Chemistry Enrichment Material-1

KENDRIYA VIDYALAYA SANGATHAN
(CHANDIGARH REGION)
CONTENT ENRICHMENT STUDY MATERIAL
SESSION : 2023-24
CLASS : XII
SUBJECT : CHEMISTRY
KENDRIYA VIDYALAYA SANGATHAN
(CHANDIGARH REGION)
CONTENT ENRICHMENT STUDY MATERIAL

SESSION : 2023-24
CLASS-XII
SUBJECT : CHEMISTRY
CHIEF PATRON MRS. NIDHI PANDEY IIS
COMMISSIONER KVS (HQ) NEW DELHI
CO PATRON MRS PREETI SAXENA

DEPUTY COMMISSIONER KVS RO CHANDIGARH
SHRI T BRAHMANANDAM
ASSISTANT COMMISSIONER
KVS RO CHANDIGARH
SHRI JUGAL KISHORE

PATRONS
KVS RO CHANDIGARH
SHRI PC TIWARI
KVS RO CHANDIGARH
CHIEF COORDINATOR Mr. RAKESH KUMAR

PRINCIPAL
KV KAPURTHALA CANTT
MS.NARINDER CHUMBER
PGT CHEMISTRY
KV No.1 JALANDHAR CANTT
MR.SURENDER KUMAR
COORDINATORS:
PGT CHEMISTRY
KV No.4 JALANDHAR CANTT
MRS.KOMAL CHAHAL
PGT CHEMISTRY
KV No.1 HUSSAINPUR
Mr. Kuldeep Kumar
KV Shikarpur
Ms. Kavita Kaur

KV No.1, Adampur
Ms.Asha Rani
KV No.2 Pathankot
Ms. Simran Kaur

KV No. 3 Amritsar
Mr. Ajay Singh

KV No. 2 RCF, Hussainpur
SUBJECT EXPERTS :
Mr. Ajay Kumar

KV Mohali
Ms .Deepa Parmar
KV Chandigarh 3 BRD
Mr. Sudhir Maingi

KV No.1, Pathankot
Mr. Vijesh Kumar

KV Bhunga
Ms. Priya Goel
KV Barnala
FOREWORD
It gives me immense pleasure in presenting the Students' Support Material to all KV students
of class XII. The material has been prepared keeping in mind your needs of all the
stakeholders. This material will support you in better vision and bird eye view revision of the
content
A team of dedicated and experienced teachers with expertise in their subjects has prepared
this material after a lot of exercise. This material should not be taken as a substitute to the
NCERT text book but it is designed to supplement it.
The Students Content Enrichment Material has all the important aspects sample paper issued
by CBSE indicating the design of the question paper, syllabus, concepts in the form of Gist,
mind maps, flow charts, master cards, level wise questions and information in tables for easy
reference, sample practice questions from every chapter and questions from previous years
Board exam question papers.
I am sure that the Support Material will be used by both students and teachers and I am
confident that the material will help the student in improving their performance in CBSE
Board Examination.
Happy learning to all!
- Chief Coordinator
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CLASS XII (2023-24)
CHEMISTRY 043 (THEORY)

Time : 3 Hours Maximum Marks :70
S.No. Unit Page No. No. of Periods Marks

1 Solutions 3 - 15 10 7
2 Electrochemistry 16 - 35 12 9
3 Chemical Kinetics 36 - 49 10 7
4 d -and f -Block Elements 50 - 60 12 7
5 Coordination Compounds 61 - 80 12 7
6 Haloalkanes and Haloarenes 81 - 92 10 6
7 Alcohols, Phenols and Ethers 93 - 108 10 6
8 Aldehydes, Ketones and Carboxylic Acids 109 - 141 10 8
9 Amines 142 - 163 10 6
10 Biomolecules 164 - 190 12 7
Total 108 70
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UNIT 1 - SOLUTIONS
SYLLABUS
Types of solutions, expression of concentration of solutions of solids in liquids, solubility of gases in liquids,
solid solutions, Raoult's law, colligative properties - relative lowering of vapour pressure, elevation of
boiling point, depression of freezing point, osmotic pressure, determination of molecular masses using
colligative properties, abnormal molecular mass, Van't Hoff factor.
TYPES OF SOLUTIONS
Brass (mixture of copper and zinc)

German silver (mixture of copper, zinc and nickel)
Bronze (mixture of copper and tin)
By homogenous mixture we mean that its composition and properties are uniform throughout the mixture.
that is present in the largest quantity is known as solvent and present in less quantity are solute .
Binary solutions contains two components.
Types of solutions -
S.No. Solute Solvent Types of Solutions Examples
1. Solid Solid Solid in solid = Solid Alloys - brass, bronze,
2. Liquid Solid Liquid in solid = Solid Sodium Amalgam (Na- Hg)
3. Gas Solid Gas in solid= Solid Solution of H2 in Pd, dissolved gases in minerals.
4. Solid Liquid Solid in liquid = liquid Sugar solution, salt solution, I2, in CCl4.
5. Liquid Liquid Liquid in liquid = liquid Benzene in toluene, alcohol in water.
6. Gas Liquid Gas in liquid= liquid CO2 in water, NH3 in water etc.
Iodine vapours in air, camphor vapours in N2.
7. Solid Gas Solid in gas =gaseous
Aerosols (fine solid/liquid particle in air)
8. Liquid Gas Liquid in gas =gaseous Water vapours in air, CHCl3 vapours in N2.
9. Gas Gas Gas in gas=gaseous Air
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EXPRESSION OF CONCENTRATION OF SOLUTIONS OF SOLIDS IN LIQUIDS
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑊1)

