl chloride 2- Chlorobutane

(CH,),CCH,CI
neo - Pentyl chloride 1-Chloro-2,2-dimethylpropane
(i)
tert– Butyl chloride 2-Chloro-2-methylpropane
(iii) (CH,),CCI
Chloroethene
Vinyl chloride
(iv) CH, = CHCI
ses II
PU Chemistry
<br>

Publications
199
order of dipole moments
of C-X bond
The in alkylhalides is
CH,-Cl> CH, F> CH,- Br> CH,I

Carbon - halogen bond length

increases from
C- F to C- I. Give reason.
Because size of halogen atom increases from fluorine
to iodine.
CCl bond is more polar than C-F bond. Give
reason.
C-CI bond is longer than
: clectronegativity difference.C-F bond. Therefore, C-CI bond is more polar
than C-F bond despite of smaller

Multiple Choice Questions (McQs)

The homologous series of alkyl halidcs are c) sp hybridised carbon atom of carbon
represented by general formula carbon triple bond
a) C,H2n+X b) CHnX d) all of these
) CHzn-X, d) C,H,n+2 5. Carbon-halogen bond in alkyl halide is
If halogen atom polarised because
is attached to the carbon
a) halogen atoms are more electronegative
stom containing two alkyl groups, then it is
than carbon
called
b) halogen atoms are less electronegative than
a) primary alkyl halide
carbon
b) secondary alkyl halide
c) halogen atoms are. more electropositive
c) tertiary alkyl halide
than carbon
d) none of these
d) all of these
compounds in which the halogen atom is
The

bonded to an sp hybridised carbon atom 6. The compound CH, = CH-CH, -CI is

adjacent to carbon-carbon double bond are a) Vinyl chloride b) Benzyl chloride
a) Allylic halides b) Benzylic halides
c) Allyl chloride d) Isopropyl chloride
c) Vinylic halides d) Aryl halides
7. Vicinal chloride is
which the halogen atom is
4
Vinylic halides in
bonded to a) Dichloromethane b) 1, 2-Dichloroethane
a) sp hybridisedcarbon atom of carbon c) Vinyl chloride d) Allyl chloride
carbon double bond
b) sp' hybridised carbon atom of carbon
carbon single bond
Answer Keys
1 2 3 4 5 67
C b

G4 Methods of Preparation of Haloalkanes

alcohols? March 2014, July 2016, March 2015]
Ans:
How
do you prepare alkyl halides from
are
ZnCl, (Groove's process): Alkyl halides
) conc. HCI and Anhydrous
From alcohol using concentrated HCI.
alcohols with anhydrous ZnCl, and
otained by heating
udent's
II PUChemistry
illuminatQ
<br>

Haloalkanes
and
Ha
+
HCI
Anh-ZnCl,
R-CI
+
H,0
R-OH
alcohol Alkyl halide

AnhZnCl,, C,H, -Cl +H,0

Example: C,H, -OH +HCI
Ethyl alcohol Ethyl chloride
(Ethanol) (chloroethane) hha

) From alcohols using thionyl chloride (Darzen's process) When alcohols are treated wiith
chloride, alkyl chiorides are produced. tis

R-OH +SOCI, - Pyridine

R-CI+ SO, (g) + HCI(e)
Example: C,H, - OH+SOCI, yTdne C,H, -Cl +SO,(g) + HCI(g)
Ethyl alcohol Ethyl chloride
(EthanoD (chloroethane)

Note: Thionyl chloride is preferred for the preparation pure

of alkyl chlorides because the other t
products are escapable gases.
(iii) From alcohols using PX: : Alkyl halides are formed
when alcohols are treated with phosnhr
trihalides.
3R–OH+PX, 3R-X
+
H„PO,
Alcohol Alkyl halide Phosphorous
acid
(a) Alkyl chlorides are prepared by treating
alcohols with PCl;.
3R–OH +PCI, 3R -CI + H,PO,
Alcohol Alkyl chloride Phosphorius
acid
Example: 3C,H, -OH+ PCI, 3C,H, -Cl +H}PO,
Ethyl alcohol Ethyl chloride
(ethanol)
(chloroethane)ek ritz
(b) Alkyl bromides or alkyl iodides are
obtained from alcohols by treating
respectively. PBrs and Pl, are
and iodine respectively.
generated insitu by the reaction with PBr, r
of red phosphorous with ba
r
RedP
R-OH R-X
X,=Br, or l,
Examples Red P
CH, -OH
Methano! Brg CH, -Br
Bromomethane

CH, -0H Red P

Methanol I2. >CH, –I
lodomethane
Note: PBrg and Ply (unstable
or iodine respectively. compounds) are prepared by the reaction of
redphosphorus witn
(iv) From alcohols using NaBr
with sodium bromide and H,SO: Alkyl bromides can
and conc. sulphuric acid. also be prepared by treating alc

R-OH+NaBr + H,SO,
Yent's illuminator R-Br +
NaHSO, + H,o

i l PUChe
<br>

Example: C,H, -OH+

Ethanol NaBr + H,SO, 201
From alcohols using C,H,Br+ NaliSO,+
() PXs or PCl: Bromoethane H,0
R-OH+PX,
alcohol R-X + HX
+POX,
Alkyl halide
Example: C,H, -0H+PCI,
Ethyl alcohol C,H, -CI +HCI +
POCI,
(ethanol) Ethyl chloride
(Chloroethane)
the preparation of isomeric
Give
haloalkanes
Wher alkanes are byfree radical
ns:
-
treated with Cl, or Br halogenation of alkanes.
mono- and poly haloalkanes are presence
in of UV
formed. light (or heat), a complex mixture of isomeric
For example, n-butane
is treated with
chlorine
chlorobutane. in the presence of UV light gives 1-chlorobutane
and 2-

C1
CH,CH,CH,CH, + CI, UVlight
CH,CH,CH,CH,
n-butane
Heat
-Cl + CH,CH, CHCH,
1-chlorobutane
Note: Free radical 2-chlorobutane
halogenation of alkanes is not advised for preparation
(i) complex mixture of isomeric mono of haloalkanes because
and polyhaloalkanes are formed
pure compound. and difficult to separate as
The yieldof any single compound is low.
(ii)
How do you prepare
alkyl halides from alkenes by adding (i) Hydrogen
examples. halides (ii) halogens. Give
Ans:
(i) Addition of halogen halides: Addition [March 2015]
of HCI, HBr or HI to alkene gives corresponding alkyl
halides. Inhigher alkenes addition of hydrogen halide
takes place according to Markovnikovs rule.
According to this rule negative part of hydrogen halide
(HX) is added to double bonded carbon of
alkene containing less number of hydrogen atoms.
CH, =CH, +HX CH, -CH, -X
(where X= C1, Br or F)

Examples:
-CH,CH,CH, –I
1-lodopropane (minor, 19%)
CH, – CH CH, + HI–
=

L CH, -ÇH. -CH,

2-Iodopropane (major, 81%)

Note: 1) Addition according to Markovnikov's rule is an example of electrophelic addition

reaction.
to the
2) In the presence of peroxide catalyst, addition of HBr takes place against
Morkovnikovs rule. This is called Anti-Markovnikov's addition or peroxide effect.
an example of free radical addition
3) Addition according Anti-Markovnikov's rule is
reaction.
<br>

Haloalkanes
and
202
only for addition of HBr and not for addition H
Peroxide effect is applicable of
4)
Because H-Cl bond is difficult
to break to form freeradicals and in case of Hl
HI,
froe radicals are fomed but
they are unstable and combined to form iodine molecue.
the
ik
react with halogens in carbon tetrachloride to form vicinal
() Addition of halogens: Alkenes halide
,Br - CH,
Erample: CH, =CH, + Br,
CCl, -CH, - Br
Ethylene dibromide
Ethene (1, 2-dibromoethane)

4 Whst are X and Y?

+ HBr
Peroxide
CH,-CH-CH<

+ HBr

Ans: = -CH,-CH-CH,-Br
Br

$. Name the halogen exchange methods

for the preparation of haloalkanes.
Ans: () Finkelstein's reaction (i) Swart's reaction.
What is Finkelstein's reaction?
Explain with an example.[July 2014,
Ans: Chloroalkane or bromoalkane on March 2015, July 2015, July 201E
heating with sodium iodide in dry acetone
is called Finkelstein's reaction. gives alkyl iodide. This reaö

R-X+ Na dy 2cetone
R-I+ NaX where (X=C1,
B)
Example
dry acetone
C,H-CI +Nal C,H,-I +
NaCl
Ethyl chloride
Ethyl iodide
C,H,– Br +Nal dry acetone
C,H, -1 + NaBr
Ethyl bromide
Ethyl iodide
Note: Addition of dry acetone precipitates
formed NaBr and NaCl to prevent backward
the forward reaction according reaction. It facilts
the Le Chatelier's principle.
What is Swart's reaction? Explain with an
Ans: Alkyl chloride or example. [March 2014, July 2016, March
alkyl bromide on heating with metallic fluoride 20IS, April 2024
alkyl fluoride. This reaction is called like AgF, HgFz, CoF: or SbF; etc
Swart's reaction. le
R-X+Ag F.
R-F + AgX where (X=Cl, Br)
t R-f+
Alkyl fluoride R-x
Example:
C,H,-Br +Ag F C,H, -F + AgBr
Ethyl bromide Ethyl fluoride

8. Name the reaction: H,C- Br+ AgF H,C-F+ AgBr

Ans: Swart's reaction.

dent's iluminator Chems

II PU
<br>

Publications
h

Preparation of Haloarenes 203

Givepreparation of o -
the and p-
chlorotoluene
enbstitution reaction, and o- and p-bromotoluene by electrophilic
CH,
ÇH,
+ 2C1, Fe CI ÇH,
dark
+ + 2HCI
Toluene
0-Chlorotoluene
C1
CH, CH, p-Chlorotoluene
CH,
.Br
+ 2Br, Fe
dark + 2HBr
Toluene
o-Bromotoluene
p-Bromotoluene
Give the preparation
of aryl halides
by Sandmeyer's reaction. (Discussed
ns: Aromatic primary in Unit 13)
amines react with nitrous acid (prepared
insitu from NaNO, and a mineral acid such as
HCI) at low temperatures
(273 -
278 K) to form diazonium salt.
This reaction is called diazotisation.
Freshly prepared diazonium
salt is treated with cuprous chloride or cuprous
aryl bromide. This bromide to give aryl chloride or
reaction is called Sandmeyer's reaction.
NH,
NX,

+ NaNO,+ 2HX 273-278K

+ NaCl + 2H,0

Aniline Benzene diazonium halide

Br

Cu,C1/HCI
+ Nf

Chlorobenzene
Br

Benzene Cu,Br/HBr.
diazonium salt +N

Bromobenzene
Note: Iodobenzene can beprepared by simply by shaking the diazonium solution salt with potassium iodide
solution.

NX,

+KI | + Nt KX
<br>

Haloalkanes

204

6.6 Physical Properties

in water. Why?
1. Haloalkanes are slightly soluble polar nature to break the existing
H-bonding in water
molecul
have sufficient
Because haloalkanes donot
Ans:
of haloalkanes and
haloarenes are higher than parent hydrocarb,
points
2. The melting and boiling
to
Why? molecular masses of organic halides compared correspondingalk
Due to greater polarity and higher van der Waal's forces) are stronger halo
Ans:
(dipole-dipole interactions and in
forces
the intermolecular melting points of alkyl / aryl halides are higher than the correspon
and
derivatives. Therefore, boiling
parent hydrocarbons. halides having same alkyl grog
points among different alkyl
Writethe decreasing order of boiling
3.
Give reason. group:
boiling points in alkyl halides having same alkyl
Ans: Decreasing order of
R-I> Br> R-Cl> R-F.
R-
with increase in size and mass of halogen atom, the magnitude of
van der Wal t
This is because
increases.
boiling points of isomeric haloalkanes decrease with increase in branching.
Note: The
bromide and tert-butyl bromide, which has higher boiling point? WVhy?
4. Among isobutyl as the branchi
higher boiling point than tert-butyl bromide. This is because
Ans: Iso-butyl bromide has
increases boiling point decreases.
increasing boiling points.
5. Arrange each set of compounds in the order of
Dibromomethane
() bromomethane, Bromoform, Chloromethane,
(ii) 1-Chloropropane, Isopropyl chloride, 1- Chlorobutane.
< Dibromomethane < Bromoform Since boiling point increas=
Chloromethane < Bromomethane
Ans: ()
with increase in molecular mass. chloride being brandt
< 1- Chloropropane < 1- Chlorobutane> Since isopropyl
(i1) Isopropyl chloride
has lower boiling point.
higher melting point as compared to their ortho- and meta- 150t
6. In haloarenes, para- isomers have
[July 20I6/
Why?
in crystal lattice better as compared to ortho and meta isou
para isomers that fits
Ans: It is due to symmetry of
How does density of halogens changes with
increase in number of carbon atoms?
7.
Ans: Density increases.
on density of halogen compounds?
8. What is the effect of different halogen atoms
increasing atomic mass of halogen atoms.
Ans: Density of halogen compounds increases by
which has higher density?
9. Among n-propyl iodide andn-propyl bromide,
-
Ans: n propyl iodide.
reason.
10. Haloalkanes are less soluble in water. Give watel
Because they do not have sufficient polar nature to break the existing hydrogen bonding in
Ans: alnx
are
11. Haloalkanes are soluble organic solvent. Why? molecules
molecules and organic solvent
Ans: This is because the attractive forces between haloalkane
same.
<br>

Chemical Reactions 205

ractions of haloalkanes may be dividcd
heNicdeophilic,substitution into the following
categorics.
Elimination reactions
Reaction with metals,
)
cleophilic substitution reactions:
1What are nucleophiles? Give an
example.
Electron rich species or nucleus
lovingspccies are called nucleophiles.
Examples. OH CN
etc
Hydroxyl ion Cyanide ion
What is meant by nucleophilic substitution
reaction
Ans: The replacement
of halogen
atom of an alkyl halide inC1,alkyl halides?
euhstitution reaction. (– Br) by a
nucleophile (OH) is called nucleophilic
Nuclcophile initiated the substitution
reaction and halide ion is the leaving group.

Nu +
Nu + X

How does alkyl halides react with aqueous KOH (potash) or aqueous
NaOH or with AgOH
(moist silver oxide)? Give equation.
Ans: Alkyl halide on heating with aqueous KOH or aqueous
NaOH or moist silver oxides gives corresponding
alcohol.

R-X + KOH (a) Ay R-OH + KX

R-X +NaOH (aq) R-OH+ NaX

2R-X+2AgOH2R-OH +2AgX (Ag,0+ H,02AgOH)

Moist
Examples:

A CH, – OH + NaCl
a) CH,–CI + NaOH (aq)
Methyl alcohol
Methyl chloride
+ KBr
b
C,H,- Br + KOH (aq) A C,H -OH
ethanol
Bromoethane
H
2C,H,-OH + 2AgBr
c)
2C,H,- Br + Ag,0
ethanol
Bromoethane
4.
Name the reagent used to get substitution
product R- OH from alkyl halides.
Ans: Aqueous NaOH or KOH.
alcoholic KCN |Potassium cyanide]? Give equation.
n0w do alkyl halides react with potassium cyanide gives
allkanenitrile (cyanoalkane).
Ans:
Alkyl halide on heating with alcoholic

R-X + KCN(alc) A, R-CN + KX

Examples,
+ KI
CH,I + KCN (alc) CH, –CN
Ethanenitrile
lodomethane I| PU Chemist
udent's ittuminator
<br>

208
CH, -CH,
-CN+ KBr [July 2015, March
cquation. 202
C;H,Br+ KCN Propanenitrile
Give (carbylaimine).
Brvethahe alcohollc AgCN? isocyanide
halides react
with gives alkyl
How docs
alkyl
with
alcoholic AgCN
heating
halide on
Ans: Allyl NC + AgX
R-X+AgCN(alc) R-
AlRyl isocyanide

Examples:
CH, - NC+ AgBr
CH,Br + AgCN(alc) A Methylicocyanide
Rromeethane

ACH, –-CH,
- NC+ AgBr
C,H,Br+ AgCN(alc) Ethylisocyanide
Bromoethane
carboxylic acids? Give equation.
alkyl halides reacts with silver salts of
does
7. How
on heating with silver salt of
carboxylic acid gives ester.
Ans: Alkyl halide
RCOO 4Ag + X-R R-CO0 - R+Ag- X
Ester

Examples,
– +
CH,C00Ag + I-CH, CH, CO0-CH, Ag- I
Silver acetate Methyl iodide Methyl acetate
i)

CH,C00 -Ag + B-C,H, CH,-CO0 - C,H, + Ag- Br

Silver ethanoate Ethyl bromide Ethyl ethanoate

8. How does alkyl halides react with alcoholic

ammonia?
Ans: When an alkyl halide is heated
with alcoholic ammonia in a sealed tube,
tertiary amine and finally quaternary primary amine, secondary amin
ammonium salts are formed.
R-X+NH, R-X
-H> RNH, R,NH RX
-HX >R,N. R-X

9.
alkyl halide

Give the reaction

1° amine 29amine
3°amine
R,NX
quaternary ammonium salt
between alkyl halide
(LAIH). with (a) KNO, (b) AgNO, (c)
Lithium aluminium hydro
Ans: (a) With potassium
nitrite |KNO,]
Alkyl halide on
heating with potassjum
RX + KNO, nitrite gives alkyl
heal
R-ONO+KX nitrite.
alkyl nitrile
Example:
C,H,Br+ KNO, heat

(b) With silver

Bromocthane
C,HONO+ KBr
nitrite |AgNO,I Ethyl nitrite

When an
akyl halide is
heated with
R-X+AgNO, silver nitrite,
>RNO, nitroalkane
nitroalkane
+AgX is formed.
Example:.
CH,CH,Br
Bromocthane
+ AgNO,
(c) Reactlon
withlithium RNO, + AgBr
When an aluminium
alkyl halide
nitroethane

reduces hydride
akylhalides is heated with LiAIH,
RX +H AIAIHH, to alkanes. alkane
is formed.
Student's
illuminator RH+X LiAIH4
is a better reducing agent
<br>
Publications

Evample: 4C,H,Br +
LiAlH,: 20
Bromocthane
4C,H,+ AlBr,
+LiBr
1What are ambidentate nucleophiles?
Ethane
Give an example.
Groups likes evanides and nitrites
possess
calledambidentate nucleophiles. two nuclcophilic ccntres
Cyanide group but links through one centre at a tíme are
a resonancc
is hybrid of two contributíng structures
Hence, cyanide actts as a
nucleophile in
alkyl cyanides and anotherthrough
two different ways. One
nitrogen atom lcading by linking through carbon atom resulting in
Writethe formula of the nucleophile obtained to isocyanides.
and C,H, - Br.
during the nucleophilic substitution
between AgNO,

s: Ag-0-N=0
Which class of organic
compound is formed during the nucleophilic
alkyl halide and NH,? substitution reaction between an
as: Primary amine.
Haloalkanes react with KCN to form alkyl
cyanides as main product while AgCN forms isocyanides as
the chief product. Explain.
me KCN is ionic. Although
both carbon and nitrogen atoms are in a position to donate electron pairs,
attack takes place mainly through carbon atom and not but the
through nitrogen atom because bond is more
stable than C- C

C- N bond. But, AgCN is covalent in nature and nitrogen is free to donate electron pair forming
isocyanide as the main product.
Name the types mechanisms of nucleophilic substitution reactions.
ns:
There are two types of mechanisms in nucleophilic substitution reactions.
(a) reaction (Unimolecular nucleophilic substitution reaction)
SNl
(b) SN2 reaction (Bimolecular nucleophilic substitution reaction)
S.
What is S1 reaction?
ns:
Sxl stands for unimolecular nucleophillic substitution reaction.
DNl reactions are generally carried out in polar protic solvents.

Explain the mechanism of SN1 reaction or explain the mechanism involved in the conversion of tertiary
of 2
butyl bromide into tertiary butyl alcohol. OR Explain the mechanism involved in the conversion
bromo-2-methyl propane into 2-methyl-propan-2-ol. (Mareh 2014, July 2014, March 2015,
March 2016.
Mly 2017, March 2018. July 2018, March
2019, March 2020, July 2020)
SNl mechanism follows first order kinetics.
1ertiary alkyl halides, undergo SNl reaction.
aqueous NaOH gives tertiary butyl alcohol.
Lxample: Tertiary butyl bromide on hydrolysis with
ÇH,
ÇH,
Br + NaOH CH,--OH + NaBr
CH,
CH,
CH, Tertiary butyl alcohol
Tertiary butyl bromide on
involves two steps. It follows first order kinetics. Rate of reaction depends
Mechanism: mechanism
Sl
Oncentration of tertiary butyl bromide.
bromide ionises slowly to give sp° hybridised planar tertiary butyl
I Step: (slow Tertiary butyl
step):
arbocation and bromide ion. II PU Chemistry
Sudent'o
ill
<br>

208
CH,
Slow and rate
determining sten
CH, + BO
slow,
CH,-Š CH,
H,C
CH, Tertiary butyl
carbocation carbocation
aqueous NaOH attacks planar
on
Tertiary butyle bromide etther
OH from s
The nucleophile
I Step: (Fast step)
to give tertiary butyl alcohol.
CH, CH,

+
Fast CH, -C-OH
OH
H,c CH, CH,
Tertiary butyl alcohol

SNl reactions results in the

formation of racemic mixture.

Order of reactivity: 3°> 2°>1°>CH,X

very fast. Give reason.
3° alkyl halides undergo S1 reaction
17. In case of alkyl halides,
carbocations.
Ans: Due to the higher stability of 3°
carbocation involved in SN mechanism?
18. What is the type of hybridisation of
Ans: sp
solvents. Give reason.
19. S1 reactions are carried out in polar protic
energy required for breaking of C-X bond is obtained
throm

Ans: Because in step-1 of Sl reaction, the

salvation of halide ion with proton of protic solvent.
20. Which mechanism gives racemic mixture as the product?
Ans: SN

21. What is the order of reactivity among 1°, 2°, and 3° alkyl halides in Sx1 reaction?
Ans: The decreasing order of reactivityof haloalkanes is 3° > 2° > 1° > CH; -X. This due to 3° carbocations
are more stable.
22.
Allylic and benzylic halides show high reactivity towards Syl reaction? Give reason.
Ans: Because formed carbocations are stabilised by the following resonance.
AIklyl carbocation:

H,CCHCH, H,–HC–CH,
Benzyl carbocation:

CH,
CH,
CH, H,

23. Out of CH-CH-CH,Cl and

CH-CH,-CH,CI which is more reactive
Ans: towards Sy1 reactioni
CH,-CH-CH,CI is more reactive
following resonance
towards Sl reaction, Because formed
carbocation is stabilised
by t

HcCHCH, H,C-HC=CH,
24. What is SN2 reaction?
Ans: SN2 stands for bimolecular nucleophilic
substitution reaction.
Student's illuminator
<br>

Explain, S2 mechanism or explain

the mechanisminvolved in the conversion of chloromethane
(methyl chloride) into methanol (methyl alcohol).
JJuly 2015, July 2016, March 2017]
Prinary alkyl halides undergo Sy2 reaction. SN2 mechanism
follows 2 order kinetics.
Example: Methyl chloride reacts with aqueous
NaOH to give methyl alcohol.
-
CH, -CI NaOH()
Methyt
CH, -OH + NaCI
Cride Methy akobol
(chromethne) (Mehnol) .

Mechanism: Sy2 mechanism involves only one

step. It follows 2d order kinetics.
The nucleophile
OH attacks electron carbon atom
deficient carbon atom from the rear side (back side) of the
-
n form a transition state. It 1S unstable. In the transition state a partial (HO ) bond is formed and parua
cCIbond is broken. The product methyl alcoholobtained has inversion configuration.
H
OH

H
-cr

H
HO –
H

H H
C
Ci H
H
–H

H
+CI

Methyl chloride Transition state Methyl alcohol

What is the order of reactivity among 1°, 2°, and 3° alkyl halides in Sy2 mechanism?
of haloalkanes is 3° < 2° < 1° < CH; -X. This is due to more steric
ns: The increasing order of reactivity
hindrance in 3° alkyl halides.

Give any two differences between Sy1 and S2 reactions. Jmant

Ans:
Sy2 Reaction
SL No. Sy1 Reaction
It is bimolecular reaction.
i It isunimolecular reaction. It follows 2
order kinetics.
It follows 1order kinetics. alkanes is
of halo alkanes The decreasing order of reactivity of halo
The decreasing order of reactivity CH,-X>1°> 2° > 30
– X.
is 3° > 2° > 1°>CH; halide
on concentration of alkyl Rate depends on the concentration of alkyl
Rate depends only the Rate =k[R-X][Nu]
and nucleophile.
halide. Rate = k[R-X]
a racemic mixture. The product obtained has inversion configuration.
The product obtained is
V
Substitution Reactions
tereochemical Aspects of Nucieophilic
isomerism?
What is optical
and same structural formula but they differ in the direction
same molecular formula is called optical
optical isomers and the phenomenon
Ats: Compounds
having the are called
of rotation of plane polarised
light
isomerism. of rotation or specific rotation.
isomerism or angle
measure optical
the instrument used to
19,
Name
Ars: Polarimeter.
0. How produced?
plane polarized light is ordinary light through Nicol prism.
passing
Plane Polarized light is produced by
Ans:

substance? right is called dextro

direction ofiplane polarized light to the
31.
What are
dextrorotatory rotates the
As: The solution substance which
ofthe
FOtatory substance.

It is denotedi by (+) sign or 'd'.

Example: or 'd'-lactic acid. II PUChemistry
(+) lactic acid
<br>

sctee
<br>

Publications
h
211
is nchiral molecule? Give an cxamnple
Wha
objccts which arc superimposable for achiral molecule. (March 2017]
The
: not contain asymmetric ontheir mirror
images arc callcd achiral molecule. Achíral molecule
docs carbon atoom.
H Example: Propan-2-ol.

CH,ÇCH,
OH
Propan-2-ol is nchiral molecule
and optically inactive.
propan-2-o1, groups Explain.
In all the four attached to thc tctrahedral carbon
ins:
tetrahedral carbon is not asymmetric atom are not different and hence the
and some of its mirror images are superimposable. Therefore propan-2-
lis achiral moleculc. Duc to the absencc of chiral carbon in its molecule. propan-2-ol is optically inactive.
H,c) CH, H,)
-OH
-OH HO
H
CH,) H,ci
H H
A B 1800

rotating B by 1800
Cis obtained by
Cis superimposable on its mirror image A
2 What is the condition for optical isomerism?
Ans: Compound should contain chiral carbon atom.

What are enantiomers?

July 20I5]
Ans: Optically active isomers which non-superimposable
on their mirror images are called enantiomers.

Example: 2- Bromobutane
CH; CH;
H,C.
C,H,
H¢-OH HOC-H
-Br
C-Br COOH COOH
C,H, H,C acid
H (+) -
Lactic acid (-)-Lactic
(+)-2-Bromobutane
(O-2-Bromobutane
among enantiomers?
What is the difference in property one of the enantiomer is
of plane polarised light. If
**.

Enentiomers differ only with

respect to the rotation
: dextrorotatory, the other will be
laevorotatory.
compounds.
each of the following pairs
of
molecules in
ldentify chiral and achiral
HO H
H H CH,
H,C H,Cmy OH
(b)
(a) OH Br H, CH,
Br
Br (ii)
()
(ii)
(i)
CH,CH,CH,CH,Br
CH, CH CH,CH,
()
Br
(i)
(i)
A: Chiral molecules
II PUChemistry
udent's
i
<br>

Publications
only compound 213
IA'isthe obtained, the process
is called retention of
configuration.
fB'isthe
only compound formed,the
process
amounts of
both A is called inversion of configuration.
Ifequal and B
are formed,
optically
inactive. the process is called racemisation and the resulting product is
S,2
reactions of optically active halides are
accompanied
by inversion of configuration. Explain with
example.
sn
Reason: During Sy2 mechanism,
the nucleophile attacks the stereocenter from the side opposite to the
halogen
atom to avoid the repulsion between leaving halide ion of
configuration takes place. and nucleophile. Hence inversion

Erample:
When -2-bromooctane is heated with aqueous sodium hydroxide, (+)-octan-2-ol is formed. Here the
()
OH group occupies the position opposite to that of bromine. Hence inversion of configuration takes place.

OH CH, CH,
Br > HO -C + Br
C,H,, C,H,,
(-2-Bromooctane (t)-Octan-2-ol
racemisation. Explain with an
S
reactions of optically active alkyl halides are accompanied by
[March 2020]
example.
formation of carbocation. Here the carbon atom
s: Reason: In Syl mechanism, the first step involves the structure.
carbocation is sp hybridised. Hence carbocation has planar
containing positive charge in
carbocation from both the sides giving mixture of andI
d

Therefore, the nucleophile can attack this planar

recemisation).
isomers forming racemic mixture (partial a racemic mixture
with aqueous solution of sodium hydroxide gives
Example: 2-Bromobutane on heating (dl)-butan-2-ol or
-butan-2-ol. Hence the mixture is called
containing 50% d-butan-2-ol and
50%

(t)- butan -2-ol.

ÇH, ÇH,

-Br
+ Br
C,H,
H
C,H,
CH,
(-isomer)
C-OH
C,H,
CH,
)-Butan-2-ol
+ OH
CH, i
'c,H,
(planar carbocation)
HO – (d-isomer)
(Slightly larger yield) :

NCH,
(-Butan-2-ol

I| PUChemistry
<br>

Elimìnation ReNRctions

Bcimiatin

R-H-CR=H-R+K- HO

S-R-
-R-A--H-KR-RO

Reactions wth Netals

<br>

ublications 215

you prepare Grignard reagent from alkyl halides?

low do
rcagents are July 2014, March 2016|
Grignard prepared by thc action of magnesium on in dry ether.
organic halides
dry cther
RMgX
RX+ Mg Grignard reagent

Euample:
dry cther
CH,CH,Br + Mg CH,CH,MgBr
Ethyl
bromide Ethyl magnesium bromide

Explainthe nature of bonding in Grignard reagent.

ihe Grignard reagent, the C-Mg bond is covalent but highly polar, with carbon pulling electrons
from
destrophositive magnesium and the magnesium halogen bond is essentially ionic.
pesctions involving Grignard reagents are carried out in dry ether. Give reasons.
are highly reactive.
ec ) Grignard reagents
They react with any source of proton (water, alcohols, amines) to give hydrocarbons.
RMgX + H,0. RH +Mg(OH)X
Therefore it is necessary to avoid traces of moisture from a Grignard reagent.

Explain Wurtz reaction with an example.