Mass percentage. w/w % = 𝑋 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑊1+𝑊2)
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉1)

Volume percentage. v/v % = 𝑋 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
PPM = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑋 106
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Mass / volume percentage. w/v % = 𝑋 100
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

Mole fraction = 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑋 100 ;
𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠
For a solution sum of all the mole fractions is unity =1

XA + X B = 1 ; XA = 1 - XB
Molarity (M) : number of moles of solute dissolved in per litre solution (mol per litre)
𝑀𝑂𝐿𝐸𝑆 𝑂𝐹 𝑆𝑂𝐿𝑈𝑇𝐸 𝑛2 𝑋1000
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝐿𝑖𝑡𝑟𝑒𝑠 𝑜𝑟 𝑣 𝑚𝐿
Molality (m); number of moles of solute per kg solvent ( mol per kg)
𝑀𝑂𝐿𝐸𝑆 𝑂𝐹 𝑆𝑂𝐿𝑈𝑇𝐸 𝑛2 𝑋1000
𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦 (𝑚) = 𝑜𝑟
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝐾𝑔 𝑊1 𝑔
Mass % , ppm , mole fraction and molality are independent of temperature whereas molarity is a function
of temperature because volume depends on temperature but mass do not.
SOLUBILITY OF GASES IN LIQUIDS

Solubility depends on nature of solute and solvent , temperature pressure .In a solution of solid in liquid ,
the surface has both solute and solvent molecules; thereby the fraction of the surface covered by the
solvent molecules gets reduced. Consequently, the number of solvent molecules escaping from the
surface is correspondingly reduced, thus, the vapour pressure is also reduced.Solubility of gas increases
with decrease of temperature. It is due to this reason that aquatic species are more comfortable in cold
waters rather than in warm waters
Henry’s Law:At constant T , the solubility of a gas in a liquid is directly proportional to the partial pressure
(p) of the gas.
p = KH .X KH = Henry’s constant ( higher the KH value lower the solubility of a gas in liquid )
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Gas solubility α 𝐾𝐻
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Application of Henry’s Law
1. To increase the solubility of CO2 in soft drinks, the bottle is sealed under high pressure.
2. To avoid bends, Divers use cylinders filled with 56. 2% N2 , 11.7% He and 32. 1 % O2 gas to avoid
solubility of nitrogen gas in blood , under water pressure.
3. At high altitude due to less air pressure , the solubility of oxygen in blood decreases and it develops
confusion , nausea in mountaineers ,is called anoxia.
Raoult’s Law
For the solution of volatile liquids, the partial vapour pressure of each component is directly proportional
to its mole fraction present in solution .
P1 α X1 ; P1 is partial vapour pressure
P1 = P10 X1 ; P10 is vapour pressure of pure component
P2 = P20 X2
Ptotal = P1 + P2 (Dalton’s law of partial pressure )
Ptotal = P10 + ( P20 - P10) X2
When KH (Henry constant ) equals to P10 ( v.p of pure component ) Henry ‘s law becomes Raoult ‘s law.
Ideal and non ideal solutions
The solutions which obey Raoult’s law over the entire range of concentration are known as ideal solutions.
( For ideal solution Δmix H = 0, Δmix V = 0)
Example ( perfectly ideal solutions are rare )but nearly ideal solution are:-
Solution of n- hexane + n- heptane ,bromoethane + chloroethane ,benzene + toluene
When solution does not obey Raoult’s law over the entire range of concentration are known as non ideal
solution.
The vapour pressure of such a solution is either higher or lower than expected . if it is higher , the solution
show positive deviation and if it is lower it show negative deviation .
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Positive deviation : A – B interaction is weaker than A – A or B – B molecule interactions and the vapour
pressure of solution get increase that results in positive deviation . (PA+ PB> PA XA+ PB XB )
Example: C2H5OH + Water , Mixtures of ethanol and acetone , mix of CS2 and acetone etc.
Negative deviations :
(i) A – B interaction is stronger than A – A or B – B molecule interactions and the vapour pressure of
solution get increase that results in positive deviation . (PA+ PB < PA XA+ PB XB ) .
Hydrogen bonds are also responsible for stronger A- B interaction in mixture.
Example- A mixture of phenol + aniline. A mixture of chloroform + acetone .
AZEOTROPES :- some liquids on mixing form binary solutions that having the same composition in liquid
and vapour phase and boiled at a constant temperature and not easy to separate by fractional distillation.
(i) Minimum boiling azeotropes: the solutions that show large positive deviation at a specific
composition from Raoult’s law. Example; ethanol and water. (C2H5OH + H2O)
(ii) Maximum boiling azeotropes: the solutions that show large negative deviation at a specific
composition from Raoult’s law. Example, 68% Nitric acid and 32% water at boiling point 393.5
(HNO3 + H2O).
COLLIGATIVE PROPERTIES AND DETERNMINATION OF MOLAR MASS
We know that the vapour pressure of solution get decreases when a non-volatile solute is added to
the solution and some properties . Colligative properties are the democratic properties of solution
which depend upon the relative number of moles and not on the nature of solute particles. The
four colligative properties of solutions are:
(1) Relative lowering of vapour pressure (2) Depression in freezing point . (3) Elevation in boiling
point (4) Osmotic pressure .
1) Relative lowering of vapour pressure

P1 = P10 X1
𝑃10 −𝑃1 𝑛2 𝑃10 −𝑃1 𝑤2 𝑋 𝑀1

= OR =
𝑃10 𝑛1 𝑃10 𝑀2 𝑋 𝑤 1
2) Elevation in boiling point

∆Tb =Tb – T°b = elevation in boiling point
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∆Tb = Kb m
Kb X 1000 𝑋 𝑤2 Kb X 1000 𝑋 𝑤2
∆Tb = 𝑀2 𝑋 𝑤1 OR M2 = ∆Tb 𝑋 𝑤1
Kb = Ebullioscopic constant /Boiling point elevation constant / Molal Elevation Constant (K.Kg/mol)
3) Depression in freezing point
∆Tf =Tf – T°f = Depression in freezing point
∆Tf = Kf m
Kf X 1000 𝑋 𝑤2 Kf X 1000 𝑋 𝑤2
∆Tf = OR M2 =
𝑀2 𝑋 𝑤1 ∆Tf 𝑋 𝑤1
Kf = Cryoscopic constant /Freezing point depression constant / Molal depression Constant

(K.Kg/mol)
Applications (Importance) of depression in freezing point.
(i) In making antifreeze solutions: - The running of a car in sub-zero weather even when the
radiator is full of water (which freezes below 273 K) has been possible due to the fact that
depression in freezing point of water takes place when appropriate amount of a suitable
solute (usually ethylene glycol) called antifreeze is dissolved in the water.
(ii) In melting of ice on the roads: -In winter or in the hills where it snows heavily, common salt
(NaCl) or calcium chloride (CaCl2) is scattered on the roads to melt ice. This is because salt-ice
mixture has very low freezing point.
4) Osmotic pressure
Used for heavy molecules like protiens and polymers and macromolecules molecular mass
calculation.
Movement of solvent molecules through a semi permeable membrane from pure solvent to
solution is called Osmosis.
𝑤2 𝑅𝑇
𝝅 = 𝑪𝑹𝑻 OR M2 = 𝝅𝑽
if a pressure higher than the osmotic pressure is applied on the solution, the solvent will flow from
the solution into the pure solvent through the semi-permeable membrane. The process is called
reverse osmosis (R.O.).
Salty water can be de-salined by reverse osmosis. Cellulose acetate can be used for purification of
saline water.
When RBCs placed in water containing less than 0.9% (m/v) salt, the blood cells swell due to flow of
water in them by osmosis.
People taking a lot of salt /salty food experience water retention in tissue cells and intercellular
spaces because of osmosis. this resulting puffiness /swelling is called Edema.
Abnormal molar masses