[March 2019)
reaction is called Wurtz
ng Alkyl halides on heating with metallic sodium in dry ether gives higher alkane. This
reaction.
dry ether
2RX +2Na R-R+2NaX

Examples: 2CH,CI +2NaCH, -CH,+ 2NaCI

Methyl chloride Ethane

2C,H,Br +2Naye CH, -CH, -CH, -CH,+ 2NaBr

n-Butane
Ethyl bromide
are formed.
two different alkyl halides is subjected for Wurtz reaction, three alkanes
Note: If a mixture of
CH, -CH, -CH,
Erample: CH,Cl+C,H,CI Na her CH, -CH, + CH, -CH, -CH, -CH,+
butane Propane
Ethane
reasons.
towards nucleophilic substitution reactions. Give
RAryl halides are less reactive IMarch 2014, March 2015, March 2017, July 2017, July
2020]

Less reactivity of aryl halides is due to:

acquires partial double bond character due to
resonance and hence -Y
(T Resonance effect: C-X bond
difficult to break.
bond becomes stronger and it is

CI
cit Ci

-
<br>

rece

eitsensCtmittsecaarisE
etrefttrstri
tiS.
S

ine

NuceihiicStsiurian
RastHuaae
gittteatsrinuihmI
<br>

tPublications
217

OH

() NaOH, 443 K
H
(ii)

NO,
4-Nitrochlorobenzene NO,
C1 p-Nitrophecnol
OH
NO,
(i) NaOH, 368 K
NO,
H
(ii)

NO,
2,4-dinitrochlorobenzene NO,
2,4-dinitrophenol
:CI:
OH
0,N NO, O,N NO,
warm
H,0

NO, NO,
2,4,6-trinitrochlorobenzene 2,4,6-trinitrophenol (picric acid)
para- positions. However, no effect
pronounced when (-NO,) group is introduced at ortho- and
The effect is
presence of electron withdrawing group at meta-position.
on reactivity
of haloarenes is observed by the
presence of electron withdrawing group at m- position of haloarene?
.What is. the effect of the presence of electron withdrawing group at meta- position.
ns: No
effect on reactivity of haloarenes due to the to resonance. Hence
In haloarenes, there will be negative charge at 0- and p-carbon atoms due
Reason: case of meta position,
groups withdraws electrons from o- and p-positions. But in
electron withdrawing
negative charge is not there.

lectrophilic Substitution Reactiono- haloarenes. Explain.

place at andp- positions ofpara- positions.
Electrophillic substitution reaction takes
density increases more ortho- and
at
resonance, the electron reason.
This is due to
haloarenes compared to benzene. Give
occurs slowly in haloarenes have some
Electrophillic substitution reaction eftect of halogen atom,
deactivating group. Due to -I a ring gets deactivated
as compared to
Halogen atom is slightly ring. As result,
from the benzene conditions.
tendency to withdraw electrons reactions occurs slowly and requires drastic
Oenzene and hence
electrophilic substitution
chlorobenzene? ferric chloride / iron filings / red
Explain halogenation of presence of anhydrous
-As: Chlorobenzene reacts with chlorine in the
and para isomers.
Pnosphorus catalyst give ortho
ÇI
C1
FeCl, + 2HCI
Cl,
2 2-Dichlorobenzene (minor) C
1.
Chlorobenzene
1,4-Dichlorobenzene (major)

I| PUChemistry

dent's itl
<br>

Halr

mclting point is more than

218 ofp-dichlorobenzcnc, its
symmctry in thc structurc
Note: Due to
o and m-dichlorobenzcnc. (March 2020]
chlorobenzenc. prescnce of concentrated H,SO. to give
72. Explain nitration of concentratcd HNO, in the
with
Ans: Chlorobenzcnc reacts
p-nitrochlorobenzenc.
chlorobenzene and C

CI
NO,
conc. H,SO, +
+ 2H,0
conc. HNO, heat

o-Nitro chlorobenzene
Chlorobcnzene
(minor) NO,
p-Nitro chlorobenzene
(major)

A3. Explain sulphonation of chlorobenzene. acid 'and

Ans: Chlorobenzene on heating with
concentrated H,SO4 gives o-chlorobenzene sulphonic
p-chlorobenzene sulphonic acid.
C
CI CI
SO,H
heat
+ H,SO4 2H,0
(Conc.)
Chlorobenzene o-Chlorobenzene

.
sulphonic acid SO,H
(minor)
p-Chlorobenzene
sulphonic acid (major)
Explain Friedel - Crafts reaction. (July 2019)
Ans: The alkylation and acylation reactions of haloarenes with alkyl halide or acyl halide in the presence
catalyst like anhydrous aluminum chloride is known as Friedel-Craft's reaction'.
Friedel-Craft's alkylation: Chlorobenzene reacts with alkyl chloride in the presence of anhyu
aluminium chloride to form o-methyl chlorobenzene and p-methyl
chlorobenzene.
ÇI
CH,
+ CH,CI Anhydrous
AlCI, + 2HCI
Chlorobenzene
o-Methyl chlorobenzene
CH,
p-Methyl chlorobenzene
Friedel-Craft's acylation: Chlorobenzene reacts
aluminium chloride to give with acetyl chloride in the presence o
o-chloro acetophenone and p-chloro
acetophenone.
Çl Ç!
COCH,
+CH,COCI Anhydrous,
AICI, +
Acetyl chloride +2 HCl
(ethanoyl chloride)
Chlorobenzene
0-Acetyl chlorobenzene
(o-Chloroacetophenone) COCH,
p-Acetyl chlorobenzene
(p-Chloroacetophenone)
ent's illuminator
<br>

Publcations 219

ldentity the major produet

A
in the following renction:
CI anhydrous AICI,
A

CH, - CH- CH,

Isopropylbenzene (cumene)
(2-phenylpropane)

eaction with Metals 2018]

Explain Wurtz-Fittig reaction with an example. (March 2016, July
This
halide reacts with an alkyl halide in the presence of sodium metal in dry ether gives alkylarene.
zs: Aryl
reaction is called \Vurtz-Fittig's reaction.
R

dry cther + 2NaX

+
2Na + R-X
Alkylarene
Haloarene
=
Where R = alkyl group, X halogen presence of dry sodium and dry ether gives
on heating with bromomethane in
Example: Bromobenzene
toluene. Br
Br
Dry ether + 2NaBr
CH,
+2Na + Br–
Bromomethane
Toluene
March 2017, March 2018]
Bromobenzene JMarch 2014, March 2015, called
reaction with an example. ether to give biphenyl. This reaction is
K Explain Fittig arvl halides reacts with sodium metal in dry
S: Two molecules of
Fittig reaction. + 2NaX
dry ether

x+ 2Na+X- Diphenyl/Biphenyl
Haloarene
Haloarene method as
follows:
prepared by Fittig
biphenyl can
be
Forr example, +
dry ether 2NaBr
+ Br -
-Br+ 2Na Dipheny/Biphenyl
Bromobenzene

Bromobenzene

I| PU Chemistry
<br>

Multiple Choice Questions (MCQs)

1. The best reagent used for the preparation of
8. The reactivity of alkyl halides
alkyl halides from alcohols is thionyl chloride. towards
reaction S
This is because
a) The byproduct formed are gas (SO, and
a) primary halide
(1)> secondary halide
> tertiary halide (3) (
HCI) and escapable
>
b) Nobyproduct are formed
b) secondary halide (2°) tertiary halide
> primary halide (1°) (3
c) Thionyl chloride is easily available and
c) tertiary halide (3°) > secondary halide
non-toxic
d) all of these > primary halide (1") (
d) secondary halide
2. The name of the reaction (2)> primary halide (1
> tertiary halide (3")
R-X+ Nal. dryR-I+ HX is
acetone 9.
a
Wurtz reaction Syl reactions are generally carried out in
b) Fittig's reaction
c), Swartz reaction d) Finkelstein a) polar solvents b) nonpolar solvents
reaction c) either (a) or (b)
3. Which of the following is Swarts d) none of these
reaction
a) -
CH, Br + AgF CH,
-F+ AgBr 10. Sy1 reaction
b) 2CH,CI+ Na dry a) follows first order kinetics
ether
CH, -CH, +2NaCi b) intermediate carbocation is formed
C) 2Ar-C1+ Na: dry
Ar-Ar + 2NaCl c) rate of reaction depends only on the
ether
d) None of these concentration of alkyl halide
4. The boiling points d)
all of these
of isomeric haloalkanes 11. Allylic and benzylic
with increase in branching halides show high
a) increase b) decrease reactivity towards
c) remains same a) S2 reaction
d) none of these
5. Melting points of p-dihalobenzenes are b) SNl reaction
high c) both Sy2 and Syl
compared to their ortho and meta isomers. It reaction
d) none of these
is due to
a) symmetry of p-isomers that fits in crystal 12. The stereoisomers
related to each other 25
lattice better compare to their 0- and m
non-superimposable mirror images are calleo
isomers. a) Enantiomers b) Recemers
b) non symmetry of p-isomers that fits in c) Anomers
d) All of these
crystal lattice better to ortho and meta 13. The preservation
of the spatial arrangeme
isomers of bonds to an asymmetric centre
chemical reaction or during 2
c) symmetries are same in all types of transformation is calle0
isomers. a) Inversion
b) Racemisation
c) Retention
d) none of these d) All of these
14. Tertiary alkyl halides are
6. SN2 reaction follows least reactive
towards S2 reaction
a) first order kinetics because of
a) Inductive effect
b
second order kinetics b) Steric effect
c) Resonance effect,
c) zero order kinetics d) Electromeric effeci
15. The alkyl halides reacts
d) fractional order kinetics with A' gives alkyl
7. In Sy2 reaction cyanides. The A' is
a) AgCN
a) the rate depends upon the concentration of b). KCN
c) HCN
both the reactants d) All of these
b) no intermediate is formed
c) inversion of configuration takes place
d) all of these
<br>

rets mgsizmin ry
AAs Bztmtis of cnfguratt
tRacoeisattt
Soc the reom ofcntfiguntt
becatsef
CHCHH
-CHCHCHCH–C

Answer Keys
123
13 15 1S

Polyhalogen Compounds
The
Wut are phalgnmnds
Gve the S
s
Lrirementsl armfal

Exur
aHigb

wh th
<br>

Uses: Dichloromethane is used

removers.
(i) paint strippers and paint
In

(ii) As a solvent in the manufacture of drugs.

processes for the electronics industry.
(11) Inmetal cleaning and finishing
(iV) As an aerosol spray propellant for paints and insecticides.
3. What are the uses and environmental harmful effects of trichloromethane (Chloroform)9
Ans: Harmful effects:
(i) Breathing about 900 parts of chloroform per million parts of air (900 parts per million) for a
shorttinm
can cause dizziness, fatigue, and headache.
(i) Chronic chloroform exposure may cause damage
to the liver (where chloroform is metabolised
phosgene) and to the kidneys.
(11) Some people develop sores when the skin is immersed in chloroform.
(iv) Chloroform is slowly oxidized by air in
the presence of light to give an extremely poisonous o
carbonyl chloride (phosgene).
Uses:
() Chloroform is used as a solvent for
fats, alkaloids, iodine
(ii) Chloroform is used in the production
(iii) It is used as a precursor in of the freon refrigerant R-22.
Teflon manufacturing (non-stick).
(iv) It was once used as a
general anaesthetic in surgery
anaesthetic such as ether. but has been replaced by less toxic,
safe
4. Chloroform is stored in closed
Ans: Chloroform is slowly dark coloured bottles. Why?
oxidised by air in presence [April 2022/
known as phosgene. of light to a highly poisonous gas,
Therefore chloroform is stored carbonyl chloride, also
air is kept out. in closed dark coloured
2CHCI, + O, Light bottles completely filled so that
2COCl, + 2HCI
Phosgene
Give uses of iodoform
(Triodomethane).
Ans: (i) It is used as an ingredient
in many ear powders
oxide andpropanoic acid. for dogs and cats, to prevent
(i) Earlier. it was used as an infection along with zinc
antiseptic. Due to
formulations containing its objectionable
iodine. smell, it has been
(The antiseptic properties are replaced by other
due to the liberation
6. Give uses of tetrachloromethane of free iodine and not
(carbon due to iodoform
Ans: (i) It is used to make refrigerants tetrachloride). itsel).
(ii It is used as a dry and propellants for aerosol cans.
cleaning agent
(ii) It is used as degreasing agent
(iv) It is used fire
extinguisher
(v) It is used as pesticide
and general solvent.
(vi) It is used as
feedstock in the synthesis of
and other chemicals. chlorofluorocarbons
(CFC's), pharmaceutical
7. What is the effect of carbon manufacturing
tetrachloride on human health
Ans: (i) Excessive exposure
to tetrachloromethane may cause and environment?
eyes, kidney, skin, health effects on
and may cause liver cancer. the brain,
() The most common effects are digestive system,
permanent damage to nerve dizziness, light headedness, nausea and
cells. vomiting,
(iii) In severe cases, which can cause
these effects can lead rapidly
Stùdent's illuminator to stupor, coma, unconsciousness
or death

II PUChemistry
<br>

Publications

Exposure to CCl, can make 223

() contact,
the heart beat irregular or
stop. The chemical may
iritate the eyes on
Environment effect: When carbon
tetrachloride is
depletesthe 0zone layer. Depletion of released into
the ozone the air, it rises to the atmosphere and
to increased layer is
believed to increase human exposure to ultraviolet
ays, leading skin cancer, eye diseases
and disorders, and possible disruption of the immune
ystem.
1What are freons?
The chlorofluoro compounds of methane [July 2014]
and ethane are called freons.
Write a short note on properties and uses
of Freons.
Freons are extremely stable, unreactive,
i) non-toxic. non-corrosive and easily liquefiable gases.
Freon-12 (CCl,F2) 1S One of the common Freon
i) used in industries. It is manufactured from Col4
Swartz reaction.
These are usually produced for acrosol propellants,
refrigeration and air containing purposes.
What is the major effect of freons in the environment?
Photochermical dissociation of freons and related chlorofluorocarbons (CFCS) was a major cause of the
apparent degradation of the Earth's ozone layer. Depletion of the 0Zone could create threat to animal life on
a

the earth because ozone absorbs ultraviolet radiation that can induce skin cancer.

the effect of DDT (P, p'-dichlorodiphenyltrichloroethane) in the environment?

What is
. DDT is non-biodegradable compound because it has low water solubility and high fat solubility.
Iarge DDT residues remains in human tissues because of its non-metabolism in animal tissues.

Write the structure of DDT.

H

CI-CCI
CI
Mention the uses of DDT. as insecticide because of its
insecticide. The DDT is used enormously
DDT is the first chlorinated organic
spreads malaria and lice that carTy typhus.
Cllectiveness against the mosquito that
Questions (MCQs)
Multiple Choice a) Finkelstein reaction
b) Sandmeyer's reaction
Ihe chemical name of phosgene 1s
chloride c) Fittig's reaction
a) Acetyl chloride b) Methyl
d) Swarts reaction
3Carbonyl chloride d) Chloroform coloured The chemical
name of DDT is
Chloroform is stored in closed dark 4.
p,
p'-dichlorodiphenyltrichloroethane
bottles because it is oxidised by air
in the a) p'-dichlorodiphenyltrichloromethane
p,
presence of highly poisonous gas b)
2) Acetyl
light to form Phosphoryl chloride c) p, p'-dichlorodiphenyltrichloropropane
chloride b) dichlorotrichloromethane
chloride p, p'-diphenyl
d) Methyl
) Phosgene d)
from
Freon-12 manufactured
is
etrachloromethane Dy Answer Keys 4
3

12
C d
IIPU Chemistry
<br>

exercises
questions and
224
a Single monochloro compo
NCERT important intextreact with chlorine in dark but gives
not does
1. nydrocarbon CH., general molecular forme
Identify the hydrocarbon.
A
a
sunlight. group with
CsH,Cl in bright CçHjo belongs to the
molecular formula,
Ans: hydrocarbon with the
A

or a cycloalkane.
an alkene
CnHzn Therefore, it may either be be an alkene.
Thus, it should be a cycloalka
cannot
chlorine in the dark, it
Since hydrocarbon does not t react with with chlorine in bright sunlig
CsH,Cl by reacting
monochloro compound, are
Further,the hydrocarbon gives a single must contain H-atoms that all equivalent.
hydrocarbon
Since a single monochloro compound is formed, the a cycloalkane. Hence, the abovesa
must be
equivalent, the hydrocarbon
all H-atoms. of a cycloalkane are
compound is cyclopentane.
structure of the major organic product in each of the following reactions.
2 Write the
acetone
(i) CH,CH,CH,CI+ Nal heat
1-Chloropropane (Finkelstein
reaction)

(ii) (CH),CBr + KOH ethanol

heat
2-Bromo-2-methyl propane (Dehydroha log enation)

(ii) CH,CH(Br)CH,CH, + NaOH Water

2-Bromobutan

(iv) CH,CH,Br+KCN Alcoholic

Nucleophili
Bromoethane substitution

(v) CH,0 Na' +C,H, -CI aq.ethanol

Nucleophilic
Sodiumphenoxide substitution

Pyridine
(vi) CH,CH,CH,0H+ SOCI,
1-Propanol

(vi) CH,CH,CH =CH,+ HBr Peroxide

(Anti-Markovnikov's
But-1-ene addition)

(viii) CH,CH = C(CH,), + HBr

(Markovnikov
2-Methylbut-2-ene addition)

Ans: (i) CH,CH,CH,1+ NaCl

I-Iodopropane

CH, -C=CH, + KBr + H,0

(ii)
CH,
2-Methyl propene

(iii) CH,CH(OH)CH,CH,+ NaBr

Butan-2-ol

(iv) CH,CH,CN + KBr

Cyanoethane

(v) C,H, -0-C,H, + NaCl

Ethoxybenzene

(vi) CH,CH,CH,CI+SO, +HCI

1-Chloropropane

(vii) CH,CH,CH,CH,- Br
-Bromobutane

Student's illuminator
<br>

Br

CH, -CH, -C-CH,

CH,
2-Bromo-2-methylbutane

Primary alkyl halide

C,H,Br (a) reacted with alcoholic
KOH to give compound (b). Comnpound (b) is
with HBr to give (c) which is an
rescted isomer of (a), When (a) is reacted with sodium metal it gives
compound (d), CH1s which is different from the compound
formed when butyl bromide is reacted n-
sodium. Give the structural formula of (a) and write the equations for all
with the reactions.
There are two primary alkyl halides having the formula,
S
CH, -CH, -CH, -CH, - Br - Br
CH, -CH-CH,
CH,
n- Butyl bromide Isobutyl bromide
Therefore,compound (a) 1s either in – butyl bromide or isobutyl bromide.
The complete set of reactions is

Br

-CH-CH, -
–
CH,-CH-CH,– Br
alc.KOH
>CH, –C= CH,. Hbr CH,– Na
C-CH,eCH, CH, CH- CH,

CH, CH, CH, CH, CH,

a) (b) (c) (d)
(an isomer of 'a')
C&Hs which is different
Compound (a) reacts with Na metal to give compound (d) of molecular formula
– butyl bromide reacts with Na metal. Hence, compound (a) must be
from the compound formed when n
isobutyl bromide.
2Na/dry
eherCH,CH,CH,CH,CH,CH,CH,CH, + 2NaBr
2CH, -CH, -CH, -CH, -Br (Wurtz reaction
)

n-Butyl bromide n-Octane

Ihus, compound (d) is 2, 5– dimethylhexane.
2 Na/dry ether CH, - CH- CH, –CH, -CH-CH,
CH, -
CH-CH, – Br wurtz reaction
CH, CH,
CH, (b)
(a)
KOH to. give compound (b). Hence, compound (b) is
IS
given that compound (a) reacts with alcoholic
2- methylpropene. + HBr
CH, - –
CH-CH, Br
CH, -C= CH,
CH,
CH, 2-Methylpropene
Isobutylbromide (b)
(a)
(c) which is an isomer of (a). Hence, compound (c) is
Also, compound HBr to give compound
Gbromo-2-methylpropane.
(b) reacts with
Br

HBr
CH, (Markovnikov addition)
CH,- C- CH,
CH, -Ç= CH,
CH, 2-bromo-2-methylpropane
2-Methylpropene (c)
(an isomer of (a))

ent'siluminnit I| PU Chemistry
 S,
<br>

Phenols UNIT
and Ethers 7
1Whatare alcohols2 Alcohols
s: The hydroxy derivatives of hydrocarbon
called alcohols. in whichthe
-OH group is attached to
the aliphatic carbon chain are
1Vrite the general formula of alcohol.
oneral formula of alcohol
is R-OH, where R is an alkýl,aralkyl
or vinyl group.
Classification of Alcohols
4

Civethe classification
of alcohols on the basis of number
Based on the number of of -OH groups?
-OH groups
trihydric and polyhydric alcohols.
present in a molecule, alcohols are
classified as monohydric, dihydric,
() Monohydric alcohols: They contain - OH group in their molecule.
only one
Examples:
CH,-OH Methyl alcohol
CH,- CH, –OH Ethyl alcohol
(ii) Dihydric alcohols: They contain two -OH groups in their molecule.
Example: Ethylene glycol or glycol CH,OH
CH,-OH
Ethane-1, 2-diol
(ii) Trihydric alcohols: They contain three-OH groups in their molecule.
Example: Glycerol ÇH, OH
CH-OH
CH, OH
Propane -1, 2, 3-triol
(iv) Polyhydric alcohols: They contain many -OH groups in their molecules are called polyhydric
alcohols.
Give the classification of monohydric alcohols on the basis of hybridisation.
: Monohydric alcohols are classified according to the hybridisation of the carbon atom to which the hydroxyl
group is attached.

)Compounds containing C., - OH bond: In this class alcohols,

of the -OH group is attached to a sp³

hybridised carbon atom of alkyl group.

These as
compounds are further classified
(a) Saturated aliphatic monohydric alcohols
dent's illuminator I| PUChemistry
<br>

236
(b) Allylic alcohols

(c) Benzylic alcohols the -OH group is attached to alkyl

these alcohols, gog
monohydric alcohols: In
(a) Saturated aliphatic as
compounds are further classified
These
-OH group is attached to a primary carbon
Primary(1) alcohols: In
these alcohols, the
one adjacent carbon atom).
a
) atom bonded to
an alkyl group (i.e., carbon
a
of
Examples
General formula
Functional group
H H H

-CH, -0H
R-C-OH H-Ç-OH H,C-¢OH
Primary (1°) H H H
1

Methyl alcohol Ethyl alcohol

(one R group)
a
(i) Secondary(2°) alcohols: In these alcohols, the -OH group is attached to secondary d
atom of an alkyl group. (i.e., carbon atom bonded to two adjacent carbon atoms).

Functional group General formula Example

R
R-(-OH H,C-¢-0H
>CH-OH
Secondary (2°) H

is
2°
(two R groups) Isopropyl alcohol
(iii) Tertiary (3°) alcohols: In these alcohols, the -OH group is attached to a tertiary carbon atom
an alkyl group. (i.e., carbon atom
bonded to three adjacent carbon atoms).
Functional group General formula Examples
R ÇH,

Tertiary (3°)
R--0H H,C-(-OH
R

CH,
30
(three R groups) tert-Butyl alcobol
(b) Allylic alcohols: In these alcohols
carbon double bond. These may the-OH group is attached to sp hybridised
be primary, secondary or carbon atom next to
Example: Allylic cartbon
tertiary alcohols.

CH,= CH- CH,– OH

Primary (1)
CH,
=CH-Ç-0H
H

CH, =
-
CH--OH :t
Secondary
Tertiary
<br>

Benzylic aleohols:
In these alcohols,
carbon atom next to the aromatic the -OH groun
alcohols. ring. They may is attached
be primary,
to a sp hybridisecd Benzylic carbo
Example: sccondary or tertiary
CH,0H
H

OH
-OH

Secondary
Tertiary
D Compounds containing
bonded carbon
C.a-
OH bond: In
sp
these alcohols,
atom (sp") the - OH group bonded
of aliphatic
chain. These alcohols are is directly to double
Example: CH, known as vinylic alcohols.
=CH-OH Vinyl alcohol

2 Nomenclature
Common names: The common
name of alcohol
adding the word alcohol to it, is derived from the common name
of the alkyl group anc
IUPACSystem: In this system
(a) The name of alcohol is derived
from the name of the alkane
substituting e' of alkane with the from which the alcohol is derived
suffix 'ol'. by
(b) The position of the substituents
and alcoholic group are indicated by numerals.
(c) The longest carbon chain is
numbered starting at the nearest to the hydroxyl group.
(d) In polyhydric alcohols, the
'e' of alkane is retained and the ending 'ol' is added.
(e) The number of-OH groups is indicated adding multiplicative
prefix di, tri, tetra, etc., before 'ol'.
() The positions of -OH groups are indicated by appropriate locants.
(g) In cyclic alcohols, the prefix cyclo is
added before the root word and considering the -OH group
attached to C– 1.

*Write the IUPAC names of following compounds

Compound Common name IUPAC name

CH,-OH
Methyl alcohol Methanol
,CH,-CH,-OH Propyl alcohol Propan-1-ol
H-CH-CH,
Isopropyl alcohol Propan-2-ol
OH
CH,-CH n-butyl alcohol Butan--ol
-CH,-OH
ÇH-CH,-CH sec- Butyl alcohol Butan-2-ol
OH

Suden
<br>

Alcohols, Phenols
andE
238 2-Methylpropan-1-ol
Isobutyl alcohol
CH,-ÇH-CH-OH
CH,
2-Methylpropan-2-ol
CH,
ler-Butyl alcohol

CH,-¢-OH
CH,
CH Glycerol
Propane-1,2,3-triol
çH
OH OH ÒH
OH Cyclohexanol Cyclohexanol

HO-CH,-CH, -OH Ethylene glycol Ethane-1,2-diol.

QH 2-Methylcyclopentanol
CH,

7.3 Structure of Alcoholic Functional Group

4. Explain the structure of alcoholic functional group by taking
methyl alcohol as an example.
Ans: In alcohols, the oxygen of the -OH group is attached to
sp' hybridised carbon by a
sigma bond formed by the overlap of sp hybrid orbital
of carbon with a sp hybrid H
orbital of oxygen. The figure shown illustrates 108.9°
the bonding in methanol. The
H bond angle in alcohol is slightly C-O
less than the tetrahedral angle (109°28). It
to the repulsion between the is due H
unshared electron pairs of oxygen i.e.,
lone pait - bond Methanol
pair interaction.

7.4 Methods of Preparation of Alcohols

1. From Alkenes
1. How would you prepare alcohols
Ans: by acid catalysed hydration
Alkenes undergo hydration of alkenes? Explain with an exampl
(addition of water across
alcohols. C=C bond) in the presence of dilute H,S04 to produt
-no
Alkene Excess
H OH
In case of unsymmetrical Alcohol
the
Markovnikov's rule. alkenes, addition of water to w
the double bond accordance
Example: is in

OH
CH, - CH= CH, + HO
CH- CH- CH, + CH, –
Propene Excess
2-Propanol
-
CH, CH,
–0H
(major product) 1-Propanol
(minor product)
Ydent's illu
 Publications
<br>

ath mechanism of
Esplain the hydration 239
of alkenes
Mechanism: to alcohols.
mechanism of hydration
The of alkenes involves
Protonation of alkenc to the following threc steps:
Step 1: form carbocation by clectrophilic
attack of H,O.
H,0 + H+ H,0+
H

H,
Alkene
Carbocation
Sten 2: Nucleophilic attack of water on carbocation.
H H
+ H,0

Oxonium ion
Step 3: Deprotonation to form an alcohol.

H H H :ÖH
+ H,0 + H,9*

Alcohol

E.
What is hydroboration - oxidation reaction? Give an example.
on oxidation with hydrogen peroxide in the
Ans:
Alkenes react with diborane to give trialkyl borane, which
– oxidation. During this
presence of dil. NaOH gives alcohol. This reaction is called hydroboration
atoms.
to the sp carbon carrying greater number of hydrogen
reaction, boron atom of diborane gets attached
Example,
THF
CH, CH=CH, + (H-BH), CH,–ÇH- ÇH
Diborane H BH,
Propene
CH,-CH=CH,

CH-CH=CH, (CH,-CH,-CH),BH
(CH,– CH,–CH),B
HO 3H,0,, OH

+ B(OH),
3CH-CH– CH,- OH Boric acid water to alkene according to
formed by addition
of
Propan-1-ol is
Sote: product alcohol
i) In this method, the
antimarkovnikov's rule. obtained in excellent yield.
alcohol is
In this reaction, reaction.
4 hydroboration oxidation
Name
the oxidising agent used in
Ans:
Hydrogen peroxide

II PUChemistry
<br>

2 Frum cartri cmgns

-CE-CE
R-CHr oote
CH -CHD-H-CH-(E

E-0E

E-E-CHD-E
-E-E-E

-0-E 2-H-R

-
TE
<br>

Publications
ah onmmercial method 241
Give the for
carboxylic acids commercially? Give
the preparation of aleohols OR How
Commercially, carboxylic cquation. do you prepare alcohols from
acids are reduced
t rduction using hydrogen in the presence of to alcohols by converting
Ni or Pd catalyst. them into esters followed by their
H+

R.
-COOH+R -OHR-COOR'
Cartotvbcacid
Ester Catalyst(Pd or Nij
Ni) >R-CH,OH+ R'-OH
Eample: 1°Alcohol

H+
CH.-COOH+C,H, –OH
Ethyl alcohol CH, -COOC,H, H,
N,
Acetic acid
Ethyl acetate
Caalyat(Pá CH, -CH,OH
Ethanol
+C,H -OH.
Name the type alcohol formed when carboxylic
acids react with lithium aluminium hydride.
1°- alcohols.

From Grignard reagents

you prepare 1", 20 and 30 alcohols
. How do
When Grignard reagent is treated
from Grignard reagent? Write the general reactions.
with aldehydes or ketones, addition products (magnesium salt) are tormed.
These products on hydrolysis give alcohols.

+ R OH
=) -MgX H,0
Mg(OH)X
Carbonyl compound
R
Adduct Alcohol

Formaldehyde on reaction with Grignard reagent gives primary alcohols

H-CH0+
Farmaldehyde
RMgX RCH,0 MgX HOR-CH,0H+ Mg(OH)X 1° Alcohol
Addition compound
on
(ü) Aldehydes other than formaldehyde give secondary alcohols and ketones give tertiary alcohols
reaction with Grignard reagent.
H
R
R'
R-=0+R'MeX Elher>R - CH-OMgx R-H-OH + Mg(OHx
Aldehyde Addition compound 2° alcohol

R
R
R
Mg(OH)X
CH-OMgX-R-CH-OH+
R-C=O+ R'MgXhe>R-
Ketone R'
R' 3° alcohol
Addition compound

Physical Properties of Alcohols

. number of carbon atoms. Give reason.
The increase with increase in the
boiling points of alcohols
This due to increase in van der Waals forces.
Any,
is with increase in
branching. Give reason.
In alcohols, the boiling points decrease
decrease in surface area.
Aas.
Because van decreases due to
der Waals forces classes of organic compounds like hydrocarbons,
Boiling are higher than othermasses. Give reason.
points of alcohols molecular
ethers, haloalkanes of comparable presence intermolecular hydrogen bonding in them
Ans: are mainly due to the masses.
The high alcohols
boiling point of with comparable molecular
which compounds
is lacking in other organic

| PU Chemnistne
<br>

242 bonding
Intermolccular hydrogen

R-0-H R R
H
water. Why? intermolecular hydrogen bonds with
Alcohols are soluble in ability to form
4. water is due to their
Ans: The solubility of alcohols in
increase in size of alkyl group.
decreases with
molecules. The solubility

Chemical Reactions of Alcohols - broken when alcohols reac

7.6 - bond: The bond
between O H
O H
is
of cleavage
Reactions involving the
nucleophiles. are acidic i
reacts with metals? Explain. OR Show that alcohols
1. What happens when alcohols
with an example. etc tos
metals such as sodium, potassium, aluminium,
electropositive alkali
Ans: Alcohols react with highly
hydrogen gas.
corresponding alkoxides with the liberation of
2R-0-H+ 2Na 2R–0- Na + H,
Sodium alkoxide

CH, CH,
3H, t
6CH,-C-OH + 2A1 > 2
CH,-¢-o]Al +
CH, CH,
tert-Butyl alcohol Auminum
tert-butoxide
The above reactions show that alcohols are acidic in nature.
2. Name the gas liberated when alcohols reacts with active metals like Na, Al?
Ans: Hydrogen gas.
3. What is the effect of electron donating substituents on acidity of alcohols?
Ans: Electron donating groups decreases the acidity of alcohols.
Explanation: The acidic nature of alcohols is due to the polar O-H bond. An electron donating alkylg
increases the electron density on oxygen atom and decreases the polarity of O-H bond and also decrease
stability of alkoxide due to + I efect. This decreases the acidic strength of alcohols. The acidic streng
primary, secondary and tertiary alcohols is in the following order:
R
R
R--CHOH > >>
CHOH R--C -OH
R
R
1-alcobol 2°-alcohol 3-alcohol
Acidic strength of alcohols
4. Alcohols are weaker acids than water.
Give reason.
Ans: In alcohols, due the electron
donating nature of alkyl group, the
alcohol) décreases. stability of alkoxide (conjuga

R-+H--HR-0-H H
basic
acid conjugate conjugate
acid base
These reactions
show that water is a better w
proton than alcohols. Hence, alcohols are than
weaker acid
dent's illuminator
<br>

Publications
h
Alsoabove reaction shows that' alkoxide 243
lkoxides are stronger.
ion is a
better proton
acceptor than OH ion, which suggest
Note: (i) The strength of an acid
more stable, then
is detcrmincd
that acid is strong by the stability
of its conjugate base, If conjugate base is
acid and vice-versa.
(ii) Alcohols acts as Bronsted bases as
well, It is due
ONygen, which makes them
proton acceptors. to the presencc of lone pair of electrons on
(ii) Sodium ethoxide is stronger base
acceptor than hydroxide ion.. than sodium hydroxide
because alkoxide ion is better proton
What is esterification reaction? Give an
example.
reaction between carboxylic acid
n: The and alcohol
esterification. n presence of conc. H,S0, to give an ester and water is
called

+
OH H-0-RH -0-R' + H0
Acid
Examples: Alcohol Ester

. 1. CH,
OH +
H-0-CH, H CH, -0-CH,+ HO
Acetic acid (glacial)
Methyl alcohol Methyl acetate

-CH,CH, + H,0
ii.
Bthanol
Ethyl benzoate
Benzoic acid
presence of conc. H,SO,? Give equation.
What happens when ethanoic acid reacts with methanol in
What is the namne of the reaction?
Ans: Methyl acetate, an ester is formed.
cone H
CH, -COOH+ HO-CH,; $O,CH, -CO0-CH,+H,0
Methyl acetate
Ethanoic acid Methanol

The name of this reaction is esterification reaction.

or alcohols.
Name the confirmatory test for carboxylic acids
Ans: Esterification.
What is the role of
conc.
sulphuric acid during esterification?
Ans: Acts as a dehydrating agent.
acylation of alcohols.
ame the product formed during
9.
Ans:
Esters.