CH3COOH get dimerise in benzene due to hydrogen bonding and the molar mass counts double to
120 g/ mol.
𝐧𝐨𝐫𝐦𝐚𝐥 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬
i= 𝑎𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
Van’t Hoff factor for CH3COOH= 0.5, KCl = 2 ; K2SO4 = 3
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OBJECTIVE TYPE QUESTIONS
MCQ
1. which one of the following aqueous solution should have the highest boiling point
a) 1.0 M HCl b) 1.0 M Na2SO4 c) 1.0 M NH2CONH2 d) 1.0 M KNO3
2. What will happen if blood cells are kept in hypertonic solution
a) they shrink b) they swell c) they die d) they remain same
3. The increase in temperature of an aqueous solution will results in
a) molality to increase b) molarity to increase c) mole fraction to increase d) molarity to decrease
4. Which of the following solution containing components A and B follow Raoult's Law?
a) A-B attraction force is greater than A-A and B-B
b) A-B attraction force is less than A-A and B-B
c) A-B attraction force remains same as A-A and B-B
d) Volume of solution is different from sum of volume of A and B
5. The vapour pressure of the solution containing non-volatile solute is:
a) greater than vapour pressure of pure solvent
b) lesser than vapour pressure of pure solvent
c) equal to the vapour pressure of pure solvent
d) the sum of the vapour pressure of the solute and the solvent
6. Elevation of boiling point is inversely proportional to
a) Kb b) molality c) molar mass of solute d) weight of solute
7. Which of the following solutions shows positive deviation from Raoult’s law?
a) Acetone + Aniline b) Acetone + Ethanol c) Water + Nitric acid d) Chloroform + Benzene
8. If molality of the dilute solution is doubled, the value of molal depression constant (K f) will be
a) Halved b) Tripled c) Unchanged d) Doubled.
9. Which of the following statements is correct?
a) Solutes that dissociates in water experience a decrease in colligative properties
b) Colligative properties are independent of the number of particles of the solute in the solution
c)Solutes that dissociate in water have molar mass higher than the molar mass of the solute
calculated theoretically
d)Solutes that associate in water have molar mass higher than the molar mass of the solute
calculated theoretically
10. In which expression the concentration of solution remains independent of temperature
a) molality b) molarity c) w/v % d) v/v%
11. The snow is sprinkled with NaCl, then its:
a) its boiling point will be elevated b) its freezing point will be depressed
c) its vapour pressure will be lowered d) all of the above
12. 1.00 g of a non-electrolyte solute dissolved in 50 g of benzene lowered the freezing point of
benzene by 0.40 K. The freezing point depression constant of benzene is 5.12 K kg /mol. Find the
molar mass of the solute.
a)254 g /mol b)256 g /mol c) 265 g /mol d)245 g /mol
13. An azeotropic solution of two liquids has boiling point lower than either of them when it:
a) shows negative deviation from Raoult's law b) shows no deviation from Raoult's law
c) shows positive deviation from Raoult's law d) is saturated
14. The colligative property used for determination of molar mass of proteins and polymers
(CBSE 2023)
a) Relative lowering of vapour pressure b) Depression in freezing point
c) Elevation in boiling point d) Osmotic pressure of solution.
15. Low concentration of oxygen in blood and tissues of people living at high altitude is due to:
a) high atmospheric pressure b) low temperature (CBSE 2023)
c) low atmospheric pressure d) both low temperature and high pressure
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16. The Solutions boiled at a constant temperature are called:
a) Amorphous b) Azeotropic mixture c) Ideal solution d) Super saturated solution
17. The value of Henry’s Law constant is:
a) larger for gases with higher solubility b) larger for gases with lower solubility
c) constant for all gases d) not related to the solubility of gases
18. An unknown gas ‘X’ is dissolved in water at 2.5 bar pressure and has mole fraction 0.04 in solution.
The mole fraction of ‘X’ gas when the pressure of gas is doubled at the same temperature is:
a) 0.02 b) 0.04 c) 0.08 d) 0.92
19. The boiling point of a 0.2 m solution of a non-electrolyte in water is ----------------------------
(Kb H2O = 0.52 K Kg /mol)
a)100.29 ℃ b)100 ℃ c) 100.52 ℃ d) 100.10 ℃
20. Which of the following liquid pairs shows a positive deviation from Raoult's law?
a) Water-hydrochloric acid b) Benzene-methanol c) Water-nitric acid d) Acetone-chloroform
ASSERTION -REASON-ASSERTION TYPE QUESTIONS

(a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
(c)Assertion is correct statement but reason is wrong statement.
(d)Assertion is wrong statement but reason is correct statement
21. Assertion: Ethanol in water is a real solution.
Reason: As 95% aqueous solution of ethanol is called as absolute alcohol.
22. Assertion: Molarity of a solution in liquid state changes with temperature.

Reason: The volume of a solution changes with change in temperature.
23. Assertion: Depression of freezing point is a colligative property.

Reason: The depression of freezing point for a solution is directly proportional to the molality
of the solution
24. Assertion: When methyl alcohol is added in water, boiling point is increased.
Reason: When a volatile solute is added in a volatile solvent elevation in boiling point
is observed.
25. Assertion It is difficult to separate Azeotropic Mixture.
Reason: Azeotropic mixture boils as a single component at a constant temperature so that
fractional distillation doesn’t work.
26. Assertion: When a solution is separated from pure solvent by a semi-permeable membrane, solvent
molecules pass through it from solvent side to solution side.
Reason: Diffusion is the movement of particles from an area of higher concentration to lower
concentration.
27. Assertion: in an ideal solution Δmix H = 0
Reason: in an ideal solution, A-B interaction are not equal to A-A and B-B interactions
28. Assertion: 1M solution of KCl has less osmotic pressure than 1M solution of glucose
Reason: in solution KCl dissociates into a greater number of particles.
29. Assertion: an ideal solution obeys Henry’s law (CBSE 2020)
Reason: in an ideal solution, solute – solute as well as solvent solvent interactions are similar to
solute solvent interaction.
30. Assertion: Osmosis is the process used in desalination of sea water.
Reason: the direction of osmosis can be reversed if pressure is smaller than the osmotic pressure
applied to the solution side.
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Case based question
Read the paragraph answer the questions:
1. In the case of osmosis, you can once again think of molecules—this time, water molecules—in
two compartments separated by a membrane. If neither compartment contains any solute, the
water molecules will be equally likely to move in either direction between the compartments.
But if we add solute to one compartment, it will affect the likelihood of water molecules
moving out of that compartment and into the other—specifically, it will reduce this likelihood.
Three terms—hypertonic, hypotonic, and isotonic—are used to describe whether a solution will
cause water to move into or out of a cell. If a cell is placed in a hypertonic solution, there will
be a net flow of water out of the cell, and the cell will lose volume. A solution will be hypertonic
to a cell if its solute concentration is higher than that inside the cell, and the solutes cannot
cross the membrane. If a cell is placed in a hypotonic solution, there will be a net flow of
water into the cell, and the cell will gain volume. If the solute concentration outside the cell is
lower than inside the cell, and the solutes cannot cross the membrane, then that solution is
hypotonic to the cell. If a cell is placed in an isotonic solution, there will be no net flow of water
into or out of the cell, and the cell’s volume will remain stable. If the solute concentration
outside the cell is the same as inside the cell, and the solutes cannot cross the membrane, then
that solution is isotonic to the cell.
1. What happens if blood cells are kept in hypertonic solution
a) they swell b) they shrink c) they remain same d) they die
2. Desalination can be done with
a) osmosis b) reverse osmosis c) diffusion d) edema
3. Excess intake of salt inhuman body can create a condition named
a) anoxia b) edema c) bending d) diabetes
b) Osmosis can happen through --------------.
a) cell membrane b) plasma membrane c) semi permeable membrane d) all of these.
B.) Raoult’s law state that for a solution of volatile liquids, the partial pressure of each component of the
solution is directly proportional to its mole fraction present in solution. Dalton’s law ofpartial pressure
state that the total pressure over the solution phase in the container will be sum of the partial pressure of
the components of the solution and its given as P total = P1+P2.
If we compare Raoult’s law with Henry’s law, it can be seen that the partial pressure of volatile component
or gas is directly proportional to its mole fraction. When KH equals to P10, the Raoult’s law becomes special
case of Henry’s law.
1. Is Raoult’s law applicable to non-volatile liquids ?

Ans: yes
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2. In what condition Raoult’s law becomes Henry’s law?
Ans: When KH equals to 𝑃10 , the Raoult’s law becomes special case of Henry’s law.
3. What kind of deviation is shown in above graph?
Ans: negative deviation.
4. A solution of two liquid boils at a temperature more than the boiling point of either of components.
what type of deviation may be shown by the solution as per Raoult’s law?
Ans: negative.
SA TYPE -I QUESTIONS ( 1 MARKS)
1. Calculate the molarity of NaOH solution obtain by dissolving 2g NaOH in 50 ml of its

solution.
Ans: 50 ml NaOH contains = 2 g of NaOH
So 1000ml will contains 2/50 x 1000 = 40g NaOH
So, number of moles = 40/40= 1 mol and molarity will be 1M
2. Why molarity changes on changing temperature?
Ans: molarity depends on volume and volume can be vary with temperature.
3. On high altitudes someone feel tired.
Ans: On high altitudes partial pressure of oxygen gas is less so solubility of gases decreases
in blood.
4. Define azeotropes.
Ans: some liquids on mixing form binary solutions that having the same composition in
liquid and vapour phase and boiled at a constant temperature. and not easy to separate by
fractional distillation.
5. The molar mass of acetic acid observed 120 g/mol instead of 60 g/mol, on mixing some
solvent.
Ans: due to association, because of hydrogen bonding.
6. What are colligative properties?
Ans: properties depend on the number of solute particles irrespective of their nature
relative to total number of particle present in solution are called colligative properties
7. In hilly areas salt is sprinkle on roads during snow fall?
Ans: By adding the salt the freezing point of water get decreases.
8. It is better to add salt, while cooking dal?
Ans: On adding salt the boiling point get increases and it get easily cooked.
SA TYPE -II (2 MARKS)
1. What is Henry’s law? Give one application of it? (CBSE 2023)