Explain acetylation of alcohols with

an example.
presence of pyridine to give corresponding esters. This
chloride in the
The reaction of alcohols with acid
Ans:

alcohols.
2eaction is called acetylation of HCI
Pyridine,R-COOR'+
R-OH+ R'COCI
Alcohol
Ester
Acid chloride
Example: + HCI
Pyridine CH,CO0CH,
CH, –OH + CH,COCI
Methyl acetate
Methyl alcobol Acetyl chloride I| PUChemistry
Sude
<br>

Give equation and what is the name

chloride? of r
244 reacts acetyl
when cthanol
11. What happens
reaction?
Ans: Ethyl
acetate, an ester is formed. C.H, -OOC-CH, + HCI
Iydine
+ CH, -CO-CI- of alcohols.
C,H, -0H acctylation reaction
reaction is
The name of this acylation of alcohol1? reaction. Or It helps to remove HCI
pyridine during during the
12. What is thea role ofwhich neutralises HCI formed
Ans: Pyridine is base
Pyridine +R-COOR'+ HCI
R-OH+ R'COCI
Ester
Alcohol Acid chloride
bond: The bond between
C
-0 is broken when alcohols
r
Reactions involving the
cleavage of
C
-0
electrophiles. alcohols by using Lucas reagent?
would you distinguish 1º, 2° and 3°
13. What is Lucas reagent? How [July 20l6, April 2022)
chloride and concentrated hydrochloric acid is called Lucas reaent
zinc
Ans: A mixture of anhydrous in three types of aleok.t.
for the appearance of turbidity with Lucas reagent is different
The time taken
alcohols.
used to distinguish 1º, 2° and 3° (anhydrous ZnCI, + conc. HCI)
Organic compound + Lucas reagent

2° alçohol 1° alçohol
3° alcohol

turbidity turbidity
immediate
turbidity after 5 minutes only on heating

14. Explain dehydration reaction of alcohols with an example.

Ans: Alcohols on heated with protic acids like concentrated H,SO, or H,PO, or anyd. ZnCl; (or) Alumina, t
undergo dehydration (removal of water) to form alkenes.
H OH
HSO,, heat
+ H,0
Alcohol Alkene
Example: Ethanol undergoes dehydration by heating it with concentrated H,SO, at 443 K.
CH,-CH, -OH2CH, = CH,+
443 K
H,0
Ethanol Ethene
Sccondary and tertiary alcohols are dehydrated under milder conditions.
For example,
OH
CH, - CH-CH, 85% H,PO
CH. - CH= CH, +
440 K H,0
Isopropyl alcohol (2) Propene
ÇH,
CH.-- OH2020
HO
358 K
CH, –-CH, + H,0
2-Methyl propene
CH,
tert-Butyl alcohol (3")

Therefore, the case of dehydration alcohols

of follows the order: 3° > 2° > 1°.
Vdent's illuminator
<br>

Explain the mechanism

of dehydration
farch 2016,
July 2018, March of ethanol 245
so, 2019, July to cthenc.
CH, -CH,-OH- RK >CH,
2019, March 2020, [March 2015, March 2017, July 2017,
Ehanol =CH,+
Ethene H,0 J uly 2020, April 2022)
Step 1:
Formation of protonated alcohol
H H
+ H Fast
H-CC9H H-¢-¢---H
H
H H
Ethsnol
H H
Protonated alcohol
(Bthyloxonium
Step 2: Formation of carbocation: ion)
Protonated alcohol
is the slovwest step and hence, losesthe water
the rate determining step of molecule to form the carbocation. It
H H H the reaction.
Slow H H
H--¢-H H- + H,0
H H H H
Carbocation
Sten 3: Elimination of proton: Elimination proton
of from carbocation to form an alkene.
H H
H H
+ H*
H H H H
Ethene
6 What is the order of dehydration of different alcohols?
Ans:
3°> 2° > 1°
I1. Explain oxidation of alcohols.
as 0) Oxidation of primary alcohols with PCC (Pyridiniumchlorochromate) gives aldehyde: PCC is a
complex of chromium trioxide with pyridine and HCI [(c,H,NH) CICro; ]

CH,-HH
CH-CH,OH PCC> CH,-CH=CH-CHO + H,

Crotanaldehyde
But-2-en-1-ol
(1) Secondary alcohols are oxidised to ketones by chromic anhydride (CrO,).

OH
-R' (0) R-R
2'-alcohol Ketone
Example
H,O
R-ÇH-R'
OH
oR -R'+

2'-alcohol Ketone
reaction easily.
(ii) Tertiary. alcohols donot undergo oxidation cannot used for this, explain.
Note: Name a following conversion. KMnO, V

reagent for the CHO4I

CH,OH
Ans: POCC
(pyridiniumchlorochromate) carboxylic acids by strong oxidising agents like
aldehydes and then to
Alcohols undergo oxidation to can be used as better oxidising agent.
aldehydes, CrO; or PCC
KMnO4.7 Therefore for isolation of
| PUChemistry
Sudent's
iluminator
<br>

Alcohols,
Phends
246 andE
vapours of 1., 20 and 3º alcohols passed
over heated Cu at 573 K?
18. happens when
What Epain
alcohols. (March 2014)
an cxample. OR Explain dehydrogenation of
dchydrogenation when passed over heated copper or Silver
Ans: (a) Primary alcohols undergo caayo
S73K to give aldehydes.
Cu or Ag + H2
R-CH, -OH ,R-CHO
573 K
1° alcohol Aldehyde
Cu or Ag CH, -CHO H,
+

Example: CH, -CH, -OH 573 K

Ethyl alcohol Acetaldehyde
over heated copper or
(b) Secondary alcohols undergo dehydrogenation when passed silver catalys

573K to give ketones.

R-CH-R R-C-R+ H,
573 K
OH
2° alcohol Ketone

Exanple.:
Cu or Ag
CH, CH CH, 573 K
CH,-Ç-CH, + H,
OH
Isopropyl alcohol Acetone
(c) Tertiary alcohols undergo dehydration to form corresponding alkene when passed over heated Cur
Ag catalyst at 573K.

ÇH,
CH, -Ç-OH
Cu or

573 K
Ag CH, -= CH, + H,0
2-methylpropene
CH,
t-butyl alcohol

19. Tertiary alcohols do not undergo dehydrogenation.

Ans: Due to the absence of tertiary Why?
hydrogen atom.
20. Writethe IUPAC name of the product formed
when the vapours or
heated copper at 573 K. Write the of
isopropyl alcohol passed
reaction.
Ans:
CH, - CH-CH, Cu
yCH, - -CH, + H,
OH
Isopropyl alcohol
Propan-2-one

21. Name the transition metal

which is used as dehydrogenating
Ans: Copper or Silver. agent.

7.7 Some Gommercially

1. Describe the manufacture Important Alcohols
of methanol (wood spirit)
Ans: Carbon monoxide is from.water gas.
mixed with catalyst
573K to 673K and 200 hydrogen and passed over zinc oxide
to 300atm to give and chromium trioxide
methangl,
<br>

S8CO+2H, Zn0-Cr,O, 247

200-300
atm, 573--673 K
of CO and hydrogen
Mixture CH,OH

(i) Methanoliis also known as wood(CO+ H;) is called Methanol

water gas.
uses of methanol. spirit, was
produced by
1rite any two (wood spirit)
destructive distillation of wood.
Methanol is mixed with ethanol
and sold in
Methanol is used as a
major solvent the market as denatured
for paints and varnishes. spirit.
+ Methanol is usedfor making
formaldehyde.
It is also used as an antifreeze
for automobile radiator.
.Itis usedfor denaturing ethyl alcohol.
Mentionthe
properties and health effects of
method.
Methanol is a
colourless liquid and boils at 337 K.
It is highly poisonous in nature.

Ingestion of even small quantities of methanol can

cause blindness and large
Doseribe the manufacture quantities causes even death.
of ethanolfrom fermentation sugar
e Ethanol is prepared by fementation of molasses. Molasses isofthe (molasses)
non-crystalline product of sugar left behind
in sugar industry. It mainly
contains sucrose which gets broken down to ethanol. The fermentation is
initiated by yeast, which secretes two enzymes called invertase
and zymase. The sugar in molasses is
converted into glucose and fructose (both of which have the formula
CH,,0), in presence of the enzyme,
invertase. Glucose and fructose undergo fermentation to form ethanol in the presence of another enzyme,
zymase, which is also found in yeast.

Invertase + C,H,0,
CH,O,+ H,0 CH,0,
Glucose Fructose
Sucrose

Zymase
CH,,0, 2C,H,OH + 2CO,
Glu cose or Ethyl alcohol
Fructose
an important role in maintaining the anaerobic condition.
The carbon dioxide liberated here plays
Note: (i) Fermentation must be carried out in
anaerobic condition, because if air gets into fementation
taste of alcoholic drinks.
mIxture. The oxygen oxidises ethanol
to Ethanoic acid which in turn destroys the

(1) Ethanol is a colourless liquid with

boiling point 351 K.

Yrite any two uses of ethanol.

paint industry. as motor
Ethanol is used as solvent in
Ans: i. a
+ 20% ethyl alcohol + traces of benzene) which is used
. It is used in power alcohol (80% petrol
fuel.
Ii. It is used in alcoholic beverages.
6
What is rectified spirit? spirit.
Ans; water is called rectified
95.5% ethyl alcohol and 4.5%
What is absolute alcohol? absolute alcohol.
100% pure ethyl alcohol is called
Ans:
it a colour)
alcohol? mixing with some copper sulphate (to give
What is denaturation--of by
Ans: unfit for drinking It known as denaturation of alcohol.
The Commercial alcohol is made methanol. is
and pyridine (a foulsmelling
liquid) and
II PUChemistry
<br>

249

1what are
phenols?
Phenols
are the hydroxy
Phenols derivatives of aromatic
directly attached to the benzene
hydrocarbons
is ring. in which -OH group(S) OH
Example: Phenol: It is common
name and
also in accepted
Phenol is also known as carbolic IUPAC name.
acid. It was first
isolated from
coal tar.
Classification of Phenols Phenol
, How do you classify the phenols?
and their
IUPAC Names
Explain with an example.
Based on the number of
s: -OH groups directly attached to
onohydric, dihydric and trihydric
phenols. In phenols OHthe
benzene ring, phenols are classified as
atom of benzene ring. group is attached to sp² hybridised
carbon
(a) Monohydric phenols: They contain only one group
hydroxyl directly attached to benzene ring
Example:
OH OH OH OH
CH,

CH,
CH,
Common name : Phenol o-Cresol m-Cresol p-Cresol
IUPAC name: Phenol 2-Methylphenol 3-Methylphenol 4-Methylphenol

(b) Dibydric phenols: These compounds contain two -OH groups directly attached to benzene ring.
Examples:
OH OH OH

OH

OH
OH
Resorcinol Quinol or Hydroquinone
Common name:Catechol Benzene-1,4-diol
Benzene-1,2-diol Benzene-1, 3-diol
IUPAC name: groups directly attached to benzene ring
(C)
Trihydric phenols: In these compounds, three -OH
Examples OH
OH OH

OH OH

OH
HO OH

OH
Hydroxy quinol Phloro glucinol
Pyrogallol
Common name:Benzene-1,2,3-triol Benzene-1,2,4-triol Benzene-1,3,5-triol
IUPAC name: II PUChemistry
<br>

Alcohols,,Phenols
250
SG

group.
2, Explain the structure of phenol functional
group is attachcd to sp² hybrid carbon atom of an aromatic ring. The C-0-H
Ans: ln phcnol, the -OH bondangd
bond length (136pm) in phenol is slightly less than that
inphenol is 109°, The carbon-oxygen in methank
(142pm).
1090 H

136 pm
Phenol
3. O-H bond length in phenol is slightly less than that in methanol. Give two reasons.
Ans: This is due to
() partial double bond character of C-0 bond in phenol on account of conjugation lone pair of of
ielectros
of oxygen with aromaticring in phenol (resonance effect).
(i) sp hybridised state of carbon to which oxygen is attached.

7.9 Methods of Preparation

1. How would you prepare phenol from chlorobenzene?
Give equation.
Ans: Chlorobenzene is fused with NaOH
at 623 K and 300 atmospheric pressure
acidification gives phenol. to form sodium phenate which cn
Ç1
ÖNa OH

+ NaOH 623 K HCI

300 atm

Chlorobenzene
Sodium phenoxide
Phenol
2. How would you prepare
phenol from benzene via
Ans: Benzene is treated sulphonation?
with oleum to give benzene
acidification gives phenol. sulphonic acid which on
heating with NaOH followed
So,H
OH
Oleum () NaQH
Sulphonation
(i) H
Benzene
Benzene
sulphonic acid Phenol
3. Howwould you prepare
Ans: Diazonium
phenol from diazonium
salts are hydrolysed to phenols
salt?
by warming with water. [March 2022]
N=N-CI
O-H
+ H,0 Warm
S0°C + N, + HCI
Benzene diazonium
chloride
Phenol
Note: A
diazonium salt
is formed by treating aromatic
273-278K (diazotisation). primary amine with nitrous + HCI) at
acid(NaNO,
Student's illuminator
<br>

Publications

Name the product formed when 251

benzene diazonium
Pheno! salt is warmed with water?
Ans:
ethe gas liberated when benzene diazonium
Nitrogen (N) gas salt is warmed with
water?
Esnlain cumenc procesS
Tor the preparation
cumene? of phenol or How would you prepare
phenol rom
.Cumene (1Sopropyl benzene) is oxidised prescnce of air to (March 2015, March 2014, March 2014]
the in
treating with dilute acid gives give cumene hydroperoxide followed
phenol and acetone. by
CH,
CH,
CH, -C -H H,C-C-0-0-H OH

H
100-130°C + CH, -C-CH,
Acetone
Cumene Cumene
hydroperoxide Phenol
7 What is the chemical name of cumene?
Ans: Isopropyl benzene.
8. Name the byproduct formed during cumene process.
Ans: Acetone (propan-2-one)

7.10Physical Properties
1.
Phenols have higher boiling points. Give reason.
Ans: In phenols the hydrogen atom of-OH group is bonded to an electronegative oxygen atom. Therefore, it is
capable of forming intermolecular hydrogen bonding.
Intermolecular hydrogen bonding
H H H

other classes of compounds namely

Hence, phenols have higher boiling points than the corresponding molecular masses
comparable
hydrocarbons, ethers and halo alkanes / haloarenes of
Phenols are soluble in
. water. Give reason.
due to their ability to form intermolecular hydrogen bonds with water
ns: The solubility of phenols in water
molecules.

11 Chemical Reactions
reactions show the acidic nature of phenols.
which
. Write the
acidic nature ofphenols
Ans: The following reactions showthe
react with highly electropositive alkali metals like sodium, potassium,
with metals: Phenols with liberation ofhydrogen
gas.
(a) Reaction corresponding alkoxides
etc., to yield

l PU Chemistry
<br>

Phenos
and,
252 ONa
OH
+ H.
2 + 2Na

Sodium phenate to form sodium phenoxide

Phenol with aqucous sodium hydroxide ,
with alkali: Phenols react
(b) Keaction
reaction.
alcohols are neutral to this
ONa
OH

+ NaOH
+ H0

Phenol
Sodium phenate
are acidic in nature.
The above reactions show that phenols
2. Explain the acidity of phenols or phenols are acidic in nature. Explain. [March 2015)
a proton
Ans: Phenol is slightly acidic in nature. It dissociates partially in water to give phenoxide ion and
OH

+ H

Phenol. Phenoxide
iit 10nif
Phenoxide ion is stabilised by the following resonance
structures.
0:

I II
In resonance structures of phenoxide IV
delocalised in benzene ion, there is no charge aryg
ring. Hence the separation and
phenoxide ion is more
resonance the -ve charge of
+0-H stabilised than pheno.
+0-H 7+0--H O--H

phenol resonance II
structures
ion. have charge
separation and Dhenait
3. Alcohols are less acidic
hence phenol molecule than
Ans: In alcohols,
than phenols. Give is less stable
alkoxide reason.
ion is not stabilised
by resonance.
Hence, alcohols [March 2018/pheno
become than
less acidic
<br>

Publications
nevth 253
Give a chemical reaction to show phenols are morc
4
acidic than alcohols and water. {March 2018]
The reaction of phenol with aqucous sodium hydroxide indicates that phenols arc stronger acids than
Ans:
alcohols and water.
sVhat is the effect of clectron donating group on acidity
Eleectron donating groups
of phenols? Explain.
Ans: decreases the acidity of phenols.
Explanation: Electron donating groups like methyl group (-CH.) increase the clectron
density on oxygen Or
phenoxide 1on and the stability of phenoxide jon decreases. Hence, acidic
strength decreases. Therefore,
cresols are less acidic than phenol.
What is the effect of electron withdrawing groups on the
Electron withdrawing group increases the acidity of phenol.
acidity of phenols? Explain.

Explanation: Electron withdrawing groups like nitro group (-NO,) decrease the electron density on oxygen
of phenoxide ion and the stability of phenoxide ion increases, Hence, acidic strength increases. Therefore,
nitro phenols are more acidic than phenol.
What is effect of the following substituents on acidity of phenol? (a) -CH, (b) -NO:
Ans: (a) -CH; is electron donating group. It decreases the stability of phenoxide ion by increasing the electron
density on oxygen atom of phenoxide ion due to + Ieffect. Therefore acidity of phenol decreases.
(b) - NO, is electron withdrawing group. It increases the stability of phenoxide ion by decreasing the
-
electron density on oxygen atom of phenoxide ion due to I or -R effect. Therefore acidity of phenol
increases.
8 Among o-nitrophenol and phenol which is having higher pka value.
Ans: Phenol (:: greater the pKa value lesser the acidic strength).
9. Explain acylation of phenols with an example.
Ans: Phenols react with acid chlorides or acid anhydrides presence of pyridine to give esters. This reaction is
called acylation of phenols or esterification of phenols.
CH,OH+ (RCO),0 bas
C,H,COOCH, +CH,COOH
Acid anhydrous Phenylacetate
Phenol

C,H,OH+(CH,CO),O– NaOH
,CH,COOCH, +CH,COOH
Phenyl acetate

C,H,OH + R'COCI Pyridine C,H,0COR+ HOl

Phenol Acid chloride Ester

C,H, -OH+ CH,COCI Pyridine C.H,0COCH,+ HCI

Acetyl chloride Phenyl acetate
Phenol presence of
10. Name the product formed when phenol treated with acetic anhydride/ acetyl chloride in
Pyridine.
Ans: Phenyl acetate.
salicylic acid?
How do you prepare aspirin from presence of concentrated sulphuric acid to give aspirin
Ans: Salicvlic acid reacts with acetic anhydride in the
(acetyl salicylic acid).
COOH
COOH
OCOCH,
OH H' + CH,COOH
+ (CH,CO),0
Acetic anhydride
Aspirin (Acetyl salicylic acid)
Salicylic acid
salicylic acid.
12.
reagent used to prepare aspirin from
Ans:
tane the
Acetic presence of conc. H,SO.
anhydride in
Student's illuminator
I| PU Chemistry
<br>

salicylic acid).
aaspirin(acetyl
13 Write the IUPAC
name of the
salicylic acid treated with 2cetic anhytrt,
2-4cetorybenoicacid. formed when
Anss product
14 Name the pharmsceutical
preseace of conc. H,SO
Ans Aspirin acid.
Write the IUPAC name of salicytic
15
Ans 2-Hydroryhenzoicacid
2spirin as 2 medicine. antipyretics.
16 Give the tse of 2 anti-inflzmmatory and
as n2lgesic,
As Aspirin ised phenols with an rample. conc. sulphuric acid to give
esters Thisreads
17. Erplain
esterification of presence of
carboxvic 2cids in the
Ars Pbenols react with
called esterification.

R-COH H-0-CH R-0-CH + HO

Es

Erample
H
-COH
÷
H-0-cH
Penyi berzogte

18 Wht happens when phenol is treated with benzoic acid in presence of conc. H;S0,?
Ars Paeyl bezote esser is focned
19. Electrophiic substitution reaction of phenol occurs at ortho and para position. Give reason.
Ans Phenol is more reactive towzrds electrophilic substitution
reactions than benzene. This is becanse a
gop tich increzses electron density in benzene ring by donating the lone pair of electrons ca
z0m of he-OH group. Moreover phenol is stabilised by resonance as given.
-0-H +0-H 7+0-H ö-H

I
tis clezr fron the zbone structures IV V
charge. As 2 result cdectrophiles that in phenol, carbon atoms
attack these at ortho and para positions acquire3
positions to form ortho
28. What happens whtn phenol and para derivatíves.
Ars: Paenol reacts rezcts with dil HNO;?
wth dilte nitric acid at lorw tenperzture
Write the reaction?
(30456) átrophenols (298 K) to give a ortho-(15)
mixture of
OH
OH
OH
Gune HNO, NO,

Phetxc + 2H.0
-Nitrophenol
(minor)
NO,
Studes ihniatr p-Niophenol
(jor)
<br>

Publications

o-nítrophenol is steam volatile 255

- -Nitrophenol but not p-nitro
is steam volatile duc phenol. Explain.
to intramolecular
t due to
intermolecular hydrogen
bonding(which causeshydrogen bonding. while p-nitrophenol is less volatile
s the association
the of molecules).
H

H
HO -
o-Nitrophenol
(Intramolecular H-bonding)
p-Nitrophenol
Name the (Intermolecular H-bonding)
method used for the separation of o- andp- nitrophenols.
nS: Steam distillation.
Among 0- and p-nitrophenols which one has (a) higher boiling
point (b) higher vapour pressure.
n8:
(a) p-nitrophenol (b) o-nitrophenol

4 What happens when phenol treated with conc. HNO,? or How do you prepare picric acid
phenol? irom
(July 2019,July 2018]
ns: Phenolreacts with conc. HNO, in the presence of conc. H,SO, to give
2,4,6-trinitrophenol commonly known
as picric acid.
OH OH
NO,
conc. H,SO,
+3HNO,

Phenol
NO,
2,4,6-Trinitrophenol (Picric acid)
A yellow crystalline solid

Write the IUPAC name or chemical name of picric acid.

Ans:
2,4, 6- trinitrophenol
Name the product formed when phenol is treated with nitrating mixture.
Ans:
Picric acid.

l, Explain thebrómination of phenol.

Ans:
f24 nol
<br>

and para- bromophenols.

or to givc ortho-
in CHCl, CS,
256 OH
brominc
(b) Phenol reacts with OH

Br
+ 2HBr
Br, in CS,
273 K
o-Bromophenol
Br
Phenol Minor product p-Bromophenol
Major product (80%)
Bromine in CS,/ CHO,
with (a) Bromine water (b)
formed when phenol treated
28. Name thc products
(b) o- andp- bromophenol
Ans: (a) 2,4, 6
- tribromophenol (white ppt) to salicylic acid by Kolbe's
reaction
you convert phenol
reaction or How do 2019, July 2020, March 2022
29. Explain Kolbe's 2017, July 2017, March
March 2014, July 2015, Marchdioxide gas at 413 and 6-7 atm K
pressure gives sodium salic

This reaction is called Kolbe's

on heating with carbon
Ans: Sodium phenate (2-Hydroxybenzoicacid).
salicylic acid
which on acidification gives
OH :ONa OH
COOH
(i) CO,, 413 K
NaOH
6-7 atm
(ii) H
Phenol Sodium phenate 2-Hydroxybenzoicacid
(Salicylic acid)

30. Name the product formed when phenol treated with CO; at 413 K followed by acidification. Name t
reaction.
Ans: Salicylic acid
Reaction name: Kolbe's reaction.
31. What is the role of CO, in Kolbe's reaction?
Ans: C0, acts as a weak electrophile.
32. What is Reimer-Tiemann's reaction? Explain. [July 2016, July 2011]
Ans: Phenol on heating with chloroform in the presence of sodium hydroxide at
gives o-hydroxy benzaldehyde (salicylaldehyde). This reaction is known as
340 K, followed by hydrns
- Reimer Tiemann
reaction.
OH ONa'
aw O
Na"
OH
CHCI, CHO CHO
CHCI, + aq. NaOH
NaOH
HCI
-NaCI
Phenol
Intermediate Salicylaldehyde
Note: In place of chloroform, compound
if we take CCl4, we get salicylic
33. Name acid.
the product formed when followed b
phenol treated with (a) CHCI,
hydrolysis. (b) CCI, presence
in of NaOH followed by
in presence of NaOH
Ans: (a) Salicyaldehyde hydrolysis.
(b) Salicylic
acid
34. Write the IUPAC
Ans: 2-hydroxy
ame of salicyladehyde.
benzaldehyde.
35. What happens
when phenol treated
Ans: Phenol on with Zn-dust? 2018]
heating with zinc
dust give benzene. March
Student's illuminator
<br>

OH
257

+ Zn
+ ZnO
Explainthe oxidation of Phenol
phenols. Benzenc

(a) Theoxidation of phenol (March 2015]

Ouinones are not by chromic acid, forms a
aromatic compounds. conjugate
OH They are a, B-unsaturated diketone known as benzoquinone.
ketones.

Na,Cr,0,
H,SO,

Phenol

Benzoquinone
(b) Phenols undergo slow oxidation
in the presence of air togive benzoquinone, a
OH pink coloured liqui.

Air

Phenol

Benzoquinone

Multiple Choice Questions (MCQs)

1.
Quinol is an
example for c) Neopropyl benzene
a) Dihydric alcohol b) Dihydric phenol d) Neomethyl benzene
c) Trihydric phenol d) Trihydric alcohol
6. Phenol is known as
The most acidic among the following a) Carbolic acid
2
is
b) Benzyl alcohol
a) c) Salicylic acid
Phenol b) p-Cresol
d) Salol (phenyl salicylate)
c) p-nitrophenol d) Picric acid
3 7. The IUPAC name of Salicylaldehyde is
Yhen phenol is treated with excess of
bromine water, it gives
a) 2-hydroxy benzaldehyde
a) m-bromophenol b) hydroxy benzyl alcohol
b) o- and p-bromophenol
c) 4-hydroxy benzaldehyde
c) 2,4-dibromophenol 5-hydroxy phenol
d)
) 2,4,6-tribromophenol
8. Picric acid is a yellow coloured compound. Its
acid gives
Oxidation of phenol by chromic chemical name is
a) m-nitrobenzoic acid
(a) Aldehydes Benzoquinone b) 2,4, 6-trinitrophenol
(b)
acid
(c) Acetone (d) Benzoic c) 2,4, 6-tribromophenol
3, Chemical d) p-nitrophenol
name of cumene is
2) Isomethyl benzene
b) Isopropyl II PUChemistry
benzene
Students
<br>

1)
c) Acetone presence of
13. Name of the following reaction is

the
10. In substituted phenols, such as nitro OH
groups
electron withdrawing 1.CHCl/NaOH

group
Increases the acidic strength 2. H

a)
b) Decreases the acidic strength
acidic strength Williamsons reaction
c) Decrease or increase the (a) Reimer-Tiemann reaction
d) Unpredictable (b)
p-nitrophenol are reaction
11. 0-nitrophenol and (c) Kolbe's
reaction
separated by (d) Wurtz
a) Fractional distillation
b) Sublimation
c) Crystallisation
d) Steam distillation
Answer Keys
11 12 13 14
6 9 10
1 2 4 5
d C b
b b C
b d b

Ethers
1. What are ethers?
derivatives of hydrocarbons.
Ans: Ethers are alkoxy or aryloxy
2. Write the general formula of ethers. or aryl group.
general formula of ether is R-O-R, where R and R´are alkyl
Ans: The

7.11 Classificationand Nomenclature of Ethers

an example.
1. How do youclassify the ethers? Explain with
Ans: Ethers are classified into two types: or=
oxygen atom is bonded to two identical alkyl
Simple or symmetrical ethers: The ethers in which the
groups are called simple or symmetrical ethers.
Examples: Diethyl ether (C,H,-0-C,H,), Diphenylether (CH,-0-CoH,)
ally
different
ii.
Mixed orunsymmetrical ethers: The ethers in which the OXygen atom is bonded to two
arylgroups are called mixed or unsymmetrical ethers.
Examples: Ethyl methyl ether (CH,-0-C,H,)
Anisole (methoxy benzene) (C,H,-0-CH,)

Chen
PU
Student's illuminator al
<br>

1Writethe IUPAC names of

the following
ethers. 259

Compound IApril 2022/

Comon nane
CH,0CH, IUPAC name
Dimethyl cther
c.H,-0-C,H, Methoxymethane
Dicthyl ether
Ethoxyethane
C,H,-0-CH,
Ethyl methyl
cther
Methoxyethane
CH,OCH,CH,CH,
Methyl n-propyl
cther 1-Methoxypropane
CH,-0-CH, Methyl phenyl ether
(Anisole) Methoxybenzene (Anisole)
C,H,0CH,CH,
Ethyl phenyl ether ( Phenetole)
Ethoxybenzene
C,H,0(CH,) CH,
Heptyl phenyl ether
1-Phenoxyheptane
CH,0-CH-CH, Methyl isopropyl ether 2-Methoxypropane
CH,

CH,-0-CH, CH, ÇH-CH, Phenyl isopentyl ether 3-Methylbutoxybenzene

CH,

CH,-0-CH,– CH,–0-CH, 1,2-Dimethoxyethane

HC CH, 2-Ethyl-1,
OC,H, 1-dimethylcyclohexane

12 Structure of Ether Functional Group

group by taking methoxymethane as erample.
plain the structure of ether functional around OXygen are 141pm
ts: In ethers, two lone pairs of electrons angle (111.70
the two bond pairs and
arrangement. The C-0-C bond insH
<Tanged almost in a tetrahedral tetrahedral angle (109°28') due
to the
greater than the
noxymethane) is slightly groups. bond length (141 pm) in
two bulky The C-O
palsive interaction between alcohols (142 pm in methanol). Methoxymethane
ethers is almost the same as in

143
Preparation of Ethers
by
dehydration
of alcohols? Explain with
an erample.

How would you prepare ethers presence of conc. H,SO, at 413K or 140°C.
excess of alcohols in
prepared by heating K
,R-0-R+H,0
H_SO,/413
R-OH +H -0-R
I| PUChemistry
<br>

Js, Phenos
andE

K -0-C,H,+ H,0
260 -C,lI,,SO,/413 SC,H,
C,H,OH + H0- Dicthyl cther
Evample:
Ethyl alcohol alcohols.
ofmonohydric
as anhydrides ether.
Note: Ethers ae called of alcohols into involving the attack of alcohol
dehvdration
Explain the mechanism of rcaction (S2) mole
2.
of cthcr is a
nuclcophilic bimolccular
Ans: The formation
as indicated below:
on a protonated alcohol,
„H,
CH, -CH, -O
) CH, - CH, -0-H+H H
Protonated alcohol
Ethanol

H
CH,CH, + H,0
CH,- ÇH, LO
CH,CH, -)-
(ii) CH,CH,
Ethanol
-t H H
Oxonium ion

Protonated alcohol

(ii) CH,CH, 70- CH,CH, CH,CH, -– CH,CH, + H,

Diethyl ether
H
Oxonium ion

3. Name the product formed when 1° alcohols heated in presence of conc. HSO, at 413 K.
Ans: Ethers
4. Name the predominant reaction occurs when 2° and 3° alcohols are heated in presence of conc. HS0
Ans: Elimination reaction.
5. Explain Williamson's ether synthesis with an example.
(March 2014, July 2014, March 2015, July 2016, March 2019, July 2019)
Ans: Alkyl halides on heating with sodium alkoxide in alcoholic medium gives ethers. This reaction isa
Williamson ether synthesis.
R-ONa +X-R'R-0-R+ NaX

Example. (i) CH,ONa + I- CH, CH, -0-CH, + Nal

Sodium Methyl iodide
methoxide Dimethyl ether
(ii) CH, -CH, -ONa+ Br
-CH, -CH, -CCH,+NÊ
Sodium ethoxide
Bromoethane
Sy 2
CH, -CH, -0-CH,
Diethylether
6. Which of the following is better
method for the preparation
CH,
oft-butyl ethyl ether? Give reaso
CH,
C,H,ONa + CH, -c or C,H,Cl +
CH, - C-ONa
CH,
CH,
6)
(ii)
Ans: (ii)
Reason: In case
of primary alkyl halide
tertiary alkyl halides, only substitution Secondary
elimination competes reaction takes place
over substitution but in Case of
to form alkenes.
Student's illuminator
 nechanism?
<br>

Sy2
How
prepare anisole (methoxybenzene)
would you
Sodium phenate
on heating with methyl by Williamson's synthesis?
iodide gives anisole.
ONa OCH,

+ CH,-I + Nal
S2

Sodium phenate Anisole (methoxy benzene)

14.Physical Properties of
Ethers
Ethers have less boiling point than alcohols. Why?
Due to absence
of
hydrogen bonding in ethers.
water. Give reason.
Ethers are miscible in
.This is due to the formation of intermolecular hydrogen bonds with water molecules.
R
H
R
R

H..