Ans: Henry’s law: The solubility of a gas in a liquid at a particular temperature is directly
proportional to the pressure of the gas in equilibrium with the liquid at that temperature.
or
The partial pressure of a gas in vapour phase is proportional to the mole fraction of the gas
(x) in the solution. p = KHX
Applications of Henry’s law:
(i) In order to increase the solubility of CO2 gas in soft drinks and soda water.
11
2. A solution is prepared by dissolving 10 g of non-volatile solute in 200 g of water. it has a
vapour pressure of 31.84 mm Hg at 308 K. Calculate the molar mass of solute. ( v.p of pure
water at 308 K is 32 mmHg) (CBSE 2023)
𝑃10 −𝑃1 𝑤2 𝑋 𝑀1
Ans: Formula used =
𝑃10 𝑀2 𝑋 𝑤 1
𝑃10 𝑋 𝑤2 𝑋 𝑀1
M2 = (𝑃10 −𝑃1 ) 𝑋 𝑤 1
32𝑋 10 𝑋 18
M2= = 180 g/mol
0.16 𝑋 200
3. What role does the molecular interaction play in solution of alcohol in water?
Ans: Hydrogen bonds increase the magnitude of attractive forces tends to decrease and the
solution shows positive deviation from Raoult’s Law. This will lead to increase in vapour
pressure of the solution and decrease in its boiling point.
4. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 30% of
C2H6O2 by mass.
Ans: Assume that we have 100 g of solution
(one can start with any amount of solution because the results obtained will be the same).
Solution will contain 30 g of ethylene glycol and 70 g of water.
Molar mass of C2H6O2 = 12x 2 + 1x 6 + 16x 2 = 62 g /mol.
30
Moles of C2H6O2 = 62 = 0.483 𝑚𝑜𝑙𝑒𝑠
70
Moles of water = = 3.888 𝑚𝑜𝑙𝑒𝑠
18
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑙𝑦𝑐𝑜𝑙
X glycol = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑙𝑦𝑐𝑜𝑙+𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟
0.483 0.483
X glycol = = =0.11
0.483+3.888 4.371
X water = 1 - 0.11= 0.89
5. 300 cm3 of an aqueous solution of a protein contains 1.22 g of the protein. The osmotic
pressure of such a solution at 300 K is found to be 2.59 x 10-3 bar. Calculate the molar mass
of the protein.
(R= 0.083 L bar /mol/K).
Ans: 𝝅 =2.59 x 10-3 bar
V =0.300L, T=300 K , R= 0.083 L bar /mol/K , W2=1.22g;
𝑤2 𝑅𝑇
M2 = 𝝅𝑽
1.22 𝑋 0.083 𝑋300

M2 = 2.59 x 10−3 = 39096 g/mol
X0.300
SA TYPE – III QUESTIONS (3 Marks)
1. a) Differentiate between ideal and non-ideal solution (CBSE 2017 ,2023)

b) 30g urea dissolved in 846 g of water. Calculate the vapour pressure of water for this solution if
vapour pressure of pure water is 23.8 mmHg at 298 K.
12
Ans: a) ideal solution obeys Raoult’s law over entire range of concentration
b) no. of moles of urea = 30/60= 0.5 moles
No. of moles of water = 846 /18 = 47 moles
X2 = moles of urea / total moles
X2 = 0.5/47.5 =1/95 moles
𝑃10 −𝑃1
= 𝑥2= 1/95
𝑃10
23.5−𝑃1 1
= 95
23.5
P1 = 23.55 mm Hg
2. Give reasons: (CBSE 2018 , 2023)

a) Measurement of osmotic pressure method is preferred for the determination of molar masses
of macromolecules such as proteins and polymers.
b) Aquatic animals are more comfortable in cold water than in warm water.
c) Elevation of boiling point of 1M KCl is nearly double than that of 1M sugar.
Ans: a) biomolecules are generally not stable at higher temperature and polymers have poor
solubility.
b) in cold water oxygen get more easily dissolved in blood.
c) on ionisation KCl dissociate into ions and vant Hoff factor is 2.
3. An antifreeze solution is prepared from 222.6 g of ethylene glycol, (C2 H6O2 ) and 200 g of water.
Calculate the molality of the solution. If the density of the solution is 1.072 g mL-1, then what shall be
the molarity of the solution.
Ans: mass of solute = 222.6 g

Molar mass of C2H6O2 = 62 g/mol
No. of moles = 222.6/62 = 3.59 moles
Mass of solvent = 200 g
Molality = 3.59/0.200 = 17.95 mol/Kg
Total mass of solution = 222.6+200 = 422.6 g
Volume of solution = 422.6/1.072 = 394.2 m L
So, molarity = 3.59/394.2 x 1000= 9.1 mol/L