Intermolecular hydrogen bonding ether and water

715 Chemical Properties of Ethers

limited amount of HX? Explain with an example.
What happens when ether is heated with alcohol and alkyl halide.
amount of hydrogen halide gives a mixture of
Ans: Ethers on heating with limited
HX R-OH+ R –X
R-0-R+
ether limited alcohol alkyl halide

+ C,HI
Example: C,H, -0-C,H,+ HIC,H,OH Ethyl iodide
Ethanol
Diethyl ether
Excess of HI
amount of HI (b)
heated with (a) Limited
2 What happens when diethyl ether
A
C.H,–OH C,H,leasxila
t Ethyl tt a
Ans:
(a) C,H,-0-C,H, + HI
limited Ethanol iodidedttttht
Diethylether
+ H,0
(b) C,H, -0-C,H,+ 2HI
2C,H,-I
iodide
Excess Ethyl or Sy2.
Diethylether Mention whether the reaction is S1
3 equation.
Complete the following

CH,
conc. HI
CH, -C-0-CH;

CH;
<br>

Alcohols,
262 Phends
andt
Ans:
CH, CH,
conc. II
CH,--0-CH, CH,- -1+ CH,
-OH

4. How is HX is react with alkyl aryl ethers? Explain with an example. July 2015,
July2024
Ans: Alkylaryl cthers react with HX to form phenol and alkyl halide.
0-R OH

+ H-X -
+R-X
Alkyl halide
Alkyl aryl cther Phenol
Example:
Q-CH, OH

+ H-I + CH, I
Methyl iodide
Anisole
Phenol
5. Explain the halogenation (bromination) of anisole.
Ans: Anisole reacts with bromine in ethanoic March 2018, July 201
acid gives p-bromo and o-bromoanisole.
OCH, OCH, OCH,
Br
Br, in
+
Ethanoic acid

Anisole
p-Bromoanisole
Br (Minor)
p-Bromoanisole
(Major)

6. Bromination of anisole carried out

in the absence of iron
Ans: Because, in anisole - OCH, (I[)
(methoxy) group activate the benzenebromide catalyst. Why'?
7. Explain Friedel-Crafts ring. Hence it need not requires
Ans: Anisole reacts with alkylalkylation of anisole. Catg
[March 2020]
halide in the presence.of
and para alkyl anisole. anhydrous aluminum chloride as a
catalyst to gh
Example:
OCH,
0CH, OCH,

+ 2CH,CI Anhyd.AlCI, CH,

Metlyl CS, + + 2HCI
chloride
Anisole
2-Methoxytoluene
(Minor) CH,
4-Methoxytoluene
(Major)
<br>

Publications
th 263
Explainthe Friedal-Crafts ncylation of anisolc.
concts with
acctyl chloride (July 2019)
in the prescnce of anhvdrous
AICI,
and p-acetyl derivatives
to give o of
anisole.
OCH,
OCH,
OCH,
Anhyd.AICI, COCH,
+ 2CH,COCI
Acetyl + 2HCI
chloride
Anisolc
2-Methoxyacetophenon
(Minor) COCH,
4-Methoxyacetophenone
Explain the nitration of anisole. (Major)

S:
reacts with
Anisole a
mixture of conc. nitric acid and conc.
sulphuric acid to give a mixture of ortho and
para nitroanisole.
OCH, OCH,
OCH,
NO,
Conc. H,SO,
2 Conc. HNO, + 2H,0

Anisole
2-Nitroanisole
(Minor) NO,
4-Nitroanisole
(Major)
. Anisole undergo electrophillic substitution reaction at o and p position. Explain.
s: In anisole, - OCH, is electron releasing group. In resonating structures of anisole negative charge is appear

at o- and p-positions as shown below.

AOCH, ÖCH, ŽCH, oCH, ÖCH,

II V V
I II
hence, anisole undergo electrophillic
substitution reaction at o andp- positions.
Multiple Choice Questions(McQs)
2. The given reaction can be classified as
Anisole
on treatment with Conc. HNO, and
Conc. H,SO4
gives
a) Phenol ONa OCH,
b)
Nitrobenzene
c) CH,I
and p- nitro anisole
O-
d) o-nitro
anisole
The with HI a) Alcohol formation reaction
heating of phenyl methyl ether
produces b) Dehydration reaction
c). Williamson alcohol synthesis reaction
a) Ethyl chloride b) Iodobenzene Williamson's ether synthesis reaction
<br>

Aldehydes, Ketones UNIT

and Carboxylic Acids 8
Aldehydes and Ketones
What are carbonyl compounds?
e The organiccompounds Containing carbonyl functional group
(>C= 0) are called carbonyl compounds.
Examples: Aldehydes and ketones
Name the class
of organiccompounds which contains carbonyl
m6t (i)
functional group.
Aldehydes (-CHO), (ii) Ketones (>CO), Carboxylic acids
anhydride (RCO)>0), Esters (RCOOR)
(-C0OH), Acyl halides (R - COX), ACid
and Amides (R-CONH)
Write the general formula of aldehydes and ketones.
ns:

H
R-c =0 H R'
or R-C-R'
Aldehyde Aldehyde Ketone
Ketone
Name three carbonyl compounds which add fragrance and flavor to nature.
ns:
Vanillin (from vanilla beans), salicylaldehyde (from meadow sweet) and cinnamaldehyde (from cinnamon).

1
Nomenclature and Structure of Garbonyl Group
ommon names:
are derived from the common names of the corresponding
The common ames of. most of the aldehydes are
replacing the ending -ic of acid with aldehyde. The locations of the substituents
carboxylic acids by group.
so on beginning with carbon atoms next to the carbonyl
indicated by Greek letters a, B and
groups bonded to the carbonvi
are derived by naming tWo alkyl or aryl
The common names of ketones
groun. The locations of the substituents are indicated by Greek letters aa,
Bß and so on beginning with

group.
carbon atoms next to the carbonyl acetone. Alkyl phenv
have historical common names; the simplest dimethyl ketone is called
Some ketones to phenone.
are named by adding the acyl group as prefix
Ketones usually
UPAC names:
and ketones are derived from the names of the
open chain aliphatic aldehydes
The IUPAC names of
ending -e with -al and -one respectively.
by replacing the name of the
corresponding alkanes Carbaldehyde is added after the full
suMX
group is attached to a ring, the
When the aldehvde
cycloalkane.
<br>

benzene carbaldehyde. Howeve,

ring is
group on a benzene
aldehydes are named as substituted
aldehyde
Other aromatic
274 aromatic
simplest IUPAC.
The
name of the accepted by
is also
benzaldehyde
the
benzaldehydes.
names of the following
Write the IUPAC IUPACname
Ans: Common names Methanal
Formula Formaldehyde
Ethanal [July 2014)
HCHO Acetaldehyde
CH,CHO Propanal
Propionaldehyde
CH,CH,CHO Butanal
Butyraldelhyde
CH,CH,CH,CHO 2-Methylpropanal
Isobutyraldehyde 20201
CH,),CHCHO Propanone or Propan-2-one (July
Acetone
CH,COCH, Butan-2-one
CH,COCH,CH, Ethyl methyl ketone
Pentan-2-one
CH,COCH,CH,CH, Methyl n-propyl ketone
Diisopropylketone
2,4-Dimethylpentan-3-one [July 2018]
CH,),CHCOCH(CH,),
Mesityl oxide
4-Methylpent-3--en-2-one
CH,),C = CHCOCH,

.CHO

Phthaldehyde Benzene-1,2-dicarbaldehyde
CHO

CHO
3-Bromobenzenecarbaldehyde
m-Bromobenzaldehyde Or
Br
3-Bromobenzaldehyde

B-Methylcyclohexanone
3-Methylcyclohexanone

-CH,

CH,CH =CH-CHO
Cinnamaldehyde
3-phenylprop-2-en-1-al
Explain the structure
Ans: The carbonyl
of carbonyl group.
carbon in aldehydes
angle of 120° from and ketones is sp² bya
each other. The carbonyl hybridised and forms separated
TT
-electron cloud
is above and below carbon and the three threeo-bonds and
this plane, as atoms bonded to it lie in one plane
shown in figure.
<br>

T-bond
sp

The carbon-oxygen double

bond is polarised
The electrons, particularly duc higher
Oxygen a partial negative
the loscly held to
-electrons,are clectroncgativity oxygen relative to carb
of

charge and pulled": strongly towards

electrophilic (Lewis
acid), and carbonylcarbon a partial positive charge. the oxygen atom to g
have substantial dipole moments
oxygen a Thus, the carbonyl carbon is
nucleophilic
and are more polar (Lewis base) centre. Carbonyl compour
than cthers.

(A) (B)

What is the hybridisation

of carbonyl carbon atom?
Ans: sp [March 2014/

The carbon-oxygen bond

in carbonyl group is polar in nature. Why?
Ans: Due to electronegativity
difference between carbon and oxygen.

8.2 Preparation of Aldehydes and Ketones

1.
Name the organic compounds formed by the oxidation
of primary and secondary alcohols.
Ans: (i)Oxidation of primary alcohols gives aldehydes.
(ii) Oxidation
of secondary alcohols gives ketones.
2
Name the catalyst used in the dehydrogenation of alcohols into aldehydes and ketones.
Ans: Ag or Cu
3.
Name the organic compounds formed by the dehydrogenation of alcohols.
Ans: Primary alcohols give aldehydes and secondary alcohols give ketones.
4.
now wouldyou prepare aldehydes or ketones by ozonolysis of alkenes?
AnS: Ozonolysis with zinc dust and water gives aldehydes or ketones or mixt
of alkenes followed by reaction
Of both depending up on substitution pattern of alkene.

Glve the preparation of aldehydes and

ketones by hydration of alkynes.
ot
of dil H,SO, and HgSO, gives acetaldehyde. Hydration of
Ans: Addition of water to ethyne inthe presence
alkynes under similar condition gives ketones.
Preparation of Aldehydes you prepare aldehydes from ace
an example or How would
Explain Rosenmund reduction with 2014, March 2015, Juy 2015, March 2018, March
2020. J
Chloride or Benzovl chloride? March
2020]
presence of palladium catalyst supported by bariumn sulphate gi
Ans: Acid with H,
in
chlorides on reduction Rosenmund's reduction.
Cldehydes, This reaction is
called

HCI
Pd, BaSO,
Cl+ H, (Boiling
R--H+
R--
Acid chloride xylene)
in Aldehyde
<br>

276
Example 1:

rd, BasO, >CH,

-H+HCI
CH, CI+ H, Boiling in Acctaldchyde
Acetyle chloride xylenc)

Example 2:
CHO
C Pd, BaSO, + HCI
+ H (Boiling in
xylene)
Benzaldehyde
Benzoyl chloride

prepare aldehydes from nitriles?

2. How would you on with stannous chloride and hydrochloric ari4.
Nitrjles reduction
Ans: (a) By Stephen's reduction: on hydrolysis gives corresponding aldehyde. This
reaction is
imine hydrochloride which
Stephen's reduction.
SnCl, + 2HCI SnCl, +2 [H]

+ 2 [H
SnCl, + conc. HCl
R-CH=NHHCI H, boil R-c-H + NH
R-CEN Ether Imine Aldehyde
Nitrile or ethyl acetate

Example:

SnCl, + conc. HCl H0, boil

+ NH,CI
CH,-CEN + 2[H >CH,CH=NHHCI CH,-C-H
290 K Acetaldimine Acetaldehyde
Ethane nitrile
hydrochloride

(b By using DIBAL-H: Nitriles on reduction with disobutylaluminium hydride (DIBAL-H) gis

imines which on hydrolysis gives aldehydes.
- AlH((-Bu)2
R-CN 2R-CHO
2-
H,O

Example: CH, -CNAnp2 CH, -CHO

Ethane nitrile
2- H,0 Ethanal
3. How would you prepare aldehydes from esters?
Give an example.
Ans: Esters are reduced to aldehydes with
DIBAL-H followed by hydrolysis.

CH,(CH,), --0C,H, DIBAL-H

2- H,0 CH,(CH,), --H.
Decanal
4. Name the reagent or oxidising agent
uscd in Etard's reaction.
Ans: Chromyl chloride (CrO,CI,) [March 2018]

5. What is Etard's reaction?

Explain.
Ans: Toluene on
oxidation with chromyl chloride (July 2015, July 2020, April 2022 gives
benzaldehyde. This reaction (CrO,CI) gives chromium complex, which on hydrolysiss#
is called Etard's reaction.
Student's illuminator
Chemis
PU
<br>

Publications
h 277
CH,
CH(OCrOHCI), CHO
+ CrO,C1,
H,0',
Chromyl chloride
Touene Chromium complex Benzaldehyde
How would you convert toluene into
benzaldehyde by using chromic oxide or chromic anhydride
(CrO:).
. Toluene reacts with acetic anhydride în the presence of chromic oxide to give benzylidene diacetate which
an acid hydrolysis gives benzaldehyde.
CH,
K
CH(OCOCH,), CHO
273-283
+ (CH,CO),0 H,o
CrO,
Acetic
anhydride
Toluene Benzylidine diacetate Benzaldehyde

Carbonyl group is more susceptibie to the attack of nucleophiles. Justify your answer.
Because, oxygen is more electronegative than carbon. Hence carbonyl carbon acquires partialpositive charge
(acts as electrophile). So it is attached by nucleophiles.
toluene.
Explain the commercial method of manufacturing benzaldehyde by side chain chlorination of
s Chlorination toluene gives benzal chloride, which on hydrolysis gives benzaldehyde.
of side chain of
.CH, CHCI, CHO
CI/hv H,0
373 K
-2HCI
Benzal chloride Benzaldehyde
Toluene
2020]
Explain Gatterman-Koch reaction. |March 2014, March 2017, .July 2019, July
presence of anhydrous aluminium
carbon mnonoxide and hydrogen chloride in the –
s: Benzene reacts with reaction.
benzaldehyde. This reaction is called Gatterman Koch
or
chloride cuprous chloride gives
CHO
CO, HCI
Anhyd. AICI/CuCI
Benzaldehyde
Benzene

reparation of Ketones chlorides? Explain with an example.

would you
prepare ketone from acyl reaction of cadmium chloride with Grignard
ow dialkylcadmiumn (prepared by the
ns; Acyl chlorides reaact with
reagent) gives ketones. 2Mg(X)CI
R,Cd +
2R- Mg -X + CdCl,
+ CdCl,
2R
2R'-C-C1 + R,Cd

Example: -Cd-CH, -CH,

CdCl, >CH, -CH,
Diethyl cadmium
2CH, –CH, – MgBr inEther
Ethyl magnesium bromide I| PUChemistry
 Aldehydes, Ketones
<br>

and cattonjick
Jee
278
CH, – CH,
CI + CdCI,
(CH,CH,),Cd 1.
AF
ketonc
Ethyl phcnyl
Benzoylchloride
Grignard reagent. 2
ketones from nitrile by using
Give the preparation
of
2.
rcagent followed by
hydrolysis gives ketones. A
with Grignard
Ans: Nitriles react
R
, +
NH,
H,OH R-= O+ Mg(OH)X
R'MgX NMgX
R-C= N
Ether
R-=
imine salt
Ketone
Nitrile followed
reacts with methyl magnesium bromide (Grignard reagent) b
Example: 1) Ethane nitrile

hydrolysis gives acetone.

„NMgBr
H,O/H CH, + Mg(OH)Br+ NH,
CH,MgBr
T| CH, – -C-CH,
CH,
-C= N Ether CH, Acetone
Ethane nitrile

by acid hydroly
2) Propane nitrile reacts with phenyl magnesium bromide (Grignard reagent) followed
gives 1-phenylprapan-1-one.

H,0/H
C,H,MgBr Ether CH,CH, - C,H, -C + Mg(OH)Br + NH,
CH,- CH,
–C= N+
Propane nitrile CH, C,H,
(Propiophenone
or l-phenylpropane-1-one)

3. A (nitrile) + CçHsMgBr i) Ether

iü) H,0
CçHCOCHJ. Write the structure of A.
Ans: CH,CN (Ethane nitrile).
4. How do you prepare aromatic ketones by Friedel craft's acylation? Explain with an example.
[March 2019)
Ans: Benzene reacts acid chloride in the presence of anhydrous aluminum chloride
with correspondi
to give
ketone. This reaction is called Friedel-Crafts
acylation.

+R-C-CI-Anhyd.AICI,
in Ether
R
Acetyl
chloride
Aromatic ketone
Example: Benzene reacts with acetyl git
chloride in the presence of anhydrous aluminum chloride to
acctophenone.

+ CH, Anhyd.AlCI,.
--CI
Acetyl in Ether CH,
chloride
Acetophenone
Student's illuminator
<br>

Publications
279
Physical Properties
What type of attractive forces are therc betwccn
molecules of aldehydes or ketones?
Aldehydes and ketones are polar in nature
duc to the presence This
creates dipole- dipole attraction betwccn the permancnt of the carbon-oxygen double bond.
dipolcs and I with the ncarby molecules.
The boiling
points of aldchydes and
ketones are higher
molecular masses. Give reason. than hydrocarbons and ethers of comparable
is due to the weak molecular association in aldehydes and ketones dipole-dipole
arising out of the
interactions.
points of aldehydes and ketones are lower masses. Give
: Boiling than alcohols of comparable molecular
reason.
This is due to theabsence of intermolecular hydrogen bonding in aldehydes and ketones.
in water at all
Lower members of aldehydes and ketones (methanal, ethanal, propanone) are miscible
1
proportions. Why?
Recause they form intermolecular hydrogen bond with water.
points
:
Arrange the following compounds in the increasing order of their boiling
CH.CHO, CH;CH,OH, CH,0CH3, CH,CH,CH,
> CH;CH,CH,
Ans: CH;CH,OH> CH;CHO > CH;OCH,

8.4 Chemical Reactions

(1) Nucleophilic addition reactions and ketones.
mnechanism of nucleophilic addition reactions of aldehydes
1. Explain the
addition reaction, group from a direction
In base catalysed nucleophilic
the polar carbonyl
Ans:
carbon atom of
the electrophilic
A nucleophile attacks hybridised orbitals of carbonyl carbon.
perpendicular to the plane of sp² sp and a tetrahedral
alkoxide
changes from sp² to
the hybridisation of carbon
During this,
neutral product.
intermediate is produced. medium to give the electrically
reaction
intermediate captures a proton from the oxygen double bond.
iii. This across the carbon
The net result is
addition of Nu and Ht
Nu
Nu H
Nu: fast OH
slow a
step 2
step Addition product
intermediate
Tetrahedral
Give reasons.
Planar nucleophilic addition reactions.
ketones for
more reactive than electronic effect.
generally steric and to
Aldehydes are aldehydes due to hinders the approach of nucleophile
Ans: Ketones are reactive than substituents in ketones
less large
presence of two Icarbon than
i Steric effect: The in aldehydes. the electrophilicity ofthe carbonyl
than reduce
carbonyl carbon groups of ketones
ii. effect: Two alkyl reaction. Give reason.
Electronic
nucleophillic addition I| PU Chemistry
in aldehydes. towards
3 reactive
BenolHabdo is less
<br>

Catbonfc
and become less clectophilie
280 benzaldchyde is reduccd
polarity of carbonyl group in
Ans: Duc to resonancc. the
H

an example.
ketones reacts with HCN? Explain with
4. How docs aldchydecs and (hydroxynitrilee
react with hydrogen cyanide (HCN) to give cyanohydrins
Ans: Aldchydes and ketones
OH
R-C- CN
R-C-R'/H +H-C= N
Aldehydekctone R'TH
Cyanohydrin

Example:

HCN add to acetaldehyde to give acetaldehyde cyanohydrin (2-hydroxypropanenitrile).

OH
CH,--H+H-C=N CH, -C- CN
Acetaldehyde
H
2-hydroxypropanenitrile
(Acetaldehyde cyanohydrin)

5. Name the products formed when aldehydes and ketones reactions HCN.
Ans: Cyanohydrins
6. Explain the mechanism of addition of HCN to aldehyde or ketone. [March 2015
July 2016J
Ans: Step 1: The nucleophile CN- ion attacks the carbon atom
of the carbonyl group to form alkoxide xm
(Tetrahedral intermediate).
HCN +
OH
CN + H,O

-+ ÇN
Step
1

Tetrahedral
intermdiate
Step 2: Protonation of the alkoxide oxygen
gives cyanohydrin product.
CN
H

Step 2
OH
Tetrahedral Cyanohydrin
7. intermdiate
How do aldehydes and
ketones react with NalHSO;?
Ans: Aldehydes and lower Give an example.
members of ketones reacts precipitate a
"bisulphite addition with sodium bisuiphite white
compounds . to give

Student's illumingtr
<br>

Publ
yth
281
0 + NaHS0, os0,H
proton transfer
Sodium OsO,Na
bisulphite ONa
Carbonyl group
OH
Examples: Bisulphite addition
compound (crystalline)
Addition of sodium sulphite
to acetaldchyde gives acctaldchyde
sodium bisulphite compound.
OSo,H
CH, Ç + NaHSO, Proton
oSÔ,Na
CH,-(-ONa CH, C-OH
H transfer
Acetaldehyde H H
Acetaldehyde sodium
Addition of sodium bisulphite to bisulphite compound
i. acetone gives acetone sodium
bisulphite compound.
OSO,H OsoNa
CH, Ç
+ NaHSO, Proton
CH,- Ç-ONa CH,- C--OH
CH, transfer
CH, CH,
Acetone Acetone sodium
bisulphite compound
Note: The hydrogen sulphite addition compound is water soluble and can be converted back to the original
carbonyl compound by treating it with dilute mineral acid or alkali. Therefore, these are useful for
separation and purification of aldehydes.
Higher ketones like acetophenone do not reacts with NaHSOJ. Give reason.
ns: Due to steric hindrance.
-
Explain the addition of alcohols to aldehydes with an example.
presence of dry HCIto yield alkoxyalcohol intermediate
nS: Aldehydes react with one molecule of alcohol in the
known as hemiacetals, which further react with another molecule of
alcohol to give a germinal dialkoxy.
compound called acetal. OR
OH
R-C -OR'+
dry HCI R'OH H,0
R-C-H+R'OH R-C-OR'
Aldehyde Alcohol H H
Hemiacetal Acetal
(unstable) (stable)

Example:
methanol with ethanal produces the following results.
Ihe reaction of
OH

CH,
- OH CH, – C-Hh
CH, –C- H+ dry HCI
Acetaldehyde Methyl alcohol OCH,
Hemiacetal

OCH,
OH
CH, - C-H+ CH, -OHCH,-C-H+ H,0
OCH,
OCH, Acetal
Hemiacetal
with one equivalent of
What is hemiacetal? formed by the reaction of aldehydes
intermediate
hydrogen chloride.
Ans:
Hemiacetal an alkoxyalcohol
1s presence of dry
monohydric alcohol in the PU Chemistry
Student's
illumir
<br>

Aldehydes, Ketones and

Catboni,
282
presence of dry HCI.
wvhenaldchyde reactswith alcohols in
11. Name the product formed
Ans: Acetals.
12. What are acetals? groups arc present onthe terminal carbon atom.
which two alkoxy
Ans: Acetals arc gem-alkoxy alkanes in
13. How doces ketones reacts with
ethylencglycol? Write general reaction.
presence of dry HCI gas to give cyclic product knownasethye
a
Ans: Ketones react with ethylene glycol in the
glycol ketal.
R O-ÇH,
R dry HCl gas + H,0
ÇH,OH
+
C=0 CH,OH
dil HCI
R O-CH,
R
Ethylene glycol Ethylene glycol ketal
Ketone
glycol to ketone?
14. the role of dry hydrogen chloride during the addition of ethylene
What is
hence increase
Ans: Dry hydrogen chloride protonates the oxygen of the carbonyl compounds and
electrophilicity of carbonyl carbon facilitating the nucleophilic attack of ethylene glycol.
15. Name the products formed by the hydrolysis of acetals and ketals by aqueous mineral acids.
Ans: Acetals give aldehydes and ketals give ketones.
16. How does aldehydes and ketones react with hydroxyl amine? Explain with an example.
[July 2014, July 20171
Ans: Aldehydes and ketones react with hydroxylamine in weakly acidic medium to form oximes.
R R
H
c0+ HNOH C=NOH + H,o
R'H) Hydroxylamine R(H)
Aldehydeketone Oxime
Examples:
(a) Formaldehyde reacts with hydroxylamine to give fornaldoxime.
H H

+ H
-0 HNOH C=NOH + H,0
H Hydroxylanine H
Formaldehyde Formaldoxime
(b) Acetaldehyde reacts with hydroxylamine to give acetaldoxime.
CH, CH,
0+ HNOH C=NOH + H,0
H Hydroxylamine H
Acetaldehyde Acetaldoxime
(c) Benzaldehyde reacts with hydroxylamine to give benzaldoxime.

CH C,H,
+
C-0 HNOH C=NOH + H,0
H Hydroxylamine H
Benzaldehyde
Benzaldoxime
(d) Acetone reacts with hydroxylamine to
give acetoneoxime.
<br>

CH,
C-0+ H}NOH
H CH, 283
CH, Hydroxylamine
Acetone
C=NOH +
H,o
CH,
Acetoncoxime
product formed
Namethe
when aldehyde
Aldoximes reacts with
: hydroxylamine.
Name the product formed when
ketone reancts
Ketoximes with hydroxylamine.
Explain
the reaction of aldehydes amd
ketones with
hydrazine with an example.
Aldehydes s and ketones react with
hydrazine to form hydrazones. |March 2014, March 2018]
R
R
C=0+ HNNH,
C=NNH,t H,0
RH) Hydrazine
Aldehydeketone
R(H)
Hydrazone
Exanples:
(a) Formaldehyde reacts with hydrazine to give formaldehydehydrazone
H
H
H
C-0+
H NNH,
C=NNH, + H,0
H
Hydrazine
Formaldehyde Formaldehydehydrazone

(b) Acetaldehyde reacts with hydrazine to give acetaldehydehydrazone

CH. CH,,
H
=0+H,NNH, C=NNH, + H,0
H

Hydrazine
Acetaldehydrazone
Acetaldehyde
benzaldehydehydrazone
(c) Benzaldehyde reacts with hydrazine to give
C,H
C,H\ NNH, C=NNH, + H,O
C=0+ H

H
H Hydrazine Benzaldehydehydrazone
Benzaldehyde
to give acetonehydrazone
(d) Acetone reacts with hydrazine
CH C=NNH, + H,O
CH + HNNH, H,
CH C0
CH,
Hydrazine Acetonchydrazone
ketones? Explain with an erample.
Acctonc
phenylhydrazine on aldehydes and
phenylhydrazones.
form corresponding
20,
What is
the action of phenylhydrazine to
react with
and ketones
Ans: Aldehydes R
C=NNHC,H, + H,0
R HNNHC,H, H,
C-0+ Phenylhydrazine R'T)
Phenylhydrazone
R(H)
Aldehydc/ketone

Examples: I| PU Chemistry
<br>

formi
284 phenylhydrazine to give
with
Fomaldehyde reacts H
(a) NNHC,H, + H,0
C=
0+H,]NNIC,H, Fornaldelydephenyliydrazone
Phenylhydrazine
acetaldehydephenylhydrazone
Fomaldehyde
phenyhydrazine to give
Acetaldehyde reacts with CH,
(b)
NNHC,H, + H,0
CH,
0+ H, NNHC,H, H
Phenylhydrazine Acetaldehydephenylhydrazone
H

Acetaldehyde benzaldehydephenylhydrazone
phenylhydrazine to give
(c) Benzaldehyde reacts with
C,H,
CH, H - NNHC,H, + H,0
0+ H]NNHC,H,
H Phenylhydrazine H
Benzaldehydephenylhydrazone
Benzaldehyde
acetonephenylhydrazone
phenylhydrazine to give
(d) Acetone reacts with
CH,
CH,
NNHC,H,
H, NNHC,H, + H,0
0+Phenylhydrazine CH
CH,
Acetonephenylhydrazone
Acetone

How does aldehydes and ketones reacts with 2, 4-DNPH?

Give an example.
21.
to form 2,4-dinitrophenylhydrazos
Ans: Aldehydes and ketones react with 2,4-dinitrophenylhydrazine (DNPH)
(2,4- DNPH is called Brady's reagent).
NO, NO,
R, R
C-0+ H, NNH C=NNH- (O-NO, + HO
R'H) 2,4-dinitro
R'H)
Aldehydeketone phenylhydrazine 2,4-dinitrophenyl
hydrazone
Examples:
(a) Formaldehyde reacts with 2, 4-dinitrophenylhydrazine to
give
formaldehyde-2, 4-dinitrophenylhydrazone
NO,
NO,
C-0+H,NNH NNH
C=
H H

Formaldehyde 2,4-dinitro
phenylhydrazine Formaldehyde 2,4-dinitrophenyl
(b) Acetaldehyde reacts with 2,4-dinitrophenylhydrazine hydrazone
acetaldehyde-2,4-dinitrophenylhydra
to give
NO,
CH, NO,
CH,
-0+H]NNH O-No, H, + H,0
H
Acetaldehyde 2,4-dinitro
phenylhydrazine Acetaldehyde 2,4-dinitrophenyl
hydrazone
<br>

Pucations
Benzaldehyde reacts 285
(C) with 2,4-dinitrophenylhydrazinc
henzaldehyde-2, 4-dinitrophenylhydrazone to give

C,H, NO,
NO,
0+HNNH-– CH,
H
NO,
T, C
NNH
Benzaldehyde 2,4-dinitro H

phenylhydrazine Benzaldehyde 2,4-dinitrophenyl

Acetone reacts with 2, hydrazone
(d) 4-dinitrophenylhydrazine to give,
acetone-2, 4-dinitrophenylhydrazone
NO,
CH, NO,

-0+HNNH-O-No, CHn
C= NNH -NO, + H,0
CH; CH
Acetone 2,4-dinitro
phenylhydrazine Acetone 2,4-dinitrophenyl
hydrazone
How does aldehydes and ketones react
vith semicarbazide?
ec Aldehvdes / ketones react with semicarbazide to form respective semicarbazones.

R R
+ H,0
C=0+ HN NHCONH,
Semicarbazide
C=N-NHCONH,
R') R'H)
Aldehyde/ketone semicarbazone

Examples:
H H H
(a)
=0+ H,N-NHCONH, -N-NHCONH, + H0
Semicarbazide H Formmaldehydesemicarbazone
H
Formaldehyde
CH, CH,
NHCONH, H,C =N- NHCONH, +H0
(b)
H
C0+ HN–
Semicarbazide H Acetaldehydesemicarbazone

Acetaldehyde
C,H, CH,
H
C=N-NHCONH, + H,0
NHCONH,
(c)
C0+ H,N- H Benzaldehydesemicarbazone
Semicarbazide
H
Benzaldehyde
t CH,
CH, C=N-NHCONH, + H,0
H,
d) =0+ H,N-NHCONH, CH Acetonesemicarbazone
Semicarbazide
CH

Acetone c,H,
C,H, C=N-NHCONH,
+
H,0
– NHCONH, Acetophenonesemicarbazone
(e) C-0+H,]NSemicarbazide CH,
CH and ketones.
3,
Acetophenone
characterisation of aldehyde
Name
the reagent used for
Ans:
2,4-DNP.
II PUChemistry
<br>

Aldehydes, Ketones
286 and Cattonih

aldehydes and ketones with general equation.

with
24. Explain the reactions of primary amincs
to form Schiff's bases. These compounds are
Ans: Adchydes and ketones react with primary amines adlso
imines, Schiff's base or imines are organic compounds containing a carbon nitrogen c
substituted
oy
bond.
R

R
-0
+
H]N-Z
1° amine
-N-Z+
Substituted imine
H0
Aldehyde or ketone
25. How does ammonia reacts with aldehydes and ketones? Give an exanple.
Ans: Ammonia reacts with aldehydes (except formaldehyde)and ketones to formthe products called
imiines.

H,C, H,C OH H,C,

C=0+ H-NH, -H,0, C=NH
H
Ammonia H NH, H
Acetaldehyde Acedaldimine
Acetaldehyde
ammonia

(2) Reduction
1. How would you reduce aldehydes and ketones by using sodiumborohydride.
Ans: (a) Aldehydes can be reduced to primary alcohols using NaBH.
R-CHO+2[H]– ablR-CH,OH
Example: CH, -CHO + 2[H] CH, -CH,OH
Ethanal (Acetaldehyde ) Ethanol (Ethyl alcohol)

(b) Ketones can be reduced to secondary alcohols

by using NaBH4
NaBH >
R-C=0 +2[H] R -CH- OH
R R'
Example:
H,C, H,C
Ç=0+2[H) NaBH,
CH- OH
H,C propan-2-c H,C
2-one propan-2-ol
Note: Aldehydes and ketones can be reduced to 1° and 2° alcohols respectively by using LiAlH
by catalytic hydrogenation.
2. What is the Clemmensen reduction?
Give an example.
Ans: The reduction of
[July 2015, March 2017. March 202|
aldehydes and ketones into amal
and concentrated hydrochloric corresponding hydrocarbon on treatment with zinc
acid is called Clemmensen
reduction.
During this reaction, the carbonyl group of
or
aldehyde ketone is reduced to - CH,-group.
+ 4[H Zn-Hg
R-C-R' Conc. HCI KCH;-R' + HO
Hydrocarbon
Examples:

Zn-Hg
1.
H--H
Formaldehyde
+ 4[HH
Conc. HCI
CH, + H,0
Methane
<br>

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287

Zn-Hg
2.
CH,-C-H+ 4H) Conc, HCI CH,-CH,+ H,0
Acctaldehydo Ethane

Zn-Hg
C,H,-C--H + 4H) CH,-CH,+ H,0
3. Conc. HCI
Benzaldehyde Toluene

+ 4[H] Zn- Hg
4. CH; --CH, CH,-CH-CH, + H0
Conc. HCI
Acetone Propano

1 Name the reagent used in Clemmensen's reduction. [March 2019]

ins: Zinc-amalgam and con. HCI.
What is the Wolff-Kishner reduction? Give an example. [July 2020]
hydrocarbons by heating with a mixture of
int: The reduction of aldehydes and ketones into corresponding
is called Wolff-Kishner reduction.
hydrazine and strong base like KOH in ethylene glycol
KOH/ethylene glyco
R-CH, R+ N,
R-Ç0 + HN-NHR-Ç=N-NH,
- Heat Hydrocarbon
H,0
R'
R'
Examples:
KOH/ethylene glycol
CH, + N,
(a) H-ÇHO
+ H]N-NH,H-Ç=NNH, Heat Methane
Hydrazine -H0 H
H Formaldehyde
Formaldehyde hydrazone

Ç=N-NH,;
KOH/ettylene glyco cH-CH,+ N,t
+ H,N-NH, CH Heat Bthane
(6) CH,- Ç-0 Hydrazine
-H,0 H
H Acetaldehyde
hydrazone
Acetaldehyde
KOH/ethylene glycol
S CH,-CH, + N,t
CH-Ç=N -NH, Heat Toulene
+HN-NH, -H0
CH,-C-0 Hydrazine H
Acetone
H hydrazone
Benzaldehyde KOH/ethylene glycol CH,-CH-CH, + N,
-NH,
Ç=N Heat Propane
Mo CH,-
(0) CH,-ÇH0. + HN-NH
Hydrazine
CH,
Benzaldehyde
CH, bydrazone
Acetone

II PU Chemistry
<br>

Aldehydes, Ketones andCattone.

288

(3) Oxidation ketones.

betwcen aldchydes and
1. Explain the tests todistingnish
prepared Tollen's rcagent give bright silver
Ans: Aldchydcs on warming with freshly h
() Tollen's test: rcagent test.
procipitate of
silver is called Tollen's 4NH,
or black RCOO + 2Ag +2H,0+
R-CHO+ 2 [Ag(NH,),J' +30OH Black ppt or
silver mirror

to this test.
Note: Kctoncs do not respond solution, give a reddish-brown precini.s
on warming with Fehlings
Fchling's test: Aldehydes test.
(ii) called Fchling's reagent
cuprous oxide (Cu,0). This reaction is
RCO0 + Cu,O +3H,0
R-CH0+2Cu+ 5OH Red-Brown ppt

answer to this test.

Note: Aromatic aldehydes donot
2. What is Tollen's reagent?
Ans: Ammoniacal silver nitrate solution. It contains
[Ag(NH)>]
3. What is Fehling's solution?
Ans: It is the mixture of
aqueous copper sulphate (Fehling solution A) and alkaline sodium pota'
tartarateRochelle salt [Fehling solution B].
4. Aromatic aldehydes do not answer to Fehlings solution test. Why?
to alkali prs
Ans: Because these aromatic aldehyde (no a-hydrogen atom) undergo Cannizzaro's reaction due
in Fehling's solution.
5. How do you indicate the presence of aldehydie group by Tollen's and Fehling's test?
Ans: By the appearence of silver mirror with Tollen's rcagent and reddish brown precipitate of cuprous oxide
Fehling's solution.
6. What is haloform reaction? Give an example. [March 2020)
Ans: Aldehydes and ketones having at least one methyl keto group are oxidised by sodium hypohalite to soÉ:
salts of carboxylic acids with one carbon atom less than that of the parent compound and the methyl i
group is converted to haloform. This reaction is called haloform reaction.

2NaOH +I,Nal + NaOI + H,0

Sodium hypohalite

R-C-CH, + 3NaOX R-C-CX, + 3NaOH

R-C-CX, +
NaOH» R--ONa+ CHX,
Example 1:
lodofom reaction with acetone. Haloform

2NaOH +l2 Nal + NaOl +

H,0
CH,-C-CH, t 3NaOI
Acetone >CH,-C-- CI, + 3NaOH

C-CI,+ NaOH > CH,-C-ONa +. CHI,

Student's illuminator Iodoform
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ublications
289
Example 2: lodoformn reaction with acctophenonc.

C,H,-C-CH, 3NaOI
Acetophenone -C-CI, + 3NaOH

C,H,C-CI, +
NaOHCH,-CONa + CHI,
Iodoform
Is isopropyl alcohol
undergo haloform reaction?
Yes. (Because oxidation of isopropyl alcohol gives
ketones,
OH

CH, – CH-CH, (0CH,-CO-CH,)

to a-hydrogen
)

Reactions due
Explain the acidity of a-hydrogens of aldehydes and ketones.
The acidity of a-hydrogens in carbonyl compounds is due to the strong
electron withdrawing effect of the
carbonyl group and resonance stabilisation of the conjugate base.

What is Aldol condensation? Give an example. July 2014, March 2016, July 2019]
Aldehydes and ketones containing at least one a-hydrogen atom undergo reaction in presence of dilute alkali
ns:

to forn B-hydroxy aldehyde or p-hydroxy ketone respectively. This reaction is called aldol reaction. The
aldol formed on heating undergoes dehydration to form a, B-unsaturated aldehydes or ketones. This reaction
is called aldol condensation.
Example 1:
dil. NaOH
,-CHO CH, - CH= CH- CHO + H,0
2CH, – CHO
–
CH,
ÇH-CH;-H,0 But-2-enal
Ethanal OH (Crotonaldehyde)
3-Hydroxybutanal (Aldol condensation product)
(Aldol)

Example 2:
ÇH,
CH,
2CH, -- CO-CH, Ba(OH), CH,
-C-CH, -C0- -H,0
CH, -C= CH-CO- CH, + H,0 i
Propanone 4-Methylpent-3-en-2-one.tel)
OH (Aldol condensation product)
(Ketol)
4-Hydroxy-4-methylpentan-2-one

What is mixed aldol

or
condensation? Give an example.
cross aldol or or betwveen
Ans; between two different aldehydes two diferent ketones
When
aldol condensation is carried out or
an aldehyde it is called
cross aldol condensation mixed aldol condensation.
and ketone.
<br>

Aldehydes, Ketones
and cattos
290
H

Dilute
-CH,
-H,0
H 4
H,C" NaOH
293 K
OH H

Trans-chalcone
Ketol (Benzalacetophenone,
Benzaldehyde Acetophenone
IUPAC Name =
13-diphenypropleiy

a-hydrogen atoms, it gives a mixture of four products.

NOte: If both of them contain

5. Other reactions
1. What is Cannizzaro's reaction? Give an example.
2018, March 2017, July 2017, July 2019, March 2020,
(July 2014, March 2015, July 2015, July A
2022]
Ans: Twomolecules of aldehydes which do not conain a-hydrogen atom react with strong alkali and unds
a
redox (disproportionation) reaction to produce primary alcohol and salt of carboxylic acid. This reacto,
a

is called Cannizzaro's reaction.

Examples:
H
H
H
(a)
C=0. + or HCOOH
C=0+ KOH H-¢- OH+H-Q
H H (conc.) OK Formic acid
H
Formaldehyde Formaldehyde
Methanol Potassium formate

(b) 2 -CHO + NaOH CH,OH +

-COONa or
Conc.
Benzaldehyde Benzyl alcohol Sodium benzoate Benzoic acid
2.. Which type of aldehydes undergo Cannizzaro's reaction?
Ans: Aldehydes without a-hydrogen atom.
3. Why acetaldehyde does not undergoes Cannizzaro's
reaction?
Ans: Because acetaldehyde contains a-hydrogen atom.
4. Why benzaldehyde or formaldehyde does not
undergo aldol condensation?
Ans: Because they do not contain a-hydrogen atom.
5. What are the products formed when benzaldehyde
reacts with conc. alkali. Name the
Ans: Benzyl alcohol and sodium
benzoate.
racto
(Cannizzaro's reaction).
6. Explain the nitration of benzaldehyde.
Ans: Benzaldehyde undergoes
nitration to give m-nitro benzaldehyde.
CHO ÇHO

HNO,/H,SO,
273- 283 K

Benzaldehyde NO,
m-Nitrobeazaldehyde
Note: Carbonyl groups acts as
a deactivating
and meta directing groups,
<br>

291
Uses of Aldehydes and
Write the uses of fformaldehyde
Ketones
(methanal).
Methanal
is used in the manufacture of [July 2019)
bakelite, resins
and other polymers.
40% aqucous solution of
formaldehyde known as
52 watcr). It is used
% formalin (40% formaldehyde, 8% methanol and
for preserving biological
specimens.
Formaldehyde is used in the
preparation of urotronine which
infections. (Nitration is used as antiseptic for unmaly
of urotropine gives RDX a powerful
explosive).
.Formaldehyde is also used as an antiseptic.
Write the uses of acetaldehyde (ethanal).

Ans:
Ethanal is used in the preparation of a number of organic compounds like acetic acid, ethyl acetate and
n-butyl alcohol.
Paraldehyde a polymer of acetaldehyde is used in medicine as a hypnotic.
It is used in silvering of mirrors.
Write the uses of acetone (propanone).
InC: It is used as a solvent in the manufacture ofsmokeless powders (cordite), celluloid, etc.

+ It is one of the ingredients of liquid nail polish.

It is used to store acetylene gas.

4. Write the uses of benzaldehyde.

Ans: It is used in perfumnes.
green.
In the manufacture of dyes like malachite acid,
synthesis of organic compounds like benzoylchloride, cinnamic
It used as a starting material for the
etc.
It is used as a flavouring agent.
5.
Name the polymer of
acetaldehyde used as hypnotic.
Ans: Paraldehyde.
6.
Name the ketone used in liquid
nail polishes.
Ans: Acetone.
formed duringnitration of urotropine.
Name the explosive
As; RDX (Research development explosives). flavours.
wellknown for their odours and
and ketones
Mention the aldehvdes acetophenone, camphor etc.,
Ans: vanillin,
Butyraldehyde,
Questions (MCQs)
Multiple Choice b) alcohols
bonded to c) ethers
group is
1.
In aldehydes, the carbonyl d) aldehydes and ketones
2) A carbon and hydrogen Thefunctional group of
aldehyde is
3.
b) two carbon atoms b) -C0OH
a) -COOR
C) three carbon atoms d) -CHO
c) -CO0CO
4) onlya carbon atom derivatives of
2, are
Esters and anhydrides || PUChernistry
<br>

Aldehydes, Ketones
and Catone.
292
What is the product of
4. Which of the following is the structurc of the
reaction? iolly
vanillin?
CHO CO, HCI
Anhyd. AICI/CuCI
X+ HC
a)
a) C,H,CH, b) CH,CI
OCH3 c) CH,CH0 d) CH,COOH
OH 10. Oxidising agent usedin Etard's reaction
CHO
a) H, Pd - b) Cro,
OH c)
b) CrO,Cl, d) KMnO,
11. Acetophenone do not form addition
prod
with sodium bisulphite due to
a) presence of alpha hydrogen
CH=CH-CHO
b) steric hindrance
c) due to low solubility
C
d) none of these
12. Product obtained when ketone is treated a
hydroxylamine
a) OXime b) hydrazine
C c) imine d) hydrazone
d) 13. In aldehydes and ketones, carbon atom
carbonyl group is
5. Aldehyde which does not undergo Aldol a) sp hybridised b) sp hybridised
condensation reaction is c) sp° hybridised d) sp' hybridised
a) Ethanal b) Propanal 14. Name of the reaction is
c) Benzaldehyde d) Propionaldehyde COCI
CHO
6 Benzaldehyde and acetophenone on
heating H,-Pd
with sodium hydroxide BaSO,
it gives benzal
acetophenone. This reaction is called
a) Cannizzaro reaction a) Rosenmund reduction
b) Self aldol condensation b) Stephen reaction
reaction
c) Cross cannizzaro reaction c) Etard reaction
d) Cross aldol condensation d) Gattermann-Koch reaction
reaction
7. Acetone reacts with 15. When aldehyde is with
Toles
Grignard reagent warmed
followed by hydrolysis to reagent, observation is
form
a) 3° alcohol b) 2° alcohol a) Red ppt
yt b) No ppt
c) Ether c) Silver mirror
d) No reaction d) Violet color
8. Conversion of benzene 16.
to acetophenone can Product obtained when ketone is treated
be brought by hydrazine
a) Wurtz reaction amine
b) Wurtz-Fittig reaction
a) Oxime b) hydroxyl
c) imine d) hydrazone
c) Friedel Craft's of ss
alkylation 17. The use
of dry HCI in the reactionresults
d) Friedel Craft"'s
acylation aldehyde with a monohydric alcohol
Student's illuminator
IIPUChem
<br>

PAbications 293

the nucleophilicity
Haloalkancs arc converted into aldehydes
of
inerease carbonyl
d)
) group more reactive than
23. Aldehydes are generally
decrease in the nucleophilicity of carbonyl reactions due
ketones in nuclcophilic addition
group to
clectrophilicity of carbonyl
c)
increase in the a) neither steric nor electronic effect
group cither steric or electronic effect
decrease in the clectrophilicity of
carbonyl
C) both steric and electronic effect
group d) formation of hydrogen bonding
common test answered by ethanal and Cannizzaro's
The
24. Aldehydes which answers
ethanol is
reaction does not contain
a) lodoform reaction b) y-Hydrogen
a) B-Hydrogen
Carbylamine reaction
) d) 8-Hydrogen
Sandmeyer's recaction c) a- Hydrogen
Clemmenson reduction, carbonyl
Wurtz reaction 25. In
) to formn
compound is treated with
reagent used to convert carbonyl
The is corresponding hydrocarbon.
compound to hydrocarbon
a) zinc amalgam + conc.HCI
a) sodium borohydride + conc.HCI
b) sodium amalgam
lithium aluminium hydride conc.HNO,
c) zinc amalgam +
b)

zinc-amalgam and conc. HCI

d) sodium amalgam + conc.HNO;
c)

d) Hydrogen in Pt solution is called

26. Ammoniacal silver nitrate
1 The conversion of aldehyde to acetal takes
place by reacting with monohydric alcohol
in
Fehling's reagent b) Schiff's reagent
a)
presence of c) Benedict's reagent d) Tollen's reagent
a) dry HNO, b) dry H,SO4 27. Addition of alcohols to aldehydes gives
a gem
c) dry HCI d) dry H,PO, dialkoxy compound known as
. The IUPAC name of H-CHO is
a) Ketal
c) Aldol
b) Acetal
d) None of theese
a) formic acid b) formaldehyde
28. Nitriles are converted into ketones by treating
c) methanal d) methanol
with
2. In Stephen reduction reaction a) Dialkyl cadmium b) Acyl chloride
2) Alcohols are converted into aldehydes c) Grignard reagent d) Chromyl chloride
converted into
b) Carboxylic acids are 29. Carbonyl carbon is in nature.
aldehydes a) Electrophilic b) Nucleophilie
are converted into
") Nitrile compounds c) Amphoteric d) Acidic
aldehydes
Answer Keys
9 10 11 12 13 14 15
8
5 6
3 4
d C b
C
23 24 25 26 27 28 29
20 21 22
16 17 18 19
C a d b C
C C
d C C C
<br>

294
Carboxylic acids
acids?
What are Carboxylic OH or -C0OH group
1.
containing carboxyl group| C- inthet
compounds
Ans: Carboxylic acids are
molecules. carboxylic acids.
formula of R
is H, alkyl or
aryl group.
2. Write the general R-COOH, where
is
carboxylic acid
The general formula ofa
Ans:
Carboxyl Group
Structure of
8.6 Nomenclature and suffix with the -ic acid and have been deriveds.
carboxylic acids end
Common names
of
Common names:
names of their natural sources.
Latin or Greek
IUPAC names: In this system, -e in the name of the corresponding alkate
replacing the ending
carboxylic acids named by
Aliphatic
-oic acid. one.
chain, the carboxylic carbon is numbered
In numbering carbon -e of the alkanei
compounds containing more than one carboxylic groups, the ending
For naming
term oic.
are indicated by adding pefix di, tri, etc to the
The number of carboxylic groups
names of following carboxylic acids.
1. Write the common and IUPAC
Ans:

Structure Common name IUPAC name

HCOOH Formic acid Methanoic acid
CH,COOH Acetic acid Ethanoic acid
CH,CH,COOH Propionic acid Propanoic acid
CH,CH,CH,cOOH Butyric acid Butanoic acid
(CH,),CHCOOH 2-Methylpropanoic acid
Isobutyric acid
HOOC –COOH Oxalic acid Ethanedioic acid
HOOC -CH,-COOH
Malonic acid propanedioic acid
HOOC-(CH,), -COOH
Succinic acid Butanedioic acid
HOOC-(CH,), -COOH
Glutaric acid Pentanedioic acid
HOOC-(CH,), - COOH
Adipic acid
HOOC- CH, -CH-CH, -COOH Hexanedioic acid
Tricarbollylic acid or Propane-1.2,3-tricarboxylic
acid
COOH Carbollylic acid

-COOH Benzoic acid (Benzoic acit)

Benzenecarboxylic: acid
CH,COOH
Phenylacetic acid
2-Phenylethanoic acid

Student's illuminator
<br>

+uoications
295
COOH
Phthalic acid
Benzene-, 2- dicarboxylic acid
COOH
Eplainthe structure of carboxylic acid group.
carbon,atom in carboxyl group
The
bond. The remaining valency is bonded with two oxygen atoms; one by a double bond and another by
single can be satisfied
either by hydrogen or by alkyl group in aliphatic
carboxylic acids and by aryl group
in aromatic carboxylic acids.
The carboxylic acid group
is a planar structure which Suggests that the carbonyl carbon atom and two
Oxygen atoms are sp hybridised.
These unhybridised p-orbitals overlap to form pi bond which is partly delocalised between
carbon and
aNVOen atom of one
side and C-O of the hydroxy group on the other side.
Hence carboxylic acids can be represented
by two resonance structures.

Cio-H -H
IMethods of Preparation of Carboxylic Acids
How would you prepare carboxylic acids from 1° alcohols? Explain with an example.
Primary alcohols on oxidation with strong oxidising agents gives carboxylic acids.
[All strong oxidising agents like potassium permanganate in neutral
medium, potassium dichromate and
to aldehydes and then
chromium trioxide in acid medium (Jones reagent) oxidise primary alcohols
carboxylic acids].
alkaline KMnO4 ,
RCH,0H R-COOH
H,0*
Carboxylic acid
1° Alcohol
Examples:
Alkaline KMnO,
CH, -OH HCOOH
H,0*
Methanol
Formic acid
Cro,-H,SOy CH,-(CH,),COOH
CH, -(CH,), –CH, -OH (Jones reagent) Decanoic acid
1-Decanol

now wOuld youprepare benzoic acid

from toluene?
benzoic acid.
Toluene on oxidation with alkaline
KMnO, followed by hydrolysis gives
S: COOK LCOOH
CH, H,0
KMnO/KOH
Heat
Potassium benzoate Benzoic acid
Toluene [July 2014]
benzene? Give equation.
Would youprepare benzoic acid from propyl
.OW ins:
COOK COOH
CH,CH,CH,
KMn0,/KOH H0,
Heat
Benzoic acid
Propyl benzene
Dudent's
I| PUChemistry
itluminator
<br>

Aldehydes, Ketones
and
296 Catosje,
acidic medium.
is hcated with CrO, or KMnO, in the entire side
Note: i) If alkyl benzenc chain.
group irrespcctive of length of the side cha
oxidizcd to the carboxyl
group is attached to benzcne, it is not affectecd by above said oxidising
ii) If tertiary alkyl acids with above said oxidizing
agent
can also oxidized to carboxylic ,agents,
ii) Substituted alkenes
4. How do you preparccarboxylic
acids from nitriles?
in the presence of H" or OH-
as Catal..
to
Ans: Nitriles are first hydrolysedto amides and then acids

Ht or OH"
R-C
N H or
H,0
OHR-C-NH, R-COOH +NH,
Amide
Carboxylic acid
Nitrile

Examples:

H or OH H30+
(a) CH, -C=N CH,-C-NH, CH, -COOH+ NH,
H,0
Acetamide Acetic acid
Ethane nitrile

H
orOH
(b) C,H, -C=N. H,0CH,-C-NH, H30CH, -C0OH+NH,
Benzo nitrile Benzamide Benzoic acid

5. How do you prepare carboxylic acidsfrom Grignard reagents? Explainwith an example.

[July 2015, March 2018, March 2020
Ans: Grignard reagents react with carbon dioxide (dry ice) to form salts
of carboxylic acids which on a

hydrolysis gives carboxylic acids.

OMgX
RMgx c HO >R-COOH+ Mg(OH)X
Carboxylic acid

Examples:
OMgBr |
CH, MgBr + C CH,-C Ho CH,– COOH + Mg(OH)Br
Methyl magnesium
(a) bromide Acetic acid

OMgBr
CH MgBr+ C
C,H,C H,O',
Phenyl magnesium C,H,-COOH + Mg(OH)Br
(b) bromide Benzoic acid

6. A
Grignard reagent X reacts with CO,
(dry ice) followed by acid hydrolysis acid.
name the compound
X and write the reaction. gives acetic
Ans: X is
CH,-Mg-I (methyl magnesium iodide).
OMgI
CH,- Mgl -C H,0"
CH, CH,
Methyl magnesium -C-OH + Mg(OH)I
iodide Acetic acid
Student's illuminat
<br>

tPublications
297
nroduct fomed when
Namethe phenyl magnesium
hydrolysis. bromide reacts with CO, followed by acid
Benzoicacid.
How do
you prepare carboxylic
acids from acid halide
Carboxylic, acids arc prepared and anhydrides? Giveequatione
M0 by or the acid base catalysed hydrolysis of ?acid halides or acid anhydrides.
CH,COC CH,COOH +HCI
Acetyt
chloride Aceticacid

c,H,COCI - H,0
CH,COOH+ HCI
chloride Benzoic acid
Renoyl

(C,H,CO),0 + H}O2C,H,COOH
Benzoic anhydride Benzoic acid
CH,COOCO0CH, + H,0c,H,COOH+ CH,COOH t ctats not
Benzoic ethanoic Benzoic acid Ethanoic acid
anhydride

dow would you prepare carboxylic acids from esters? Explain with an example.
which on
ec Acid hydrolysis of esters gives carboxylic acids while base hydrolysis gives carboxylates,
acidification gives carboxylic acids.

Acid hydrolysis of ester: R-COOR+H,0 R-COOH +R'-OH

Ester Carboxylic acid

Examples:
HCI CH, -COOH + CH, -OH
(a)
CH,-COOCH,+ H,0
Acetic acid Methanol
Methyl acetate - OH
C,H, -COOH+ C,H,
C,H, -CO0C,H,+ H,0
(b) Ethanol
Benzoic acid
Ethyl benzonate
an ester is called saponification.
Base hydrolysis of ester:
Base hydrolysis of
+ R'-OH
R-COONa
R-COOR'+ NaOH(aq)=
Ester + NaCI
R-COONa+ HCI
R-COOH
Carboxylic acid

Example: H,0CH,CH,CH,COONa + C,H, -OH

CH,CH,CH,COOC,H,+ Ethanol
Sodium butanoate
Ethyl butanoate CH,CH,CH,COOH
H,0*
CH,CH,CH,COONa Butanoic acid

are soluble in water.

Physical Properties
(b) Carboxylic acids
8.8
higher boiling points.
have aprotic solvent.
10. Give
reason: (a)
Carboxylic acids phase
or
in association through
intermolecular
vapour mnore extensive
even in are due to
(c) exists
in dimeric form of carboxylic acids
Ans: (a)
Higher boiling
points I| PU.Chemistry

hydrogen
bonding
<br>

Aldehydes, Ketones
298 and
Carboic
H

-CH,
H,C
H

are
(6) Due to the formation of
internolecular hydrogen bonding with water, carboxylic acids soluble
in water
(c) Due to hydrogen bonding.
11. The solubility of carboxylic acids inwater decreases with increasing number of carbon atore
Higher carboxylic acids are practically insoluble in water. Why?
Ans: Due to increascd hydrophobic interaction of hydrocarbon part.

8.9 Chemical Reactions

(1) Reactions involving cleavage of 0-H bond
1. Carboxylic acids are acidic in nature. Explain.
Ans: Carboxylic acids can be easily ionised
in water and exist in a dynamic equilibrium between
ion and hydronium ion. The carboxylate ion is the carboxy
stabilised by resonance. Hence, carboxylic acids are aci
nature.

R
+ H,0 R
R-C + H,0*
0-H
2. Write the reactions to indicate the acidic
nature of carboxylic acids.
Ans:
1.
Carboxylic acids react with active
metals like, Na, K, etc., to form
hydrogen gas. their respective salts and libera

2RCOOH+2Na 2RCOONa + H,
Sodium carboxylate
ii. Carboxylic acids react with alkalis
like sodium hydroxide to
acid-base neutralisation reaction. form salts and water and show simp
RCOOH+ NaOH
RCOONa + H,O
iii. Carboxylic acids are weaker
and able to react with weaker
CO, gas. bases like sodium bicarbonate to evo

RCOOH + NaHCO,
RCOONa + CO, T +
Note: Phenols are also
H,0
acidic in nature. They can react
phenols do not react with active metal and alkalis B

with NaHCO, to liberated CO, gas to rormi D

acids. Therefore by because they are
using NaHCO, we can less acidic than ca
3. Explain the effect of distinguish between
substituents on the phenol and carboxylic acids.
Ans: Electron withdrawing acidity of carboxylic acids.
groups
carboxylate anion through -NO,,-CN etc increase
the acidity of carboxylic acids stabilisingthe
delocalisation of the by
negative charge by inductive
and/or resonance
<br>

299
EWG

Eiectron withdrawing group (EWG)

stabiliscs the carboxylate anion
and strengthens the acid
Electron donating groups
like -CH,,-C,H, ctc decrease
anion. the acidic strength by destabilising the carboxylate

EDG

Electron donating group (EDG)

destabilises the carboxylate anion
and weakens the acid
Ernlain the acidic strength of formic
acid, acetic acid and benzoic acid. [July 2016, July
. The 2017]
acidic strength of formic acid, acetic acid and benzoic
acid are in the following decreasing order.
Formic acid > benzoic acid > acetic acid

(pK, 3.75) (pk, =4.19) (pk,=4.75)

Explanation: In benzoic acid, phenyl group causes - I effect as well as + R effect. Between these two
effects, + R effect is more predominant. Therefore, benzoic acid is less acidic than formic acid.

h acetic acid, methylgroup causes + Ieffect and decreases the stability of carboxylate ion. Hence acetic acid
is less acidic than benzoic acid and formic acid.
bromoacetic acid.
Explain the acidic strength of chloroacetic acid, flouroacetic acid and
acid follows the order.
ns: The acidicstrength of chloroacetic acid, bromoacetic acid and flouroacetic
FCH,COOH > CICH,COOH > BrCH,COOH
This is
electronegativity of halogen atom increases, acidic nature of acid increases.
Explanation: As the
due to - I effect of
more electronegative halogen.
carboxylate ion increases
because to the stability of chlorine. Therefore,
chlorine and bromine is less electronegative than
Flourine is more electronegative than acetic acid is weaker than chloro
acetic
acid and bromo
than chloro acetic
ouroacetic acid is stronger acid
acid. acid and
monochloroacetic acid, dichloroacetic
the acidic strengths of acetic acid,
plain This
trichloroacetic acid. of electronegative
chlorine atoms increases.
as the number
of halogen atoms
Ans:
Acidic strength of carboxylic acid increases carboxylate ion. As the number
atoms stabilises the order of acid strengths in
is due to electronegative halogen effect. Therefore, the
carboxylate ion increases
due to
-I
increases, stability of
acetic acids is H 0
acetic acid and chloro substituted H O
CI¢-b-oH > H-¢ -OH
> H
-OH H
H Acetic acid
Monochloroacetic acid
C1 I| PUChemistry
Dichloroacetic acid
Trichloroacetic acid
Suder
<br>

7. Arrange the following in the incrcasing order of thcir acidic strength. Justify 4-methylbenzoic

4-nitrobenzoie acid, benzoie acid.