4. A 10 % solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing
point of 10% glucose in water if freezing point of pure water is 273.15 K.
Ans: Mass of sugar in 10% (by mass) solution means 10 gin 100g of solvent (water)
Molar mass of sugar = 342 g/mol
10 𝑋 1000
Molarity of sugar solution = = 342 𝑋 100 =0.292
∆Tf for sugar solution 273.15 -271 = 2.15 ℃
∆Tf = Kf m
Kf =∆Tf /m
=2.15/0.292 =7.363
10 𝑋 1000
Molality of glucose solution = = 180 𝑋 100 =0.555
13
∆Tf = Kf m
∆Tf = 7.363 x0.555 = 4.09 ℃
Freezing point of glucose solution = 273.15 -4.09 = 269 .06 ℃.
5. At 300 K, 36 g glucose present per litre in its solution has osmotic pressure of 4·8 bar. If the osmotic
pressure of the solution is 1·52 bar at the same temperature, what would be its concentration?
Ans: 𝝅 = 𝑪𝑹𝑻
𝑤2 𝑅𝑇
OR 𝝅 = 𝑴𝟐 𝑿 𝑽
36 𝑔 𝑋 𝑅𝑇
In 1 case 4.8 bar = 𝟏𝟖𝟎𝒈 (i)
𝑿𝑽
𝒎𝒐𝒍
𝑤2 𝑅𝑇
In 2 case 1.52 bar = 𝑴𝟐 𝑿 𝑽 (ii)
On dividing eq, (ii) by (i)
1.52 𝑊2
= 𝑴𝟐 X 5 mol
𝟒.𝟖
𝑊2 1.52 1
= 𝑋 =0.3167/5 =0.0633 /mol
𝑴𝟐 𝟒.𝟖 𝟓 𝒎𝒐𝒍
Long Answer Type Question (5 MARKS)
1. a) When 2.56 g of sulphur was dissolved in 100 g of CS2, the freezing point lowered by 0.383 K.
Calculate the formula of sulphur (SX). (Kf for CS2 =3.83K Kg/mol, atomic mass of sulphur = 32 g/mol).
b) blood cells are isotonic with 0.9% sodium chloride solution. What happening if we placed blood cells
in a solution containing (i) 1.2% NaCl solution (ii) 0.4% NaCl solution.
Ans:
𝐊𝐟 𝐗 𝟏𝟎𝟎𝟎 𝑋 𝑤2
a) ∆Tf = 𝑀2 𝑋 𝑤1
𝟑.𝟖𝟑 𝐗 𝟏𝟎𝟎𝟎 𝑋 2.56

0.383 = = 256
𝑀2 𝑋 100
M2 = 256 g/mol
S x X =256
X= 256/32 = 8
So, the formula for sulphur is (S8)
b) (i) shrinks (ii) swells .
2. a) Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN), when 5.5 g of C9H8O4
dissolved in 400g of CH3CN.
b) Commercially available concentrated hydrochloric acid contains 38% HCl by mass and has a density
1.19 g/cm3. What is the molarity of the solution?
Ans:
a)6.5 g of C9H8O4 is dissolved in 450 g of CH3CN,
Total mass of solution = 5.5 +400 = 405.5 g
5.5
Mass % C9H8O4 = 405.5 𝑋 100 = 1.356 %
density of HCl = 1.19g /cm3
14
mass of 1000 cm3 of commercial HCl is =1000x1.19 = 1190 g
1190 𝑋 38
mass of HCl in 1190g (1000cm3) of solution = = 452.2 g
100
molar mass of HCl = 36.5 g/mol
452.5 g HCl = 452.2/36 === 12.4 moles HCl
So 1.0 L of commercial HCl solution contains 12.4 moles of HCl
Molarity of HCl = 12.4 M
PRACTICE QUESTIONS
1. 2.9 g benzoic acid dissolved in 49 g benzene shows a depression in freezing point of 1.62 K. Calculate
the Vant Hoff factor and predict the nature of solute, if its dissociated or associated.
(molar mass of benzoic acid = 122g/mol; Kf for benzene =4.9K Kg /mol) (CBSE 2015)
2. Give reasons: a) RBCs shrink when placed in saline water but swells in distilled water
b) Cooking is faster in pressure cooker rather than a open sauce pan.
c) It is not easy to cook food at high altitudes.
3. Calculate the freezing point of a solution containing 30g of glucose in 250 m L of water. (molar mass
of glucose = 180 g/mol; Kf for water = 1.86 K Kg /mol) (CBSE 2018)
4. Define the following terms: molality, colligative properties; abnormal molar mass and Vant Hoff
factor.
5. What is meant by positive and negative deviations from Raoult’s law and how the sign ΔmixH related
to positive and negative deviation from Raoult’s law.
6. State Raoult’s law for solutions containing volatile components. Write two characteristics of
solution which obeys Raoult’s law at all concentrations. (CBSE
2019)
7. What are the similarities between Raoult’s law and Henry’s law? (CBSE 2020)
8. Give reasons: (CBSE 2019)
a) A decrease in temperature is observed on mixing ethanol in acetone.
b) KCl solution freezes at a lower temperature than water.
9. Calculate the mass percentage of benzene and CCl4, if 23 g benzene dissolved in 122 g of CCl4.
10. State two points of difference between molarity and molality.
ANS KEY
1 B 9 D 17 B 25 A 33 B
2 A 10 A 18 C 26 B 34 D
3 B 11 D 19 D 27 C
4 C 12 B 20 B 28 D
5 B 13 A 21 D 29 D
6 C 14 D 22 A 30 C
7 B 15 D 23 A 31 B
8 C 16 B 24 A 32 B
15
UNIT 2 - ELECTROCHEMISRY
CONTENTS
*SYLLABUS
*GIST OF THE CHAPTER
*IMPORTANT FORMULAS
* MULTIPLE CHOICE QUESTIONS
* CASE BASED QUESTIONS
* FIGURE BASED QUESTIONS
*VSA QUESTIONS
*SA TYPE I (TWO MARKS QUESTIONS)
*SA TYPE II (THREE MARKS QUESTIONS)
* FIVE MARKS QUESTIONS
* UNSOLVED QUESTIONS FOR PRACTICE
* ANSWERS OF MCQ
SYLLABUS
redox reactions, emf of a cell, standard electrode potential, nernst equation and its in electrolytic solutions, specific
and molar conductivity, variations of conductivity application to chemical cells, relation between gibbs energy
change and emf of a cell, conductance with concentration, kohlrausch's law, electrolysis and law of electrolysis
(elementary idea), dry cell-electrolytic cells and galvanic cells, lead accumulator, fuel cells, corrosion.
GIST OF THE CHAPTER
ELECTROCHEMISTRY: Electrochemistry is the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about non-spontaneous chemical
transformations.
GALVANIC CELL: A galvanic cell is an electrochemical cell that converts the chemical energy of a
spontaneous redox reaction into electrical energy
CELL POTENTIAL: The potential difference between the two electrodes of a galvanic cell is called the cell
potential
UNIT: Volt
E cell = E right – E left
ELECTROMOTIVE FORCE (EMF): It is the difference between the electrode potentials (reduction potentials)
of the cathode and anode when no current is drawn through the cell.
16
NERNST EQUATION
M n+(aq) + n e– → M(s)
E (M +n / M) = E0 (M +n / M) – RT ln [M]
nF [M]+n
E (M +n / M) = E0 (M +n / M) – RT ln 1
nF [M]+n
EXAMPLE 1
For an equation:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
By replacing natural logarithm to base 10 and by adding the values of R and F
Nernst equation becomes:
E (cel) = E0 (cell) – O.O591 log [Zn+2]