Ans: The order of acidic strength is
COOH COOH COOH

OCH, NO,
4-methoxy Benzoic acid 4-nitrobenzoic acid
benzoic acid (pK, =4.19) (pK, =3.41)
(pk, = 4.46)
Reason: Electron donating group (-0CH)) decreases the acidity and electron withdrawing group
(N0,
increases the acidity of aromatic carboxylic acids.
Note:
i) In isomeric halogen substituted carboxylicacids, as the
distance between halogen and carboxvie..
group increases acidic strength decreases.
Example:
CH, –CH, - CH- COOH > CH, -CH- CH, -COOH > ÇH,
–CH, – CH, -COOH
C1 CI CI
ii) Direct attachment of groups such as phenyl or vinyl to the carboxylic
acid, increases the acidity
carboxylic acid.
(2) Reactions involving the cleavage ofC- OH bond
1, Explain the formation of anhydrides from carboxylic acids
with an example.
Ans: Carboxylicacids on heating with mineral acids such as
H,SO, or with P;0s give corresponding anhydnde
For Example:

H+, A
H,C + Ç-CH3 Ç-CH,
or P,O,, A
CH,
OH H
Ethanoic acid Ethanoic anhydride
(acetic anhydride)
2. Explain esterification reaction with example.
Ans: Carboxylic acids are heated with alcohols or ordryH
gas to give ester. This reaction is
phenols in presence ofconcentrated sulphuric acid
called esterification.
RCOOH + R'OH RCOOR'
Carboxylic acid Alcohol Ester
Example:
C,H,CO0H + C,HOH H*

CH,CO0C,H,
Propionic acid Ethyl alcohol Ethyl propionate
<br>

Prbications

What is the
action of PCI, on carboxylic 301
acids? Explain.
Carboxylic acids
react with
phosphonus trichloride
3R-COOH + PCl,
toform Corresponding acid chlorides. n
3R-COCI+
i,PO,
Enamples:
3CH;-COOH + PCI,
. 3CH,-COCl + H,PO,
Acetic acid
Acctyl chloride
. 3CAH, - COOH + PCI,
3C;Hs -COCI +
H,PO,
Benzoic acid
Benzoyl chloride
What is the reaction of PCls on carboxylic acids?
Give an example.
[July 2014]
c Carboxylic: acids react with phosphorus pentachloride
to form corresponding acid chlorides.
RCOOH+ PCl, RCOCl+ POCl, + HCI
Examples:

CH,- COOH +PCl, - CH, -COCI + POC, +

HCIgatviow 2rashe 48
Acetic acid Acetyl chloride s
eih.tr atrhor tie
C&Hs -COOH + PCl, CÇHs-COCI
+
POCI, +HCI
Benzoic acid Benzoyl chloride

How does carboxylic acid reacts with SOCI,? Explain with an example.
: Carboxylic acids react with thionyl chloride (SOCI) to form corresponding acid chloride.
it
RCOOH + SOCI, pyridine, RCOCI+ SO, HCI +

Examples:
CH,-COCI + SO, + HCI
CH, –COOH + SOCI, Pu
Acetyl chloride
Acetic acid
ii. CçHs-COOH + SOCI; pyridine CH,-COCI + SO, + HCI
Benzoyl chloride
Benzoic acid
on carboxylic acids? Give an example.
What is the action of ammonia
[March 2014, March 2015, March 2017, March 2019)
to form
to form ammonium salts which on heating lose water molecule
Carboxylic acids react with ammonia
CorTesponding amide. Examples:
RCOOH+ NH, RCO0NH, ARCONH,
-H,0 Amide
Liquid Ammonium salt
ammonia CH,COONH CH,CONH,
Acetamide
1) CH,COOH + NH, Ammonium acetate
Liquid
Acetic acid ammonia
.CONH,
2) COONH
COOH -H,0
+ NH,
Benzamide
Ammoniun benzoate
Benzoic acid I| PUChemistry
udent's
illuminator
<br>

Aldehydes, Ketones
302 and

hhheh
7. How do you convert acctic acid to ancctamide?'eht
Ans: By reaction with ammonia.
CH, -CONH,
CH, -COOH+ NH,CH, -CO0NH, Ammonium ncetate
-H,0 Acetamide
Acetit acd

S. How do you convert phthalic acid into phthalimide? Give cquation.

Ans: Phthalic acid reacts with ammoniato ammonium phthalate which on further heating gives
fon phthalamie
which as strong heating gives phthalimide.

COOH coONH, CONH,

Strong heating
+ NH,
-2H,0 -NH,
COOH coONH, CONH,
Phthalic acid Ammonium phthalate Phthalamide

Phthalimide

(3) Reactions involving - coOH group

1. Explain the reduction of carboxylic acids with an exanple.
Ans: Carboxylic acids are reduced to primary alcohols by lithium
aluminium hydride or diborane (B,HA).
R-CO0OH 0
lAlH,/ether or B,H6 y
(ii) H30+
R-CH.OH
1° alcohol
Example: CH,COOH ) LAIR4/ener orbH6 ,
CH, -CH, -OH + H,0
Acetic acid (ii) H30+
Bthyl alcohol
2. What is decarboxylation reaction? Give an
example.
Ans: The process of removal
of CO, from sodium salt of carboxylic acids using dry
called decarboxylation. Decarboxylation sodalime (NaOH + Ca0)=
of carboxylic acid gives hydrocarbons.
NaOH and CaO
R-COONa R-H + Na,CO,
Sodium carboxylate Heat
Hydrocarbon
Examples:

NaOH + CaO
CH,- C-ONa CH, + Na,CO,
Sodium Bcetate heat
Methane

-ONa
NaOH + CaO
+ Na,C0,
Heat
Sodium benzoate
3. Name the product Benzene
formed when sodium acetate
Ans: Methane; decarboxylation is heated with sodaline and name the reaction?
reaction.
4. Name one decarboxylating
Ans: Sodalime (NaOH agent.
+ CaO).
<br>

substitution reactions in the hydrophobic 303

Whatis Hcll-Volhard-Zelinsky renction? Give

part
Carboxylic ocids containing an example.
a-hydrogen reacts
phosphorus toform a-halo with chlorine or March 2015I
of red acids. This reaction bromine
in thc presence of small quantities
1. XRed phosphorus is called as Hell-
-Volhard-Zelinsky's reaction.
R-CH,-C0OH
2. H,0 R-ÇH--COOH + HX
Carboxylic acid
X
X=C1, Br
a-Halocarboxylic acid
Example:
1. CIRed phosphorus
CH,- COOH
2. H,0 CICH,–COOH + HCI
Acetic acid.
Chloroacetic acid

Explain nitration off benzoic acid with equation. [July 201I7]

Benzoic acid undergoes nitration to form m-nitrobenzoic acid.
e.

COOH COOH

conc. H,SOt

conc. HNO,
NO,
m-nitrobenzoic acid
Explain bromination of benzoic acid with equation.
m-bromobenzoic acid.
ns: Benzoic acid undergoes bromination with Br,/ FeBr; to from
COOH COOH

Br,
FeBr,
Br
Benzoic acid m-Bromnobenzoic acid

not undergo Friedel-Craft's reaction. Why? to the carboxylic

.
Aromatic carboxylic acids do AICl; (Lewis acid) gets bonded
deactivating and catalyst
s Becausecarboxylic acid group is
acid.

8.10 Uses of acids

carboxylic acids. electroplating industries.
carboxylic textile, dyeing,leather and
1,
Write any four uses of latex,
Ans: used to coagulate rubber flavouring food.
Methanoic acid is for preserving and
in food industry as vinegar
Acetic acid used prservative.
as a food nylon-6, 6
used manufacture of
Sodium benzoate is the
used in
acid (adipic acid) is
Hexanedioic perfumery.
are used in detergents.
benzojc acid soops and
Esters of manufacture of
are used for the
acids
igher fatty
I| PUChemistry
<br>

304
example questions
NCERT important intext and washydrolysed with dilute sulphurie
(molecular formula CH0) chromic acid produced
Oxidation of (C) with
A

An organic compound
1. an alcohol (C). inyolee
give a carboxylic
acid (B) and
Write cquations for the reactions
compound (C) on
dchydration gives but-1-cne. an alcohol (C).
as gives a carboxylic acid (B) and
(A) is an ester it
Ans: Thc compound same number
of carbon atoms as oxidation of alcohol
and alcohol (C) contain (
The carboxylic acid (B)
gives acid (B).
it is butan-1-ol.
The dchydration ofalcohol (C) gives but-1-cne, hence,
same number of carbon .
must butanoic acid as oxidation of butanol gives acid with
The acid (B) be CrO/H,0*

CH,CH,CH, --0-CH,CH,CH,CH, CH,CH,CH, -C- OH + CH,CH,CH,CH,0H

()
(B Butanol
(A)
Butanoic acid
butyl butanoate E Hheat
|-H,0

CH, – CH, – CH= CH,

But-1-ene

Multiple Choice Questions (MCQs)

6. The major product, formed when benzi
1. Benzoic acid gives benzene on being heated
acid is heated with ammonia
with
a) Benzamine b) Benzamide
a) Soda-lime
b) Zn dust c) Benzaldehyde d) Benzene
c) Lithium aluminium hydride 7. Carboxylic acid on heating with P,0, give

d) PCC corresponding
2. Carboxylic acids are reduced to primary a) amide b) anhydride
alcohols by c) amine d) aldehyde
a) LiAlH4 b) NaBH, 8. wate
The solubility of carboxylic acids in
c) H,/Pd d) Allof these
will
3. Decarboxylating reagent is a) increase with increase in number of cartu
a) NaOH + CaO b) NaOH atoms
c) Alc. KOH d) Zinc dust b) decrease with increase in number of car
4
Ethanoic acid undergo HVZ reaction because atoms
Ca
a) It is acidic in nature c) decrease with decrease in number of
b) Contain alpha hydrogen atoms w

c) No alpha hydrogen d) neither decreases nor increases

d) Due to -CO0H group increase in number of carbon atoms
5. Carboxylic acids have a
higher boiling point 9. Carboxylic acids exists in dimeric fornn
than the corresponding alcohols,
a) vander
due to in vapour phase due to
Waals force bond
b) Intra molecular H-bonding a) hydrogen bond b) peptide bond
c) Extensive H-bonding c) ionic bond d) metallic
d) Covalent bond
Student's illuminator
<br>

UNIT
Amines
9
IAmines
1. What are amines? Give evamples.
Ans: Amines are the derivatives of
ammonia in which one or more hydrogen atonms of ammonia
alkyl or aryl groups. are replaced
by
Examples: CH, - NH,,
Methylamine
CH,-NH,, CH, – N - CH,
Aniline
CH,
Trimethylamine
9.1 Structure of Amines
Explain the structure of amines.
Ans: Nitrogen atom of amines
carries a
amines, nitrogen is sp hybridised. lone pair of electron. In
Aliphatic amines have a
pyramidal shape. Each
of the three sp hybridised orbitals
nitrogen overlap with orbitals of
upon the composition of hydrogen or carbon depending
of the amines. The fourth orbital
nitrogen in all amines contains an of H HC
to the presence unshared unshared pair of electrons.
of Due H 107° CH, 108°
pair of electrons (lone pair-bond
interaction) the angle pair Ammonia
C-N-E, (where E is C or H) Trimethyl amine
from 109.5° to 108° in case is reduced
of trimethylamine.
9.2 Classification
1. Give the classification of
amines.
Ans: Amines are classified
into three types:
(i) Primary (1°) amines,
(ii) Secondary (2°) amines,
(i) Primary (1°) amines - They are (ii) Tertiary (3°) amines
derivatives of ammonia
replaced by alkyl or aryl group. in which one hydrogen atom
of ammonu
General formula:
R- NH,
Functional group: - NH,
Example:CH,
-NH, - Methyl amine (methanamine),
(ii) Secondary (2°) amines – CçHs- NH,–Aniline (Benzenamine)
They are the derivatives
ammonia are replaced
by alkyl or aryl groups.
of ammonia in which two hydrogen atoms o
General formula:
R-NH- R'
Functional group: - NH–

Student's illuminator
<br>

–
Example: CH, NH - CH, –
Diphenylamine Dimethyl 315
amine (N-methylmethanaminc).
(N-plhenylbenzenamine)
CçH,- NH - CçH, -
Tertiary(3°) amines:
(i) They are
anmonia are replaced by alkyl the derivatives of ammonia
or
aryl groups. in which all the three hydrogen atoms of
R

General formula:
R- N-R:
Functionalgroup: - N

CH,
Example: CH, -N -CH, -Trimethyl
amine (N,N - Dimethyimethanamine)
classify thefollowing into 1°, 2°, 3° amines.

i. (C,H,),CHNH,
1° amine
ii. (C,H,), NH
2° amine
NH,
1° amine
iii.

N(CH), 3° amine

iv.

3
Nomenclature
imon name: In common system,
aliphatic amine is namedas 'alkylamine'.
or more groups are same, the pretix di, or tri is used before the
secondary and tertiary amines, when two
name
of alkyl group.
ACname:
In this system, of alkane is replaced by the word amine.
i.e., the terminal 'e'
Amines are
named as alkanamines, present at different
positions in the parent chain, their positions are
group is
In case
Inore than
one amino -NH2 groups suitable prefix such as di, tri, etc., is
atom bearinghydrocarbon
carbon is retained.
specified
by giving numbers to thee' of the suffix of the
attached to letter
the amine. The group attached to the benzene ring, suffix 'e' of arene is replaced by
In aryl is directly
amines, if- NH, name.
amine, But aniline is the IUPAC accepted

I| PUChemistr
<br>

316
March 2020
3. Give the common and IUPAC names of the following amines. (April-2015, March-2022]

Common names
IUPAC Names
Compounds
CH, - NH, Methylamine Methanamine

NH,
Isopropylamine Propan-2-amine
CH, - CH-CH,
CH,
N,N-dimethylpropylamine N,N-dimethyl propanamine
CH-CH,-CH,-N-CH,
CH,-NH-CH, Dimethylamine N-Methylmethanamine
CH,-CHNH-CH, Ethylmethylamine N-Methylethanamine
ÇH,
Trimethylamine24n N,N-Dimethyl methanaming
CHN-CH,
CH,
N,N-dimethylethylamine N,N-Dimethyl ethanamine
CH CH,-N-CH,
CH,

CH,-CH-N N-Ethyl-N-methyl propan-2-amine

CH,- CH-CH,
NH,

Aniline
Benzenamine
NH,
CH,
o-Toluidine
2-methyl benzenamine
N(CH,),

N,N-Dimethyl aniline
N,N-Dimethyl benzenamine

CH,-CH,
-CH-N
N-Benzyl-N-ethyl benzenamine

9.4 Preparation of
1.
How do you prepare
Amines
Ans: primary
amines from
Nitro compounds are nitro compounds? [April-2016, March-202)
reduced to amines
palladium or platinum. March-2020,
by passing hydrogen gas devided
nickel
in the presence of finely
<br>

NO, 317
SNH,
+311, Pd

Nitrobenzene
compounds can also
Nitro be reduccd to amines Aniline
by hcating witlh
Example: Sn and conc. HCl or
Fe and conc. HCI.
NO,
NH,

+ 6[H] Sn + conc. HCI

or Fo + HCI + 2H,0
Nitrobezcne
Aniline h
ing the reduction of nitro compounds to amincs, scrap iron and hvdrochloric
acid preferred. Give
reason,
: Because, FeCl, formed gets hydrolysed to release hydrochloric acid during the reaction. Thus, only a
small
amount of]hydrochloric acid is required to initiate the reaction.
What isammonolysis? Explainwith generalcquation. [March-2015)
- The process of cleavage the C - X bond of haloalkane by ammonia is called ammonolysis. This reaction is
of
carried out in sealed vessel at 373K.
a

RNH, R,NH R-X,R,N R-X, R,N*X

-HX
1'amine 2° amine 3°amine quaternary ammonium
salt
alkyl halide gives quaternary ammonium salt. Name the type of
An amine requires three molecules of
amine.
type of
quaternary ammonium salt. Name the
S: 1° amine
to give
An amine requires two mole of alkyl halide
amine. type of
S:
2° amine quaternary ammonium salt. Name the
one mole of alkyl halide to give
An amine reguires
amine. -quaternary ammonium salt?
: amines toform.
for 1° /2° /3
3
amine.
mnole of
alkylhalide is required
How many X required
as: For 1°
amine 3 mole R--
R X required
mole Give equation.
For 2° amine 2 required ammoniumsalt?
Forr3° amine mole R
-X quaternary treatment with strong base.
amine from
ammonium salt by
How do
you obtain primary quaternary
Primary amine is obtained by
as:
NaX
+ H,0+
RNH, X+ + NaOH- R-NH,
1° amine
Chemistry
IPU
<br>

excess of alkyl hallde,

318
whena 1° amlnerencts witlh
Namethe final
product formed
9.
ammonium salt.
Ans: Quaternary ammonolysis. and also
quu:aternary
ammonium
a disadvantage of secondary, tertiary amines ulr
10. Give primary,
a mixture of
Anmmonolysis gives
Ans:
is very dificult.
The scparation of these following renctlons.
chemical cquations for the
11. Write thc nmmonia with C}llsCI with two moles of CH,CL.
ethanolic mine so formed
() Reaction of of benzyl chloride and renction
of

(ii) Ammonolysis
Ans: CcH-CI C,H, N-C,H,
(a) NH,
C,H, Q
CH--C,H, -HCI
CH, ClhGH,-NH, -HCI C,H,
Ethanaminc
N-Ethyl cthanamino N,N-Diethyl cthanamine
Chloroethane
. 2CH,CI,
CH-CH, N-CH
(b) N
C,H, CH HCH CI, CH, NH, -2HCI
CH,
Benzyl chloride Bcnzyl aminc
N,N-Dimcthyl phenyl methanamine

nitriles? Explain with an example.

12. How do you prepare 1° amines from or Na(Hg)/C,H, - OH gives
on reduction with LiAlH, or catalytic hydrogcnation with H, / Ni
Ans: Nitriles
amines.
LiAllH,
R-C=N+4[H] H, Ni orR-CH,-NH,
Examples:
LiAlH, or – NH,
CH, -C=N+4 H,/ CH, -CH,

Ethane nitrile Ethanamine

Reduction of nitrile into amine by using sodium in alcohol is callcd Medius reduction.
H,/Ni /or NH,
CH,-CE N+4[H] Na(Hg)/C,H,OH >CH,-CH,-
Methane nitrile Ethanamine
H,/Ni or
CH3 -CH, -C=N+4[H]
Na(Hg)/C,H;OH
CH, -CH, -CH,-NH,
Ethane nitrile Propylamine
13. How do youprepare amines from amides? Explain with example.
Ans: Amides yield primary amines on reduction by lithium aluminum hydride.

| LiAIH4
R-C-NH2 2- R-CH,- NH2
H,0
Amide 1°
amineaRe2 it

Examples 1. LIAllH,
CH--NH, 2, H,0
CH,-CH,-NH,
Acctamide Ethyl amine
<br>

Publications
319

CH,- CH 1, LiAIH,
Propanamide
-NH, 2. H,0
+ CH, CH,- CH, – NH,
Note: N-substituted. and N, N-disubstituted amides Propanamine
produce 2°
and 3° amines respectively.
How you prepare primary
would
14 amine by Gabriel phthalimide synthesis? Give equation.
In this reaction,
phthalimide reacts with KOH to form potassium
phthalimide which on treatment win
halides gives N-alkyiphthalimide which on hydrolvsis
with strong alkali like pure NaOH gives primary
amine.

KOH 2NaOH o
-oNa + R-NH,
N-H NiK

-H,0 N -R (1° amine)

Phthalimide Sodium phthalate

Potassium phthalimide N-Alkyl phthalimide
Example:

KOH, CH,CI 2NaOH

-oNa
N-H NK. N-CH, + CH,-NH,
Methylamnine
-0Na
Phhalimide Potassium phthalimide N-methyl phthalimide Sodim phthalate

15. What are the advantages of Gabriel's reaction?

Ans: In this method, 2° and 3° amines are not formed as by products.
16. Give reason: Aromaticprimary amines cannot be prepared by Gabriel's phthalimide
reaction.
Ans: Because aryl halide do not undergo nucleophilic substitution with the anion formed by phthalimide.
an March-2015, April-2015,
17. What is Hoffmann's bromamide reaction? Give example. April-2014,March-2022)
Arpil-2020,
March-2016, March-2017, April-2017, April-2018, March-2019,
Ans: Amides on heating with bromine and
aq NaOH gives 1°amines. This reaction is called 'Hoffman's
bromamide reaction.
+
Br, +4NaOH(aq)>R-NH,
+
2NaBr +
Na,C0, +2H,0
R-CO-NH,
1° Amine
Amide
NH, + Br, +4NaOH(aq) ACH, -NH, + 2NaBr+ Na,CO, +2H,0
Example: CH, -CO- Methylamine
Acetamide
NH, +2NaBr
+
Na,Co, + 2H,0
C.H. -CO- NH, + Br, +4NaOH(aq)-CH,-
Aniline
Benzamide
reaction?
reaction is called degradation
Hoffmann's bromamide has one carbon atom less than the reactant amide. So
it is
Why
product amine obtained
Ans: In Hoffmannn's reaction,
called degradation reaction. following is heated with brominc and aq. NaOH or KOH.
when the
19, Name the product obtained Ans: -Methanamine
or Ethanamide Ans: -Ethanamine
() Acetamide
() Propanamide Ans: Propanamine -
(ii) Butanamide Ans: Aniline -
(iv) Benzamide I| PUChemistry
<br>

320 names of bromamidce reaction

structurcs and IUPAC Hoffmann
Write the propanaminc by benzamide.
20. which givcs degradation of
() The amide
produced by the
Hoffmann Aniline or benzenamine:
The aminc (ii)
(ii) :

(û). Butanamide
Ans: NH,
CH,-CH,-CH,C-NH,

9.5 Physical Properties

molecular masses are soluble in water. Vhy?
1. Aliphatic amines of lower
with water. mass of amines. Give
Ans: Due to hydrogen bonding decreases with increase in molar reason.
amines
2. Solubility of aliphatic primary
ofhydrophobic part. cn
Ans: Due increase in size are than non polar compounds of
secondary amines higher
3. Boiling points of primary and
molecular masses. Explain. bonding. Hence, boiling points of
nrime
form intermolecular hydrogen
Ans: Primary and secondary amines masses.
non polar conmpounds of comparable molecular
secondary amines are higher than
Boiling points of tertiary amines are less than primary and secondary amines. Why?
4. amines fr
Ans: Tertiary amines do not form intermolecular
hydrogen bonding but primary and secondary
boiling points of tertiary amines are less than primary ar
intermolecular hydrogen bonding. Therefore,
secondary amines.
why?
Among primary and secondary amines, which category of amines have higher boiling point
and
5.
Ans: Primary amines have more boiling point than secondary amines. Because intermolecular hydrogen bona
is stronger in primary amines than in secondary amines as there are two hydrogen atoms are avalable in.
amines.
Therefore, the order of boiling points in iomeric amines is;
Primary amine > secondary amine > tertiary amine.
6. Among butan-1-ol and butan-1-amine, which will be more soluble in water
and why?
Ans: Alcohols are more soluble in water than amines. Because are more
alcohols polar than amines.
Hence, butan-1-ol is more soluble in water.

9.6 Chemical Reactions

1. Amines act as nucleophile or Amines
behaves as Lewis base. Give reason.
Ans: Due to the presence of or behav
lone pair of electron on nitrogen atom of
as Lewis base. amines, they act as nucleophile
2. Explain the basic character
of amines.
Ans: The reaction of amines with
mineral acids to form
[March -2016/ ngtur
ammonium salts shows that basic in
Amines have an unshared
pair of clectrons on the amines are base. T
basic character nitrogen atom due to which they as Lewis
of amines can
be better understood in terms behaves
Larger the value
of Kb, stronger is the base. Lesser of their Ky and pK, values.
3. Aliphatic amines are stronger the value of pKb, stronger is the base.
Ans: Due to +I effect bases than ammonia. Give reason.
of alkyl group of amine, elect
pair easily for protonation. Therefore, electron density on nitrogen atom increases and donates
aliphatic amines are strong
bases than ammonia.
<br>

Publications
Jeevith 321
.omatic amines are weaker bases
than ammonia. Give reason. IApril-2018J
Dueto the clectron withdrawing nature of
Ans: aryl group(or duc to +M cffcct), clectron density on nitrogen atom
decreases. So clectron pair is not
casily available or nrotonation. Hence. aryl
ammonia. amínes are less bdsi
Why is methylamine morc
basic than ammonia?
In methanamine the electron
Ans: donating- CH, group increases the electron density on the nitrogen atom by
+|- effect lpositive inductive effect]. So the availability of electrons for donation on
inereases. Hence it is more basic than the nitrOgen ato
ammonia.
Why is dimethylamine morebasic
than methylamine?
Ans: As the number of electron donating groups increases, basicity increases.
So dimethylamine is more basie
than methanamine.

7. Arrange 1°,2°, and 3° amines in the increasing order of their basicity in gaseous medium.
Ans: 1°amine < 2° amine < 3° amine
&. Why trimethylamine is less basic than dimethylamine and methylamine in aqueous medium?
Ans: Due to steric hindrance.
9. Arrange the following in the decreasing order of basicity in the aqueous medium.
Ans: Ammonia, methylamine, dimethylamine, trimethylamine.
(CH,), NH>CH, -NH, > (CH,),N> NH,
Dimethylamine > methylamine > trimethylamine> ammonia
10. Why is aniline less basic than ammonia? [March-2016, April-2017, April-2018]
Ans: In aniline the lone pair of electrons present on the nitrogen atom is delocalised on the benzene ring due to +
R effect [resonance] or + M effect [mesomeric]. Hence the availability of electrons for donation decreases.
Therefore, it is less basic than ammonia.
11. Arrange the following in the decreasing order of basicity. NH,,CH,
- NH,,CH, - NH,
Ans: CH, - NH, > NH, > C,H, -NH,
effect (b) steric effect
Write the basicity order of 1°, 2° and 3° amines according (a) hydration
12,
to
(c) + I effect.
(b) steric effect 1° > 2° >3°, (c) + Ieffect 3°
>
20> 1o
Ans: (a) hydration effect 1°> 2°>30,
trimethylamine according to net effect of
13. Write the basicity order of methylamine, dimethylamine,
hydration, steric and + Ieffect.
Ans: dimethylamine > methylamine > trimethylamine. or
as
aqueous medium is in the order 2° > 1°>3° where in ethvt
14. The basic strength of methylamines in reasons.
1°, Explain with March-2015, March-2017|
higher alkylamines is 2° >3°> in aqueous mediumn. Therefre
methvl amines, there is no much steric hindrance to hydrogen bonding
Ans: In
methyl amines is 2° 1°>3°.
>
order of basic strength in steric hindrance to hvdeon
or alkyl amines (bigger than -CHs group) there will be
bigher
group rom=Ch3 t0 - Czs or higher alkyl
In ethyl amine group results
of nature of alkyi
bonding. Therefore, the change > 1°.
of order of the basic
strength to 2° > 3°
In the change - NH, > (CH,),N ----Methyl
amines
Therefore, (CH.), -NH> CH,
--..- Ethyl amines
N>CHH,NH,
(C,H,), NH> (C,H,),

II PUChemistry
<br>

Amines
presence of clectron releasing groups
nature of substituted aniline changes in the
15. How docs basic like
-0CH, -CH,? groun
anilinc increascs due to the presence of electron relcasing
Ans: Basic nature of substituted
presence of electron withdrawing
nature of substituted aniline changes in the groups
16. How docs basic
-
like -NO}, -S0,H, COOH,
– X? groun
decreases due to the presence of electron withdrawing
Ans: Basic nature of substituted aniline
order of thcir basic strength;
17. Arrange the following in decreasing
C,H,NH, C,H,NH,, (C;Hs),NH;
Ans: (C;H,),NH, > CH,NH,> CoH;NH;
18. Explain acylation of amines with an example.
Ans: Primary and secondary amines (both aliphatic and aromatic) react with acid chlorides, anhydrides a3
by nucleophilic substitution reaction. This reaction is known
as acylation. The products obtained
acylation reaction are known as N-substituted amides.

+ Pyridine
R-NtH CHcoCH, R-NHCOCH,t HCI
Amide
H
Examples:

) CH,
- H
HH+CI CoCH,
Acetyl chloride
Pyridine
CH, -NHCOCH, + HCI
N-Methylethanamide
Methanamine

(ii) C,H,-NH+ C1-COCH,

YIdne C,H,- NHCOCH,+ HCI
Acetyl chloride
H N-phenylethanamide
(Acetanilide)
Aniline

(iii) CH, - NH,+ (CH,CO), 0. C,H,NHCOCH, + CH,COOH

Aniline Ethanoic anhydride
Acetanilide
(N-phenyl ethanamide)
19. Name the products formed
during acylation of amines.
Ans: N-substituted amides. ,

20. What is the role of pyridine

during acylation reaction
Ans: Pyridine removes HCl
formed during acylation reaction.
of amines?
21. 3° amines cannot be
acylated. Why?
Ans: In 3° amines, there no
is hydrogen on the nitrogen atom.
22. What is benzoylation? Give an
Ans: Amines react with example with equation.
benzoyl chloride to form
Example: Methylamine N-substituted benzamide.
reacts with benzoyl This reaction is called benzoylau
-
CH, NH, + CH,COCI chloride to form N-methylbenzamide.
Methanamine Benzoyl
CH, - NHCOC,H,
chloride
(Methyl anine) N-methylbenzamide
23. What is carbylamine
reaction (carbylamine
test)?
Ans: When a primary amine [April-2014, March-2016,
is heated with chloroform April-2016, March-2019,
This reaction is called
carbylamine reaction. and alcoholic KOH gives March-204
isocyanides called I carbylamines.

Student's illuminator
<br>

Publications

R-NH, +CHCI,+3KOH-A 323

1° amine Chlorofom (Alcohohe) R-NC +3KCI+3H,0
socyanide

(a)
CH, -NH, + CHCI,
Methanamine
+3KOHA CH, -NC +3KCI +3H,0
Chloroform
(Alcoholic)
methylisocyanide
(b) CH, -NH,+ CHCI,+ 3KOH-– A

Aniline Chlorofom
C,H, - NC +3KCl+3H,0
(Alcoholic)

1ow does phenylisocyanide

aliphatic primary amines react
with nitrous acid?
Aliphatic primary amines react with nitrous
Ans: acid to give alcohols and liberate nitrogern gas.
NaNO, +
HClNaCl +HNO,
sodium nitrite nitrous acid

R-NH, + HNO, NaNO, +HCI

R-OH +N, T +H,0
1° amine nitrous acid alcohol

Example:

CH, - NH, + HNO, NaNO, +HCI CH, -OH+ N, +H,0

methylamine Nitrous acid methanol
% Name the gas liberated when aliphatic primary amine reacts with nitrous acid.
Ans:
Nitrogen gas.
26.
Name the product formed when methylamine reacts with nitrous acid.
Ans: Methanol
amine reacts with nitrous acid?
17. What is diazotisation /How does aromatic primary March-2022)
[April-2015, March-2016, March-201 7, April-2017,
diazonoium salts.
AnS: Aromatic primary amines reacts with
nitrous acid at 0- 5° C to give
This reaction is called diazotisation.
+ HNO,
Example: NaNO, + HCI NaCl
273-278K C,H,-N=N-CI + 2H,0
HNO, + HCI
CH, -N H,+ (0-5°C) benzene diazoniumchloride (BDC)
Nitrous acid
Aniline
diazotisation?
be maintained for
28. What temperature should
Ans;
0- 5°C or 273 - 278 K. you distinguish
30
between 1, 2°, and amines
by using Hinsberg

29, What is Hinsberg reagent?

How do March-2014, March 2021)
reagent.
reagent? called Hinsberg N-alkylbenzenesulphonamide which is soluble in
Ans:
Benzene sulphonyl chloride
(CçH,SO,CI) is
Hinsberg reagent to form
react with nitrogen atom.
(i) Primary aminespresence acidic hydrogen on
of
alkali due to the -S -N-C,H, + HCI
I-C,H,
N-Ethylbenzenesulphonamide
Ethylamine (Soluble in alkali)
a N,N-dialkylbenzenesulphonamide which is
Benzene sulphonyl reagent to give
Hinsberg atom.
chloride
react with hydrogen on nitrogen
(i) Secondary amines absence of 'acidic ILPUChemistry
due to the
insoluble in alkali
Studer
<br>

324 A

a--c C,H,
O
-N-C,H,
C,H,
+ HCI

N,N-Dicthylbenzenesulphonamide
Dimethylamine
Benzene sulphonyl (Insoluble in alkali)
chloride
reagent.
Tertiary amines do not react with Hinsberg
(iii)
Give reasons: (a) Benzene sulphonamides
formed from 1° amine are soluble in alkali.
30.
is insoluble in alkali.
(b) Sulphonamide formed from amine
2°
is acidic in nature d.
Ans: (a) Because, in this sulphonamide the H-atom attached to nitrogen to
group. Hence it dissolves in alkali.
electron with drawing sulphonyl
(b) Because, there is no H-atom on the N atom of sulphonamide formed from 2° amine
31. 3° amines do not reacts with Hinsberg's reagent. Why?
Ans: Due to absence of H-atom on N atom of 3° amine.
32. How does aniline reacts with bromine water? [March-2016]
Ans: Aniline reacts with bromine water to form white precipitate of 2,4,6-tribromoaniline.
NH, NH,
Br Br

Br, /H,0
+ 3Br, + 3HBr

Aniline
Br

2, 4, 6-Tribromoanilineiie 4

33. Name the product obtained when aniline

Ans: 2, 4, 6-Tribromo aniline
reacts with bromine water.
34. Give reason: Aniline cannot be
Ans: Because in aniline, the NH2 groupnitrated directly.
undergoes oxidation easily due to
in nitrating mixture. the presence of HNO; (oxidizing ag
35. How do you convert aniline
into p-bromoaniline?
Ans: Aniline reacts with acetylchloride [March-2020, Arpil-2020|
p-bromoacetanilide. The hydrolysis(acylation) to give acetanilide which on bromination
of p-bromoacetanilide gives p-bromoaniline. gives

H, H-N
H-N--CH NH,
CH,COCI
Br,
Pyridine
CH,COOH OH or H
-HCI + CH-COOH
Aniline
N-Phenylcthanamide
(Acetanilide) Br
(Major)
Br
36. Identify the products X, Y 4-Bromoaniline
and Z in the following conversion.
NH,
acetylation Br
X H,0+
CH,-COOH
Ans: X= acetanilide, Y =p-bromoacetanilide, Z
=p- bromoaniline
Student's illuminator
<br>

Publications 325

you convert aniline

How do
o
into p-nitroanilne?
Aniline reacts with acetyl chloride
Ans: to give acctanilidc which on nitration gives p-nitroacetanilide. The
hydrolysis of p-nitroacctanilide
gives p-nitroaniline.

NH,
H-N--CH, NH,

CH,COCI
conc.HN0,, conc.H,SO, OH or H

Pyridine
288 K

Aniline N-Phenylethanamide
(Acetanilide)
NO,
p-nitroaniline
8 Identify the products X, Y and Z in the reaction.
NH,

Acetylation hydrolysis
(CH,CO),0X*Th,soy
Ans: X Acetanilide
Yp-nitroacetanilide
Zp-nitroaniline
39. Nitration of aniline gives meta-product also. Explain.
Ans: In strong acidic mediunm, aniline is protonated to form the
anilinium ion which is meta directing.
40. Aniline does not undergo Friedel -Craft's reaction (alkylation or
Ans:
acylation). Why?
Because aniline is a base which reacts with AICI; (Friedel Craft's
catalyst, a Lewis acid) to form salt.
+
NH, NH,AICI,

+ AlCI,

Aniline Salt
Due to the positive charge on the N-atom, electrophilic
substitution in the benzene ring is deactivated
Hence, aniline does not undergo the Friedel-Crafts reaction.

Give the self explanatory equation of sulphonation of aniline,

Ans:

NH, NH,HSO, NH, NH,

Conc,
453-473 K
H,SO.

Aniline
Anilinium SO,H
hydrogen sulphate SO,
Sulphanilic acid Zwitter ion
(p-aminobenzene
sulphonic acid)
<br>

326

II Diazoniumsalts
1. What are diazonium salts? Give examples. diazonium salts.
general formula RN;X" are called
Where
Thc organic compounds with the
Risaryl
Ans: giN

General formula - ArN;X*

2. C,H,N;HSO;
Examples: 1. C,H,N;CI
Benzencdiazonium chloride
Benzenediazonium bisulphate

2. What is dizonium group?

Ans: The N: group is diazonium group.
3. Arenediazoniun ion is more stable than alkyldiazonium ion. Give
reason.
Ans: Arenediazonium ion is stabilized by resonance but alkyldiazonium ion is not resonance stabilized.

9.7 Method of Preparation of Diazonium Salts

1 Give the preparation of benzene diazonium chloride. [April-2018, April-2019
Ans: Benzene diazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278K. Nii
acid is produced in the reaction by mixing sodium nitrite with hydrochloric acid. This reaction is cil:
diazotisation.
NaNO, + HCI– NaCl + HNO,

CH, -N H, +0=N-OH+HCI 0-5°C -

273-278K
C,H, N=N-CI +2H,0
Aniline Nitrous acid
Benzene diazonium chloride (BDC)

9.8 and 9.9 Physical and Chemical Properties

1. Mention the physical properties of diazonium salts.
Ans: i) Benzenediazonium chloride is a colourless
crystalline solid.
ii) BDCis readily soluble in water and stable in
cold but reacts with water when warmed.
ii) BDC decomposes easily in the dry state.
iv) Benzene diaZonium fluoroborate is water
insoluble and stable at room temperature.
2. What is Sandmeyer's reaction? How do you conyert benzenediazonium chloride to chlorobenzeu
Sandmeyer's reaction? Give equation.
As: A method of introducing a halogen atom into an
aromatic ring by decomposition of a diazoniun
presence of a cuprous halide is
called Sandmeyers reaction. By this method diazogroup
benzenediazoniumhalide can be replaçed
by CI, Br and CN nucleophiles in the presence of Cu() ion
corresponding halogen acid.
CuCl /HCI
ArCi + N,
ArNX= CuBr /HBr
ArBr + N,
CuCN /KCN
ArCN + N,
Explain Gatterman reaction.
Ans: The.
 Publications
<br>

Cu/HCI > ArCl + N,+ CuX 327

ArNX
CuHBrTy ArBr
+ N,+ CuX
How do you convert benzencdiazonium
chloride into fluorobenzene.
When benzene diazoniumchloride Give equation.
uoroborate which on is treated with fluorobaricacid
heating decomposes it forms a precipitate of benzene diazonium
to formfluorobenzenc.
ArN;CI +HBE, Ar-N}BE,
BDC
A Ar-F + BE, +
N, 1
Fluorobenzene

How you convert benzenediazonium

do
chloride(BDC) into benzene?
BDC reacts with water in presence of
hypophosphorous acid(phosphinic
acid) to give benzene.
Ar-N;CI + H,0 + H,PO,
Ar-H + H,PO, +N, T +HCI
BDC Hypophosphorous acid Benzene
Phosphorous acid
How do vou convert benzenediazonium
chloride into iodobenzene? [April-2017]
1fhenzene diazonium chloride salt solution is treated with potassium iodide
solution, it forms iodobenzene.
Ar-N;CI+ A K[ Ar + KCl+ N,-I
(BDC) Iodobenzene

How do you convert benzenediazonium chloride into nitro benzene?

BS:
When benzene diazonium fluoroborate [prepared by treating BDC with HBF.] is heated with aqueous
solution of sodium nitrite in presence of copper it forms nitrobenzene.

+
N,BE, NO,
NaNO, + NaBE,
+ HBF4
N,t
Cu, A

Fluoroboric Benzenediazonium Nitrobenzene

BDC acid fluoroborate
by. hydroxyl group.
Explain the replacement of diazogroup
from benzenediazonium chloride
to rise upto 283 K, the salt gets hydrolysed to
It the temperature of the diazonium
salt solution is allowed
S
phenol.
+ HCI
ArNCI + H,0ArOH +N,
Phenol
BDC
benzenediazonium chloride.
Give the benzene from
preparation of or
(phosphinic acid) ethanol reduce diazonium salts
hypophosphorous acid
Any:
Certain mild Teducing agents like ethanal, respectively.
phosphorous acid and
oxidised to +HCI
l0 arenes and themselves get Cu,Ci, C,H, +N,T+ H,PO,Phosphorous acid
+ H,PO, + H,0- Catalyst Benzene
C,H, N;CI HCI
Benzene iazonium chloride + CH,CHO+
Cu,Cl, C,H, +N,T
+ CH,CH,OH Catalyst Benzene Ethanal
H, N;CI
BDC Ethanol are called
azo dyes. These reactions
What are coupling
reactions? or aniline to give
with phenol
: Benzenediazonium chloride reacts
IIPU Chemistry
Coupling reactions.
ude
Cent'
<br>

329 Arines

Evample l:

OH
+Ct+Ho

Benzenediazonium chloride Phenol p-Hydroxyazobenzene(orange dyc)

Example 2:

NH,+CT +
H0

Benzencdiazonium chloride Aniline p-Aminoazabenzene (yellow dye)

9.10 Importance of Diazonium Salts in Synthesis of Aromatic

Compounds
Give the importance of diazonium salts in synthesis of aromatic compounds.
Ans: Diazonium salts are highly useful intermediates in
the synthesis of large variety of aromatic compounde
These can be used to prepare many classes of organic compounds
especially aryl halides in pure state. Diazonium
salts are very good intermediates for the introduction
of -F, -CI, -Br, -I, -CN, -OH, -NO, groups into the
aromatic ring. Aryl fluorides and iodides cannot
be prepared by direct halogenation. The cyano group cannot be
introduced by nucleophilic substitution of chlorine in
chlorobenzene but cyanobenzene can be easily obtained from
diazonium salt. Thus, the replacement
of diazo group by other groups is helpful in preparing those substituted
aromatic compounds which cannot be prepared
by direct substitution in benzene or substituted benzene.

Multiple Choice Questions (MCQs)

1. The gas liberated when ethyl amine 5. Hinsberg's reagent is
reacted
with HNO, at low temperature is a) Benzene sulphuryl chloride
a) NH, b) Chlorobenzene
b) N;
Benzene sulphonyl chloride
c) H, d) 0, d) Benzene carbonyl chloride
2, The amine which cannot 6. Carbylamine reaction is answered by
be prepared by
Gabriel phthalimide synthesis is a) Phenols b) Aldehyde
a) Methanamine b) Ethanamine c) 1° amine d) 2" amine
c) Aniline d) Propanamine 7. Methyl amine is stronger base than aniline
3. Which amine will not
precipitate when due to
treated with benzene sulphonyl
chloride a) -I effect b) +I effect
(Hinsberg reagent)?
c) +R effect d) -Reffect
a) -1amine 8. IUPAC name of (CH), N is
b) 2° amine
a) Methanamine
c) 3° amine
b) N, N-dimethyl methanamine
d) Quaternary ammonium salt
c) N-methyl amine
4.. Ethyl amine when treated when nitrous acid d) N-Ethyl amine
gives
9. Amongst the following the strongest base in
a) Ethyl alcohol b) Methyl alcohol
c) Ethylnitrous acid d) Ethane aqueouS medium is
a) CHjNH, b) (CH;)N
<br>

Publications
nevith
329
., Nitration of aniline is carried out after
acylation because 17. Which of the following is not a primary
Acylation deactivates amine?
)
the- NH group
Oxidation can be prevented a) tert-Butylamine b) sec-Butylamine
b)
Ortho and para products are c) iso-Butylamine d) Dimethylamine
c) obtained in 18. What is the IUPAC name of the following
good yield.
d) Allof these compound?
Which of the following can
NH,
11. exist as zwitter
iron?
a) p-amino acetopheone a) 2-methyl-4-hexanamine
b)
b) 5-methyl-3-hexanamine
p-nitro amino benzene
c) 2-methyl-4-amino hexane
c) p-methylphenol
d) 5-methyl-3-amino hexane
d) sulphanilic acid 19. Propionamide on Hoffmann degradation
1). The basic character of methyl -amines in gives
aqueous phase is a) methyl amine b) ethyl amine
a) 3°> 2° > 1°> NH, c) propyl amine d) ethylcyanide
b) 2° >3°>1°> NH,
c)
20. Gabriel-phthalimide synthesis is used for the
1°>2° >3° NH, d) 2° >1°>3° > NH,
>

preparation of
13. Solubility
of ethylamine in water is due to a) Primary aromatic amines
b) Secondary amines
a) Low molecular weight c) Primary aliphatic amines
b) Ethyl group present in ethyl alçohol d) .Tertiary amnines
21. An alkyl or benzyl halide on reaction
c) Formation of hydrogen
bonding with water with an
d) Being derivative ethanolic solution of ammonia undergoes
of ammonia a) electrophilic substitution reaction
14. Nitrogen atom of amino group is b
nucleophilic substitution reaction
hybridized. c) free radial mechanism
a) sp b) sp d) nucleophilic addition reaction
c) sp d) spd 22. A primary amine is
formed by an amide on
15. Theshape of (CH:): N is pyramidal because treatment with bromine
and alkali. The
a) nitrogen forms three sp hybridised sigma primary amine has
bonds with carbon atoms of methyl groups a) 1
carbon atom less than amide
and there is one non- bonding electron pair. b) carbon atom more than amide
1

b) nitrogen forms three sp hybridised sigma c) 1

hydrogen atom less than amide
d) 1
hydrogen atom more than amide
bonds with carbon atoms of methyl groups 23. Which of
and fourth orbital forms T– bond the following compounds can be
prepared in good yield by Gabriel
c) nitrogen has five valencies which are phthalimide
synthesis?
arranged in pyramidal shape a) CH, - NH, b) -
CH, -CH, NHCH,
) the unpaired electron present on nitrogen is
delocalised.
10. A secondary amine
is
CH,-! - NH,
a
a) compound with two carbon atoms and an (c)
-NH2 group.
b) a
compound containing two -NH, groups
c) a NH,
compound in which hydrogens of NH,
have been replaced by two alkyl groups.
d) a
compound with an -NH, group on carbon
atom in number two position. (d)
<br>

Arrines
31. The compound obtained by heating
330
reagents would
not be of a primary aliphatic amine a miture :
24, Which of the following an nryl nitro and chlorsform
with cthanolic potassium hydroxide
R good choice for reducing
a) an alkylcyanide (KOHj
compound to an amine? in cther
a) H(cxcess)/PI b) LiAIH, b) a nitro compound
HCI
c) Fe and HCI d) Sn and c) an alkyl isocyanide
degradation reaction is
25, Hoffmann bromamide d) an amide
shown by 32. In the reaction,
b) ArCONH,
a) ArNH,
d) ArCH,NH, RNH, NaNO, +HCI ROH+ H,0+
c) ArNO,
soluble in wvater than
cthyl
a) NH, A; Ais
26. Aniline is less b) N,
amine due to c) O, d) CO,
resonance stabilisation of benzene ring 33. Primary amines can
a)
resonance stabilisation of anilium ion be distinguished from
b)
group secondary and tertiary
c) more hydrophobic nature of CHs amines by reacting
with
than C,Hs group
a) Chloroform and alcoholic
d) more hydrophobic nature of CAs group KOH
than CoHs group b) Methyl iodide
27. The correct increasing order of basic strength c) Chloroform alone
for the following compound is d) Zinc dust
NH, NH, NH, 34. The product formed
when aniline is treated
with NaNO, and dry HCI (nitrous
acid) at 273
-278 K is
a) Nitrobenzene
b) Ethyl benzene
NO, CH,
(I) c) Benzene diazonium chloride
(II)
(III) d) Phenol
a) II<II <I b) III <I<II
c)III<I|<I 35. Benzene diazoniumn chloride on hydrolysis
II<I<III d)
28. Aliphatic
amines are gives
but aromatic amines are basic than NH3 Phenol and
a) N

NHJ. basic than b) Diazonium salt

a) more, less c) Hydrazo compound
b) less, more d) Benzene
c) both 1 and 2
d) none of these
29. Substitution one 36. The general formula quaternary
of allkyl group by replacing of
hydrogen of primary amines ammonium compound is
a) increases the base strength a) R-NH, b) R,N
b) decreases the base strength c) R,NX d) NH,X
c) remains the same 37. The reaction
d) none of the above
30. Which of the following factors affect the basic ArN:CI Cu/l
ArCl+N, + CuCI 5
strength? named as
(i) Inductive effecct a) Sandmeyer reaction
(ii) Steric hinderance b) Gattermann reaction
(iii) Solvation effect c) HVZ reaction
(iv) Solubility in organic solvents d) Carbylamine reaction
a) (i) and (iv) b) (i), (ii) and (ii)
c) (ii) and (iii) d) (ii) and (iv)
Student's iet
illuminntor
<br>

UNIT
Biomolecules
What are biomolecules?
10
Ans: The molecules present in the living systems are called biomolecules.
Example: Carbohydrates, proteins, vitamins, nucleic acids, etc.

10.1 Carbohydrates
1. What are carbohydrates?
Ans: Carbohydrates are optically active, polyhydroxy aldehydes or
polyhydroxy ketones or those compouás
which yield these on hydrolysis.
Examples: Glucose, fructose, galactose, sucrose, maltose,
lactose, starch, cellulose, glycogen, etc.
2. How are carbohydrates classified?
Ans: Carbohydrates are classified into three types
based on their behaviour on hydrolysis namely:
(a) Monosaccharides (b) Oligosaccharides (c) Polysaccharides
3. What are monosaccharides? Give examples.
Ans: They are the simplest carbohydrates
and cannot be further hydrolysed.
Examples: Glucose, fructose, galactose,
ribose, deoxyribose, etc.
4. How are monosaccharides classified?
Ans: Monosaccharides are classified
into two types. (a) Aldoses
(b) Ketoses
(a) Aldoses: Sugars containing aldehydic group
(-CHO) are called aldoses.
Example: Glucose, galactose,
ribose, deoxyribose, etc.
(b) Ketoses: Sugars containing keto group
(-CO ) are called ketoses.
Example: Fructose.
Note: (i) A sugar containing aldehydic group
and 6 carbon atoms is called
Examples: Glucose, galactose, aldohexose.
etc.
(i) A sugar containing 5 carbon atoms
and aldehydic group is
Examples: Ribose, deoxyribose, called aldopentose.
etc.
(iii) A sugar containing 6 carbon
atoms and keto group
is called ketohexose.
Example: Fructose.
5. What are oligosaccharides?
Ans: The carbohydrates on
hydrolysis
gives 2 to 10 monosaccharides Oligosaccharides
are further classified are called l oligosaccharides.
into disaccharides, trisaccharides,
6. What are disaccharides? tetrasaccharides, etc.
Give examples.
Ans: The carbohydrates on
hydrolysis gives two monosaccharides
are called disaccharides.
Examples: ()
Sucrose: Hydrolysis of sucrose
gives glucose and fructose.
Student's illuminator
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Publications
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CH,O,+ H,0 tyathjyait

CH,0,+
Sucrose
cos
CH,0,
Glu e
Frctone
(ii) Maltose: Hydrolysis of maltose gives
two glucose molecules.
C,H,,O,,+ H,0- Hydrolysis
Maltose C,H,0,+C,H,,0,
Gucose Gucose
(ii) Lactosc: Hydrolysis of lactose gives glucose
and galactose.
C,H,,0,+ H,0- Hydrolysis
C,H,0,+ C,H,,0,
Lactose
Gucose Galactose

Give an example for homo disaccharide.

ins: Maltose because it contains 2 same monosaccharides.
C,,H,,0,,+ H,0- Hydrolysis
C,H,,0,+C,H,,0,
Maltose Glucose Gluctose

8 Give an example for hetero disaccharide.

Ans: Sucrose and lactose becausethey contain two different monosaccharides.

C,H,,0,+ H,0osC,H,,0,+C,H,,0,
Lactose cos e cose Glu Gala

9. What are polysaccharides? [March-2022]

Ans: The carbohydrates on hydrolysis gives large number of monosaccharides are called polysaccharides.

Examples: starch, glycogen, cellulose, etc.

Hydrolysis
(C,H,,0,). +nH,0 H+
nC,H,,0%
starch or glycogen or cellulose glucose
-
(i) Starch and glycogen on hydrolysis gives a D-(+)- glucose
units.
Note:
- units.
(ii) Cellulose on hydrolysis gives ß D -(+)- glucose
10.
What are reducing sugars? Give examples.
reagent are called reducing sugars.
Ans: The carbohydrates which reduces Fehling's solution and Tollen's group
etc. (Reducing sugars contains free aldehydic
Examples: Glucose, galactose, fructose, maltose, lactose
or a keto group adjacent to CHOH group).-
Note: Allreducing sugars undergo mutarotation.
, What are non- reducing sugars? Give an example.
solution and Tollen's reagent (due to the absence of free
Ais:The carbohvdrates which does not reduce Fehling's
group to -CHOH) group are called non-reducing sugars.
aldehydic group and keto adjacent
Example: Sucrose.
12,
Which of the following is called -
Ans:
(i) Grape sugar - glucose,
(i) Fruit sugar -fructose,
(ii) Cane sugar- sucrose
(iv) Malt sugar - Maltose
(v) Milk sugar- Lactose fructose
of glucose and
(vi)
Invert sugar- Mixture sugars.
13.
Give the chemical names of the following
Ans:
() Glucose Dextrose
Student's IIPU Chemistry
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Biomoleaues
342

(ii) Fructose - Lacvullose

(ii) Sucrose - Saccharose
14. Give two methods for the preparation of glucosc. HCI or H,SO; in alcoholic medium to
Sucrose is boiled with dil
Ans: () From sucrose (Cane sugar):
glucose and fructose in equal amounts.
H*
CH,0,,+ H,0 C,H,0, + C,H,0,
Sucrose Glucose Fructose
by boiling starch with dilute H,SO, at 393
(ii) From starch: Glucose is obtained commercially K under

pressure.

(C,H,,0,),.+ nH,0
Starch
393 K,
H*
2-3 atm n CH0,
Glucose
15. How does glucose react with hydrogen iodide (HI) or How do you show that glucose containe
6 carbon atoms in a straight chain? [March 2016, March 2020]
Ans: Glucose on heating with HI and red phosphorus gives n-hexane. This shows that glucose contains 6 carbon
atoms in a straight chain.
C,H,,O, -CH, -CH, -CH, - CH, -CH,
HI- A
Red P CH,
Gluc ose (n-Hexane)

16. How does glucose reacts with hydroxylamine (NH,-OH) or How do you show
that glucose contains
carbonyl gro upC=0)?
Ans: Glucose reacts with hydroxyl amine (NH,OH) to give an glucose oxime. This shows
that glucose contains a
carbonylgroup (C= 0)

NH,OH
(ÇHOH)," CH=N-OH +
H,0
CH,OH (CHOH),
Glucose
CH,OH
Glucose oxime
17. How does glucose reacts with hydrogen cyanide
(HCN) or How do you show that glucose contains
carbonyl(CC=0)
Ans: Glucose reacts with HCN to give glucose caynohydrin.
This shows that glucose contains acarbonyl
(CC=0) group.
CN
CHO CH OH
HCN
(CHOH), (CHOH),

CH,OH CH,OH
Glucose Glucose cyanohydrin

18. How docs glucose reacts with acetic anhydride? or

How do you show that glucose contains five
groups?
Ans: Glucose on acetylation with acetic anhydride gives glucose pentaacetate (March 2020/
groups which confirms the prese
5-OH in glucose.

's illuminator Chemistry

<br>

Publications 343
evith

CHO CHO
Acetic anhydride
(
(CHOH),
OC-CH,),
CH,OH
Glucose CH,-0--CH,
Hov does glucose rencts with bromine water (Br, water)2 or How do vou show that glucose contalns
aldehydic group?
a
Glucose on mild oxidation with Br; water gives gluconic acid. This indicates the
carbonyl group Prese
glucose is aldehydic group.
CHO ÇOoH
Br, water
(CHOH), (ÇHOH),
CH,0H CH,OH
Glucose Gluconic acid

20. How do you show the presence of primary aleoholic (- OH) group in glucose?
Ans: Onoxidation with nitric acid, glucose as well as gluconic acid yield a dicarboxylic acid, saccharic acid. This
indicates the presence of a primary alcoholic (-CH,OH) group in glucose.
CHO COOH ÇOOH
Oxidation Oxidation
(ÇHOH),
çHOH). (CHOH),
CH,0H COOH CH,OH
Glucose Saccharic acid Gluconic acid

21. Write the open chain structure of Emil Fischer's structure of glucose.
Ans: Glucose contains - HC=0
Aldehydic group (carbonyl group), H
OH
(i) 6 carbon atoms in a straight chain
– OH) group HO -H.
1 primary alcoholic (-CH, 4
(ii) OH
OH)groups
(iv) 4 secondary alcoholic (- CH–
HCOH
(v) 5–OH groups 6
CH,OH
(vi) 4- chiral carbon atoms
(v) Glucose shows =16 optical isomers.
2 = 2*

open chain structure of glucose.

T4, Give the limitations of to explain the following facts.
IAns: The open chain structure of glucose fails
groUP, oes not give Schitr's test and it
does not form nddition
Glucose. although it contains aldehyde
product with NaHSO3. amine indicating the absence of a free aldehyde group.
react with hydroxyl
not
Pentaacetate of glucose does are named as a. and B. The a-form of i
two different crystalline forms which
is foundto K)in obtained by crystallisation from concentrated solution of glucose at 303 KI
3
D(+) glucose exist
glucose (melting point 419 is crystallisation from hot and saturated aqueous solution at
obtained by
and B-form (melting point 423 K) is open chain structure of glucose.
not be explained by
371 K.This behaviour could
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344 Biomdleales

23. Explain cyclic structure of glucose.

Ans: When glucose is treated with methanol in presence of dry hydrogen chloride gas, it yields two
isomeric
monomethyl derivatives known as methyl a-D-glucoside and methyl-p-D-glucoside. These glucosides
not reduce Fehling's solution and also do not react with hydrogen cyanide or hydroxyl amine indicating
absence of a free -CHO group. Since only one molecule of methanol is used for the formation the
of methy
glucosides, these must be hemiacetals. By analogy to the formation of thesetwo methyl glucosides,
glucose
cxists in two forms a-D-glucose and B-D-glucose.
-
a-D(+) glucose Equilibrium B D(+) glucose
mixture
+ 52.50
The a- and ß - cyclic forms of D-glucose are anomers. In this case, a-anomers of glucose contain
group towards right at C-1 position the-OH
and B-anomer of glucose contains the -OH group towards left at
position.So, D-glucose exists in two stereoisomeric c,!
forms with different specific rotations and meli:
points. The structures of a- and B-anomers of carbon are shown below.

H OH H HO}--H
1
H

-OH H
6¢ H
OH OH
HO- C-H HO H
HO -C-H .

H-- OH
H
H

fOH/ H--OH
CH,OH
H--H H

6CH,0H CH,OH
a-D(+)-Glucopyranose D-(+)-Glucose B-D-(+)-Glucopyranose
These two forms are not mirror images,
and hence are not enantiomers.
24. Explain D and L configuration.
Ans: D and L indicate the relative
configuration of a stereo isomer
with the isomer of glyceraldehyde.
Glyceraldehyde contain one
chiral carbon atom and exists in two
enantiomeric forms as shown below.
CHO

H-C-OH HOC-H
CH,OH CH,OH
D-glyceraldehyde
L-glyceraldehyde
D series of sugars
L series of sugars

25, What are D andLsugars?

Ans: The sugars having the same configuration as
D -glyceraldehyde at the chiral
primary alcoholic group are carbon atom adjacent to
designated as D- sugars and those have configuration L-glyceraldehyde are
designated as L-sugars. as
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Publications
Jeevith 345
Compare the opcn chain structure of glucosc with
26. glyceraldehyde for D and I
configuration.

Ans: If
the.-OH group of the farthest chiral carbon
atom from the carbonyl group is on the
H-C-OH
right side,ithe sugar is called D -sugar. HO-C-H
1fthe - OH group on the farthest chiral carbon atom from the carbonyl group is on the H-OH
left side, the sugar is called L - sugar.
H-C-OH
17. What are anomers?
CH,OH
Ans: The sugars which differ in their configuration at C - 1 or first carbon atom are called D4+}glucose
anomers.
Example: a-D-()- glucose and ß- D- (+)- glucose are anomers.
28. What are epimers?
Ans: The sugars which differ in their configuration at any
C- atom otherthan C- Iare called epimers.
Example: Glucose and galactose.

29. Write the Haworth structure of a - D - (+) - glucopyranose. [March-2014, March-2021]

Ans: CH,OH
-0 H
H
H
QH H OH
HO
H OH
a-(D)-(+) glucopyranose
Note: Pyran means 6 membered ring.
ose Sugar, <4' indicates dextrorotatory.
ß-D-+)-glucopyranose.
30. Write the Haworth structure of
Ans: CH,OH

H OH
H

OH H H
HO
H OH
B-(D-(+) glucopyranose a-D-(-)-fructofuranose.
Write the Haworth
structure of

HOH,C
6 H,OH
Ks
H\H H/
3
OH H

-(D)-{-- fructofuranose

1
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Biondleuen
346
structure of B-D-(-)-fructofuranose.
32, Write the Haworth's
Ans:
6
HOH,Ç OH

H9/ ÇH,OH
OH H

B-(D){-)- fructofuranose
Note: Furan means S membered ring. ose means - sugar, - indicates laevo rotatory.

33. Write the Haworth structure of a-D-(+)-maltosc.

[March-2015, July-201,March-2017, July-2018, March-2019, July-2019,
July-2020, March-2022/

Ans:
CH,OH ÇH,OH
H H
H
H H
OH H OH H
HO
ÖH
H OH H OH
a-D-Glucose unit a-D-Glucose unit
Maltose
34. What is glycosidic bond?
Ans: The linkage between the two monosaccharide units through oxygen atom is called glycosidie linkage or

glycosidic bond.
35. Mention the type of glycosidic linkage in maltose.
Ans: a-(1, 4) glycosidic linkage
-
36. Give reason maltose is a reducing disaccharide.,
Ans: Maltose reduces Fehling's solution and Tollen's reagent (due to the presence
atom of II glucose unit). So it is a reducing sugar.
of free aldehydic group at

37. Write the Haworth structureof lactose. (Uuly-2015, March-2016, July-2017, March-2018|
Ans:
CH,OH
ÇH,OH
O H H OH
H
OH H
OH H
H
H OH H
H OH
B-D-Galactose unit B-D-Glucose unit
Lactose

38. Mention the type of glycosidic linkage in lactosc.

Ans: B
-(1, 4)-glycosidic linkage.
39. -
Give reason lactose is a reducing disaccharide (sugar)
atom
Ans: Lactose reduces Tollen's reagent, Fehling's solution (due C,
group at
to the presence of free aldehydic
of glucose unit). So it is a reducing sugar.
<br>

Putblications 347
Jeevith

Write the Haworth structure of sucrosc.

40.
CH,OH
Ans:
H
H

HO
QH H

H OH „a(1 -+ 2) glycosidic bond

HOH,Ç

H\H HO/ CH,oH

OH H

41. Give reason – sucrose is a non – reducing sugar.

Ans: In sucrose, free aldehydic or ketonic groups are not present (because the aldehydic
group of glucose and keto
group of fructose are involved in glycosidic bond formation). Therefore, it does not reduce Fehling's solution
andTollen's reagent. Hence it is a non-reducing sugar.
42. Mention the glycosidic linkage in sucrose or cane sugar.
- -
Ans: a-(1, 2) or Ci of a glucose and C, of ß fructose.
43. What is invert sugar?
sugar.
Ans: Equimolar mixture of glucose and fructose is called invert
44. What is inversion of cane sugar?
dextrorotatory glucose and laevorotatory fructose. Since
Ans: Sucrose is dextrorotatory but after hydrolysis give
more than dextrorotation of glucose (+52.5), the mixture is
the Laevoratotion of fructose (-92.4°) is
laevorotatory. to laevo, This is
sucrose brings about a change in the sign of rotation from dextro
Therefore the hydrolysis of sugar.
cane sugar and the product is named as invert
called inversion of
CH,o,,+ H,0 C,H,,0,+CçH,,0,
Fructose
Glu cose
Sucrose (+52,5°) (-92.4°)
Dextrorotatory
Laevorotatory

present in plants.
33, Name the storage polysaccharide
Ans: Starch.
present in starch.
46.
Name the monomer unit
Ans: a-D-(+)-glucose unit,
47. Name the components of
starch.
Ans: Amylose and amylopcctin.

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348

48, Vrite the Haworth structurcs of amylosc and amylopectin.

IAns:
CH,OH CH,OH
H H

-0 OH -0
H OH H OH
a-1,4 glycosidic linkage
Structure of amylose

CH,OH
H

OH a-1,6 glycosidic linkage

branch point

CH,OH H OH
6CH,
H H
H H H
H
-0 OH H OH
Ho
OH
H OH
Structure of amylopectin

49. Give any 2 difference between amylose

and amylopectin.
Ans:
SI.

No. Amylose
Amylopectin
It is water soluble component of starch.
It is water insoluble component
ii. It constitutes about 15-20% of starch. of starch.
It constitutes about 80-85%
111 It is linear polymer. of starch.
It is a branched
polymer.
It has 200- 1000 a-D-(+)- glucose units held
25-30 a -D-(+)-glucose units joined
It has
by Cj -
b)
CA glycosidic linkage.
It gives blue colour with iodine solution.
Ci-C and C -C%glycosidic linkages.
V.
It does not give blue colour with iodine solution.

50. Name the storage polysaccharide (carbohydrate)

present in animals.
Ans: Glycogen
Note: Glycogen is present in the liver of all animals.
Glycogen is called animal starch because its structu
similar to amylopectin and is rather more highly branched, Glycogen yeast
is also present in muscles. brain.
and fungi.
51. Mention the structural explanation of glycogen.
Ans: Glycogen contains a-D-(+)- glucose units. Glycogen is highly branched polymer. It has branches to
8 to 12 glucose units.
In glycogen a-glucose units are joined by Cj - Cs links and cross links by C,-Ca elycosidic linkages.
Chemist
hono l minato I| PU
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Publications
Jaevith 349
Write the Haworth structure of cellulose.
1Ans:

CH,OH CH,OH
H ÇH,OH
H H H H
OH H H
OH H
H OH H
H H
H OH H OH
n-2 H OH
B-D Glucose B-D Glucose B-D Glucose

53. Give any 2 difference between starch and cellulose.

SI. No. Starch Cellulose
1. It is made up of a-D-(+)-glucose units. It is made up of B-D-(+)-glucose units.
ii. It has a - glycosidic linkage. It has B-glycosidic linkage.

ii. It has C -C4 and C

-Co linkages. It has C -C, linkages.
iv. It has linear and branched polymeric chains. It is a linear polymer.
S4. Why cellulose cannot be used as a source of energy by human beings?
an enzyme called cellulase.
Ans: Human beings are incapable of digesting cellulose due to the absence of

5. Mention the importance of carbohydrates.

(starch in plants and glycogen in animals)
Ans: (1) They acts as biofuels to provide energy for living organisms
(1) They act as constituents of cell
membranes (cellulose)
paper and alcohol industry.
(11) They acts as raw materials for textiles,
are present in RNA and DNA.
(1v) D-ribose and D-oxyribose
energy by vaids in ayurvedic systemn of medicine.
(V) Honey is used as a source of
many proteins and lipids.
(Vi) Carbohydrates are found in
biosystem in combination with
cotton
the form of wood and tor making cloths in the form of
(Vi) Cellulose is used for making
furniture in
fibre.
(MCQs)
Multiple Choice Questions
c) Cellulose d) Maltose
1,
Glucose on oxidation with nitric
acid gives 4. Sucrose is made up of......
a) Saccharic acid b) Gluconic acid a) A glucopyranose and Fructopyranose
c) Glyceraldehyde d) n-Hexane b) Aglucopyranose and Fructofuranose
c) A glucofuranose and Fructofuranose
2,
Cellulose is a
linear polymer of...... d) A glucofuranose and Fructopyranose
b) B-Glucose
a
a-Glucose 5. Starch is a polymer of......
Eructose D+}-Glucose
 Reall JH group
<br>

option for corect statements.

rorrect d) allof these
of a -glucose.
is a polymer of
Starchis
0 L2. Which of the following polymer
Starch consists of amylose andamylopectin.
the liver of animals?
is stored in
() Amylose insoluble in water a)
(i)Amylopectin is Amylose b) Cellulose
soluble
) in water c) Amylopectin d) Glycogen
and (iv) b) (), (i) and (iii)
) () () (ii) L3. Sucrose (Cane sugar) is a disaccharide.
One
and ) d) (ii) and (iv)
) molecule of sucrose on hydrolysis gives
Which one of the following statement a) 2 molecules of glucose
correct.about sucrose:
is
b) 2 molecules of glucose +1 molecule of
It can reduce Tollen's reagent however fructose
cannot reduce Fehling's reagent. c) 1 molecule
of glucose +1 molecule of
It undergoes mutarotation like glucose and fructose
fructose. d) 2 molecules
of fructose

Answer Keys
1 2 3 4 6 7 8 10 11 12
a b b a d b d b
13 14 15 16 17 18 19 20 21
22 23
d b b C d C

2 Proteins
What are proteins?
s:
Proteins are complex nitrogenous substances. of very high molecular weight of the order >10,000.
are very
Proteins
essential for growth and development of both plants and animals. The chief sources
of proteins are
milk, cheese, pulses, peanuts, fish, meat, etc. They are made up
of a-amino acids. So, a-amino acids are
building blocks
of proteins.
What are a-amino acids?
eamino acids are compounds which contains bth amino group (- NH) and carboxylic acid group
(- COOH). The amino group (- NH,) is attached to the a-carbon atom with respect to the carboxylic acid
grOup (- COOH).
Example: Alanine

CH, -"CH-C00H

NH,
Note: a. - ammino acid is a bi functional compound (- NH and - COOH)

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Biomdlecules
352

3. Write the gencral formula of a-amino acid.

Ans: R-"CH-COOH
NH,

4. How many amin0 acids are known?

- -
Ans: 20 (essential a-amino acids 10, non essential a-amino acids
- 10)

5. Write the structures of a-anmino acids. JMarch-2018

Name Three letter One letter
Formula
Symbol symbol
Neutral aminoacids
COOH

Glycine Gly tai

H,N-C-H G

H
COOH
Alanine Ala
1
H,N-C-H A

CH,
ÇOOH
Valine* Val H,N-C-H V

(CH),CH
ÇOOH
Leucine* Leu
H,N-C-H L

(CH,),CHCH,

ÇOOHg
I Isoleucine*
tIle H,N-C-H I

CH,CH,CH–CH,
*
ÇOOH
Serine
Ser
H,N-C-H
HOH,
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Publicatione 353
pevth

ÇoOH
Threonine* T
Thr H,N---H
CH,CH-OH

Phenylalanine* F
Phe H,N-C-H
C,H,CH,

ÇOOH

Methionine* Met H,N-Ç-H M

CH,SCH,CH,
COOH

Cysteine Cys H,N-Ç-H C

HSCH,
ÇOOH

Tyrosine Tyr H,N-Ç-H Y

(p)-HO-C,H,CH,
ÇOOH

H,N-C-H
W
Tryptophan* Trp CH,

ÇOOH
HN -H
P
Proline Pro H,C H,
H,

Acidic amino acids

ÇOOH

H,N-ÇH D
Asp
Aspartic acid HOOCCH,sler

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 Biomolecules
<br>

ÇOOH
354

H,N-C-H E
Glu
Glutamic acid HOOCCH,-CH,
Basic amino acids
ÇOOH

Lys
H,N-C-H K
Lysine*
CH,-(CH),-NH,
ÇOOH 1

H,N-C-H
R
Arginine* Arg
HN=C-NH-(CH),CH,
NH,

ÇOOH

H,N-C-H
Histidine* His H
-CH,

H
COOH

H,N-C-H
Aspargine Asn N
H,N-Ç-CH,

ÇOOH

Glutamine
H,N-C-H
GIn
H,N-Ç-CH,CH,

(*- Essential aminoacids)

6. What are essential a-amino acids? Give one
example. [April-2014, April-201 6, July-2017|
Ans: The amino acids which are not synthesised
in the body but provided in the diet are
acids. called essential a
Example: Lysine, Valine, Leucine, isoleucine,
phenylalanine, methionine, tryptophan, threonine, arg
and histidine.
7. What are non-essential amino acids?
Give one
example. (March-2018, July-2018/
Ans: The amino acids which are
synthesised in the body are called
Example: Glycine, non-essential amino acids. glutamic
alanine, serine, cystine, glutamine,
acid. tyrosine, proline, aspartic acid, asparagine,

Student's illuminator
DUChemisüy
<br>

Publications 355
vth are acidic a-amino acids?
What Give an example.
amino acids which contain 2 carboxyl groups arc called acidic
AnS: The COOH) and 1 amino grOup (- NH)
Or The (-
amino acids. amino acids containing morc number of groups are called
carboxyl groups than amino
acidic a- aminoacids.
Evample: Aspartic acid, glutamic acid.
Whatare basic amino acids? Give an
example.
The amino acids which contains 2 amino groups
(-NH,) and i carboxylic acid group (- COOH) diG e
hasic a-amino acids. OR The amino acids containingless number of
carboxyl groups than amno g
called basic a-
amino acids.
Example: Lysine, Arginine, histidine.
What are neutrala-amino acids? Give an example.
ins: The amino acids which contains 1 amino (-NH,) group and 1 carboxylic acid (-COOH) group are called
neutral a-amino acids. OR The amino acids containing equal number of carboxyl and amino groups are
called neutral a-
amino acids.
Example: Glycine, alanine, valine etc.
11. Explain the optical activity of amino acids.
Ans: All amino acids except glycine are optically active because they contain chiral carbon atom or asymmetric
carbon atom. They exists both in D and L foms. Most of the naturally occurring amino acids have L
configuration.
12 Name the optically inactive a-amino acid. [April-201, April-2017, July-2018, July-2019)
Ans: Glycine
H

H--COOH
NH,
is optically inactive.
Glycine does not contain chiral carbon atom. So it
How is it formed? [March-2019, March-2021)
13
What is peptide bond or peptide linkage? - or peptide linkage. Peptide
is called peptide bond
Ans: The-CO NH–bond formed between two a amino acids loss water molecules.
acids with the of
bond is formed by the union of two a-amino Peptide bond

H,N--ÇH-CONH-ÇH-COOH
HN-ÇH-COOH + HN-ÇH-COOH
R R
R R Dipeptide
of peptide bond.
Name the simple molecule lost
during the formation
Ans: Water (H,0).
structure.
15. Give dipeptide. Write its
an example for
Ans: Glycylalanine
CH -COOH
H,N-CH, -CO- NH–
CH, bonds. (March-2019, July-2019, March-2021]
calculate the number of peptide
the formula to
16.
- 1), where n number of a-amino acids.
Write =
=
Ans: peptide (n
Number of bonds
peptide in
II
PUChemistry
Student's illumir
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Biomoleaules
356
Evamples:
(i) A a-amino acids and l peptide bond.
dipeptide contains 2

acids and 2 peptide bonds.

(i) A tripeptide contains 3 a-amino
4 a-amino acids and 3 peptidc bonds and
so on.
peptidc contains
(i) Atctra
17. What are polypeptides?
more than 10 a-amino acids joincd by peptide bonds.
Ans: A polypeptide is a molccule containing
a - one chain
Erample: Insulin: Insulin contains 51 amino acids (2 polypeptide chains contains
30
amino acids and another chain contains 21 a-amino acids).
18. What are protcins?
Ans: A
polypeptide with more than hundred amino acid residues, having molecular mass higher than 10,000u
is
called a protein.
Note: Insulin is considered as a protein eventhough contains only 51 aminoacids because of its well
defined conformation.
19. What are Zwitter ions or dipolar ions? (July-2015, March-2016|
Ans: In aqueous solution, the carbOxylic acid group donates a proton to amino group (-NH) giving rise toa
dipolar ion known as Zwitter ion.
H O
H,N H,N
-OH
R R
(Zwitter ion)
20. How are proteins classified based on structure or
molecular shape?
(July-2016, March-2017, March-2022)
Ans: Based on the structure or molecular shape
proteins are classified into 2 types:
(i) Fibrous proteins (ii) Globular proteins
(i) Fibrous proteins: They have fibre like structure and
insoluble in water. (In these proteins the
polypeptide chains run parallel and held together
by hydrogen and disulphide bonds).
Example: (a) Keratin (present in hair,
wool, silk etc)
(b) Myosin (present in muscles)
(c) Collagen (present in cartilage)
(ii) Globular proteins: They have spherical shape
and soluble in water. (The spherical shape due to
coiling of polypeptide chains). Example:
Insulin, Albumin, Haemoglobin,
Note: During clotting of blood fibrinogen gets fibrinogen, etc.
converted into fibrous protein.
21. Name the protein present in hair.
Ans: Keratin [July-2014, March-202]
22. Name the protein present in blood.
Ans: Haemoglobin
23. What is primary structure of proteins?
Ans: The sequence in which the amino
acids are linked together by peptide bonds to
primary structure of protein. form protein S Ca he
OR Primary structure reveals acids in the
polypeptide chains that makeup the the specific Sequence of amino
protein.t
24. What is secondary structure
Ans: The coiling or
of proteins?
folding of polypeptide chain secondary
structure. There are 2 types in a protein as a
result of hydrogen bonding is called
of secondary structure.
Student's illuminator
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Publications 357
h
a-Helix In a-helix, the chain of
u-amino acids coil into right handcd screw (helix) due to hydrogen
() bonding. Example: a-keratin
B-pleated structure In ß - pleated structurc, maximum
ti) thc peptide chains are stretched out tothe
extent and are laid side by side which are held together hy intermolecular hydrogen bonds. (
sroups are small,
thc protcin assumes ß-plcated structure.)
1What is tertiary structure? (March-2021/
represents the overall folding and superimposition of
ns: It n polypeptide chains. Tertiary structure is stabilized by
der waals forces, ionic, hydrogen and disulphide bonds.
What is quaternary structure?
The spatial arrangement of polypeptide chains with respect to each other is called quaternary structure.
i
What
isnative protein?
inc Protein found in a biological system with a unique three-dimensional structure and biological activity is
called a native protein.
What is denaturation of proteins? Which level of structure remaining intact during denaturation of
globular protein? [March-2014, March-2015, March-2020, July-2020]
is5: Coagulation of proteins is called denaturation or the loss of biological activity of native protein by heating or
change in pH and presence of salts is called denaturation. During denaturation of protein, 2° and 3°
structures
destroyed but 1° structure remains intact.
9. Give example for denaturation of proteins.
Ans: (i)Coagulation of egg white on boiling.
present in milk.
(i) Cardling a milk due to the formation of lactic acid by the bacteria
Multiple Choice Questions (McQs)
1 The number of peptide bonds in tetrapeptide
b) a- hydroxyl acids
c) D-a- amino acids
is.....
2) 2 b) 3
d) L-a- amino acids
5. Globular proteins are present in
c) 4 d) s
a) blood b) hair
k Denaturation of proteins leads to loss of its c) nails d) all of these
biological activity by
6. In fibrous proteins, polypeptide chains are
a) formation of amino acids
held together by
b) Loss of primary structure
secondary a) van der waals forces
) Loss of both primary and b) electrostatic forces of attraction
structures c) hydrogen bonds
tertiary
d) Loss of both secondary and d) covalent bonds
structures. 7. Which of the following is not a fibrous
of
Amino acids generally exist in the form
3

protein?
Zwitter ions. Thís means they contain a) Keratin b) Myosin
group
a)
basic -NH, group and acidic -COOH c) Insulin d) Both (a) and (b)
acidic -COO
b) the basic
-NH; group and 8. Primary structure of a protein is
group a) sequence in which a- amino acids are
) basic -NH, andacidic -H group group
linked to one another
d) basic -CO0 group and acidic -NH; b) sequence in which amino acids of one
4. Proteins are polypeptides of polypeptide chain are joined to other chain
a) B- amino acids I1 P
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Biomdlecles
358
c) lincar scquence of amino
c) the folding pattens of polypeptide chains polypcptide chain
acid
In
d) the pattern in whicl the polypeptide chains d) denatured proteins
are arranged
12. Coagulation of protein is known as
9. The helical structure of protcin is stabiliscd
a) dehydration b) decay
by
c) deamination d) denaturation
a) dipcptide bonds b) hydrogen bonds
c) cther bonds d) peptide bonds 13. Which ofthe following terms refers
tothe
10. Secondary structure of protcins is mainly overall three dimensional shape of a protein?
a) Primary structure b) Secondary structure
governed by
a) hydrogen bonds b) covalent bonds c) Tertiary structure d) Quaternary structure
c) ionic bonds d) disulphide bonds 14. One of essential a- amino acids is

11. Tertiary structure of protein arises due to a) lysine b) serine

a) folding of polypeptide chain C) glycine d) proline
b) folding, coiling and bonding of polypeptide
chain
Answer Keys
12 3 4 5 6 7. 8 9 10 11 12 13 14
b d a d a a d a

10.3 Enzymes
1. What are enzymes?
Ans: Enzymes are proteins, they acts as bio-chemical catalysts.
Example: Invertase, zymase, amylase, lipase etc.
2. Give one example for an enzyme catalytic reaction. i24tgh Ahi brnd s
i
Ans: (a) An enzymes maltase converts maltose into glucose.
Maltase
C,H,,O,, + H,0 2C,H,0,
Maltose cose
Glu
(a) An enzyme invertase converts sucrose into glucose and fructose.
invertase
C,H,O,,+H,0 c,H,0,+C,H,,0,
Sucrose glucose fructose
3. What are oxido reductase enzymes?
Ans: The enzymes which catalyse the oxidation of one substrate with simultaneous reduction
are named as oxido reductase enzymes. of another suos
Note: (i) Activation energy in enzymne catalysed reaction is less than normal same
catalysis of the reaeti
(ii) Enzymes catalyses the bio-chemical reaction be lowering
the activation energy.
only
Example: E, for acid hydrolysis of sucrose is 6.22 kJ/mol, but with enzyme sucrose the E,,is
i
2.15 kJ/mol.
10.4 Vitamins
1. What are vitamins? for
functions
Ans: The organic compounds required in our diet in small amounts to perform specific biological deficiency
normal maintenance of optimum growth and health of the organism are called vitamins. But their
causes specific diseases.
hemistry
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Publications 359
ith Explainthe classification of vitamins,
(March-2014, July-2017, March-2020, March-2022
Vitamins are classified intotwo typesdepending on their solubility
Ans:
Fat soluble vitamins: Vitamins which are in water.
(a) soluble in fat and oils but insoluble in water. are called fat
soluble vitamins. They are storcd in liver and adiposc
tissues (fat storing tissues). Erample.
A, D, E and K.
(b) Water soluble vitamins: Vitamin B and C are soluble in water, They must be supplied regulary
diet because they are readily cxcreted in urine and cannot be stored in our body (except vitamin bi -
Example: B group vitamins and vitaminC. Vitamin B
has sub-groups B1, Bz, B6, B2.
Mention the sources and deficiency diseases caused by different types
of vitamins.
IMerch-2015, April-2016, July-2016, March-2017, March-2018, July-2018, July-2019,March-2021|

Name of vitamins Sources Deficiency diseases

Fish liver oil, carrots, butter Xerophthalmia (hardening of cornea of eye), Night
Vitamin A
and milk blindness
Vitamin B12 Meat, fish, egg and curd Pernicious anaemia (RBC deficient in haemoglobin)
Vitamin C Citrus fruits, amla and green Scurvy (bleeding gums)
(Ascorbic acid) leafy vegetables
Exposure to sunlight, fish and Rickets (bone deformities in children) and
Vitamin D egg yolk osteomalacia (soft bones and joint pain in adults)
Vitamin B, Yeast, milk, green vegetables Beri beri (loss of appetite, retarded growth)
(Thiamine) and cereals
Vitamin B, Milk, eggwhite, liver, kidney Cheilosis (fissuring at cormers of mouth and lips),
(Riboflavin) digestive disorders and burning sensation of the skin.
Vegetable oils like wheat Increased fragility of RBCs and muscular weakness.
Vitamin E germ oil, sunflower oil, etc.
Green leafy vegetables Increased blood clotting time, haemophilia.
Vitamin K
Convulsions
Vitamin B, Yeast, milk, egg yolk, cereals
(Pyridoxine) and grams

Multiple Choice Questions (MCQs)

5. Which of the following is a vitamin?
1. The water soluble vitamin is...... b) Ascorbic acid
a) Asparticacid
2) Vitamin-D b) Vitamin-A
c) Adipic acid d) Saccharic acid
c) Vitamin-E d) Vitamin-C one whose
6. Among the following vitamins the
2
deficiency vitamin which
causes disease :
The deficiency causes rickets (bone deficieney) is
sCurvy is... a) Vitamin A b) Vitamin B
Vitamin-A d) Vitamin C
a) Vitamin-D b) c) Vitamin D
c) Vitamin-E d) Vitamin-C 7. Anaemia is caused by the deficiency of vitamin
3, The blindness
vitamin which causes night a) B6 b) B
B: d) B2
is........ Vitamin-A 8.
c)
Vegetable oils like wheat gram oil sunflower
a) Vitamin-D b)
c) Vitamin-E d) Vitamin-K oil etc. are the good source of
4. a) Vitamin K b) Vitamin E
Vitamin B, is known as
c) Vitamin D d) Vitamin A
a) Pyridoxine b) Thiamine
c) Tocopherol d) Riboflavin
I| PU Chemistry
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Biomdlecles
B
360 10. Which of the following group vitamins
storcd in our body?
can
9. Which is soluble vitamin?
a fat be
b) Vitamin B, a) Vitamin B, b) Vitamin B,
a
Vitamin A
Vitamin C d) Vitamin B, Vitamin B, d) Vitamin Bi2
c) c)

Answer Keys
7 9 10
1 2 3 4 5
d b a d
a b C
d d b

10.5 Nucleic Acids

1. What are nucleic acids? storaoe
.

present in all living system and responsible for the

Ans: Nucleic acids are vital components
transmission of genetic information (heredity characteristics).
2. Name the types of nucleic acids.
Ans: Nucleic acids are of 2 types:
(a) RNA (Ribonucleicacid)
(b) DNA (Deoxyribonucleicacid)
3. Name the components of nucleic acids.
Ans: i) Nitrogen bases
(ü) Pentose sugar
(i) Phosphoric acid
4. Name the types of nitrogen bases present in nucleic acids.
Ans: Nitrogen bases are of 2 types:
Purine bases or purines: Adenine (A) and Guanine (G)
(a)
(b) Pyrimidine bases or pyrimidines: Cytosine (C), uracil (U) and Thymine (T).
5. Name the sugars present in nucleic acids and vrite their structures.
Ans: () Ribose or B-D-ribose (ii) Deoxyribose or B-D-2-deoxyribose
5
HOCH, QH HOCH, OH

2 H
OH ÖH ÖH
D-Ribose 2-Deoxy-D-ribose
tW7 i (in RNA) 16 8t (in DNA)

6. Name the components of RNA. (Jul-201I7]

Ans: (i) Pentose sugar -B- D-ribose
(ii)Nitrogen bases (AGCU) Adenine (A), Guanine (G), Cytosine (C) and Uracil (U)
(iii)Phosphoric acid
7. Name the components of DNA.s [March-2020/
Ans: (i) Pentose sugar - ß- D - deoxyribose
(ii) Nitrogen bases (AGCT) Adenine (A), Guanine (G), Cytosine (C) and Thymine (T)

(ii) Phosphoric acid Chemistry

Student's illuminator I| PU
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Publications 361
Jeevith

Writethe structures of
hetcrocyclic nitrogenous bases.
Purine bases in nucleic acids
Ans:
NH,
H

NH,
/
H Adeninc
H
Guanine
(DNA, RNA) (DNA, RNA)
yrimidinei bases in nucleic acids
I
NH,
H,C H H

H H H
Cytosine Thymine Uracil
(DNA, RNA) (DNA) (RNA)

9. Name the nitrogenous base present in DNA but not in RNA. March-2022/
[March-2015, July-2015, July-2018, March-2021,
Ans: Thymine.
10. Name the (+) nitrogenous base present in RNA but not in DNA.
[March-2014, March-2016, March-2018]

Ans: Uracil (U)

11. Name the bases present in both DNA and RNA.
Ans: Adenine, guanine and cytosine (AGC)
12. What are nucleosides? base and pentose
sugar.
a containing nitrogen
Ans: Nucleoside is compound adenine and ribose
sugar.
a nucleoside containing
Example: Adenosine is
13. What are nucleotides? are called nucleotides.
AnS: Phosphoric acid
esters of nucleosides
(Nucleotide sugar + base + phosphoric acid) phosphate).
(Adenosine mono phosphate or adenosine -5-
Lxample: AMP
at carbon atom 5' of the pentose sugar.
Note: (esterification) takes place
phosphorylation atoms of pentose sugar.
linkage between 5' and carbon
3'
(i) In nucleotides ester
containing phosphate-
(i) Nucleotides 3' of the
14, What are dinucleotides? phosplhodiester linkage between carbon atoms 5' and
together by
joined
Ans: Two nucleotides are
dinucleotides.
Pentose sugar are called

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362
aa nuclcotide and
nuclcoside.
I 15. Write the structurcs of

base
HO– ÇH, basc

H
H
H
3 2
OH OH
OH
OH
A nucleotide
A nucleoside

What are polynucliotides?

16.
nucleotides are called polynucleotides.
Ans: Compounds containing large number of
Example: Nucleic acids (RNA and DNA)
Polynuleotides are called nucleic acids.
Note: Nucleic acids are polymers of nucleotides. OR
17. Give the difference between DNA and RNA.
S. RNA
DNA
No.
i. It has double stranded helical structure. It has single stranded polynucleotide chain.
ii. Sugar present is ß-D-2-deoxyribose. Sugar present is ß-D-ribose.
It contains adenine, guanine cytosine and thymine It contains adenine, guanine, cytosine and uracil
iii.
bases. bases.
It
iv. replicates. It does not replicates.
V. It controls transmission of genetic information. It regulates protein synthesis.
It has large molecular mass (6 - 16 million u) It has relatively low molecular mass
vi.
-
(20,000 40,000 u)
18. Explain the structure of DNA.
Ans: The structure of DNA was proposed by Dr. Watson and Dr. F. Crick.
(a) DNA contains double stranded helical structure.
(b) The double helix is stabilised by hydrogen bonds.
(C) The 2 strands are antiparallel and complimentary to each other.
(d) The two strands are held together by specific base pairing.
(e) The bases are paired through hydrogen bonds (Chargoff's rule) A =T and G C.
() The distance between the 2 successive base pairs is 3.4 and the diameter of the helix is 20A.
Å

19. How many hydrogen bonds are present between adenine and thymine?
Ans: 2 hydrogen bonds (A =T)
20. How many hydrogen bonds are present between guanine and cytosine?
Ans: 3 hydrogen bonds (G= C)
21. What is replication or duplication? or
Ans: DNA has capacity
to produce an exact duplicate (xerox copy) of itself. This is called replication
duplication.
22. Explain the structure of RNA,
Ans: (i) RNA contains single stranded polynucleotide chain coiled in a random manner.
(ii) RNA is of 3 types:
particular
(a) m-RNA (messenger RNA) It sends the message of DNA for the synthesis of
protein,
stry
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Publications 363
nevith

(b) r-RNA (ribosomal RNA) y It nrovides the site for nrotcin

synthesis in he yup
ribosomes.
(c) (-RNA (transter RNA)
synthesis.
- It carries (sunnlics) required amino acids to the site P

Jnder the direction of DNA a particular

protein gets synthesised.
Mention the biological functions of nucleic acids.
Ans: Functions of DNA
(a) DNA transfers genetic information (hereditary
characteristics)
(b) DNAcan replicate itself, so identical DNA is transferred to
off springs.
(c) DNA is responsible for maintaining identity of species of organisms over millions of years.
(d) DNAdirects and controlthe biosynthesis proteins.
of
(e) DNAsynthesizes RNA
Functions of RNA
() RNA plays a very important role in the synthesis of proteins.
() Various RNA (m-RNA, r-RNAand t-RNA)help in the protein synthesis.

10.6 Hormones
24. What are hormones? Give examples. [April-2015]
Ans: Hormones are molecules that act as intercellulr messengers. They are secreted by endocrine glands in the
body and are poured directly in the blood stream which transports them to the site of action.
Example: Insulin, oxytocin, glucagons, hydroxine, epinephrine, estrogen and androgens etc.
25. Mention the types and examples of hormones.
SI.
Type Example
No.
Insulin, endorphins, glucagons t
i. Polypeptide
Epinephrine, norepinephrine
ii. Amino acid derivatives Thyroxine (iodine containing hormone)
Estrogen and androgens
iii. Steroids
Z6. Give the functions of the following hormones.
April-2016, July-2016, Marclh-2019, July-2019, July-2020, March-2022]
to the balance of biological activities in
Ans: Hormones have several functions in the body. They help maintain
the body.
glucose level in the body.
i. Glucagon: It tends to increase the sugar level
response to the rapid rise in blood sugar level and keeps the blood
ii. Insulin: It is released in sugar level
narrowlimit. Thus, both giucagon and insulinregulate the normal
of the body with in the
in the body. responses to external stimul:
These hormones mediate
iii. Epinephrine and norepinephrine: amino acid tyrosine
gland and 1S ne lodinated derivative of
iv, Thyroxine: It is produced from thyroidleads to hypothyroidism which is characterised by lethargyness
of thyroxine
Very low concentration causes hyperthyroidism. Low level of iodine in the diet
concentration of thyroxine
and obesity. High of thyroid gland. This condition is largely being
hypothyroidism and enlargement
may lead to commercial salts (Iodised salt).
sodium iodideto
controlled by adding cortex (Glucocorticoids and mineralocorticoids)
are produced by adrenal
V. Steroid hormones: They testes in males and Estradiol produced in ovaries in females).
estosterone produced in
and gonads (Te
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Biomolecue
64
metahel:
cortex. They control the carbohydrate
(a) Glucocorticoids: Produced from adrenal
are involved in reactions to stress.
modulate inflammatory reactions and
-the level of excretion t
(b) Mineralocorticoids: Produced from adrenal cortex. They control
water and salt by the kidney.
causes the disease called Addison's disease characterized
(c) Non functioning of adrenal cortex
to stress.
by hypoglycemia, weakness, and increased susceptibility
mineralocorticoids.
(d) Addison's disease is fatal unless it is treated by glucocorticoids and
sexual
vi. Sex hormones: Hormones released by gonads are responsible for development of secondary
characters.
(a) Testosterone is the major sex hormone produced in males. It is responsible for development of
secondary male characteristics (deep voice, facial hair, general physical constitution).
(b) Estradiol is the main female sex hormone. It is responsible for development of secondary
female characteristics and participates in the control of menstrual cycle.
(c) Progesterone isresponsible for preparing the uterus for implantation of fertilised egg.

Multiple Choice Questions (MCQs)

Nucleic acids are........ 5. In DNA the linkages between different
a) Polymers of nucleotides nitrogenous bases are
b) Polymers of nucleosides a) peptide linkage b) phosphate linkage
c) Polyrmers of purine bases through c) H-bonding d) glycosidic linkage
phosphate ester bonds in a
following is not present
6.
Which of the
d) Phosphate ester bonds
nucleotide?
RNA contains..... a) Guanine b) Cytosine
a) Ribose sugar and Thymine c) Adenine d) Tyrosine
b) Ribose sugar and Uracil each.
7. DNA and RNA contain four bases
c) Deoxyribose sugar and Uracil Which of the following bases is not
presentin
d) Deoxyribose sugar and Thymine
RNA?
In DNA, the complementary bases are..... a) Adenine b) Uracil
(a) Adenine and Thymine; Guanine and c) Thymine d) Cytosine
Cytosine presentin
8. Which of the following bases is not
(b) Uraciland Adenine; Cytosine and Guanine
e: Thymine DNA?