n [Cu+2]
n=2
E (cel) = E0 (cell) – O.O591 log [Zn+2]

2 [Cu+2]
EXAMPLE 2
For the cell representation given below:
Ni(s)/ Ni2+ (aq) II Ag+ (aq)/Ag
The cell reaction is Ni(s) + 2Ag+ (aq) →Ni2+(aq) + 2Ag(s)
E(cell) = E0cell ) – RT ln [Ni ]+2

2F [Ag+]2
EQUILIBRIUM CONSTANT FROM NERNST EQUATION
E(cell) = E0(cell ) – O.O591 log KC

n
ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION

∆G is the Gibbs energy of the reaction is given by:
Zn(s) + Cu2+(aq) → Zn2+ aq) + Cu(s)
∆G0 = – nFE0(cell)
For n=2
If the concentration of all the reacting species is unity,
Then E(cell) = E0(cell )
∆G 0 = – nFE 0 (cell)
∆G 0 = –RT ln K.
CONDUCTANCE OF ELECTROLYTIC SOLUTIONS
17
CONDUCTANCE: Reciprocal of the resistance
G=1/R
UNITS=Ω -1
SPECIFIC RESISTANCE/RESISTIVITY: ρ= R A /l
Unit is ohm-cm
SPECIFIC CONDUCTANCE OR CONDUCTIVITY:

Conductivity of any conductor is the reciprocal of specific resistance and is denoted by K (Greek work
Kappa) K= 1/ρ = l/ RA
UNIT =S cm-1
MOLAR CONDUCTIVITY: It is defined as the conducting power of all the ions produced by one-gram mol of
an electrolyte in a solution. It is denoted by Λ m
Unit=S cm2mol-1
Λm= Κ X 1000
Molarity
VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION:
For strong electrolytes it decreases slightly with increase in concentration due to increase in number of
ions per unit volume. e.g KCl
For weak electrolytes it increases sharply with decrease in concentration as ionization of weak electrolytes
increases on dilution e.g CH3COOH
KOHLRAUSCH’S LAW: According to this law, molar conductivity of an electrolyte, at infinite dilution can be
expressed as the sum of contributions from its individual ions e.g.
Application of Kohlrausch’s Law
1. for calculation of limiting molar conductivity
2. for calculation of degree of dissociation
3. for calculation of dissociation constant
ELECTROLYTIC CELLS AND ELECTROLYSIS
FARADAY `S FIRST LAW OF ELECTROLYSIS: The amount of substance deposited during electrolysis is
directly proportional to quantity of electricity passed.
W= zIt
18
Z=m
nF
w=m x I x t
nF
FARADAY`S SECOND LAW: The amount of different substances liberated by the same quantity of electricity
passing through the electrolytic solution is proportional to their chemical equivalent weights.
w1 = E1
w2 E2
PRODUCTS OF ELECTROLYSIS
Na Cl (MOLTEN)
Cathode: Na+ (l) + e– → Na(s)

Anode: Cl–→ 1⁄2 Cl2+e–
Na Cl (a q)
Cathode: H2O (l) + e– → 1⁄2 H2(g) + OH–
Anode: Cl–→ 1⁄2Cl2+e–
H2SO4 (dil)
Cathode: H+ + e-→ 1⁄2 H2
Anode: 2H2O (l) → O2 (g) + 4H+ (aq) + 4e–
H2SO4 (conc)
Cathode: H+ + e-→ 1⁄2 H2
Anode: 2SO42– (a q) → S2O82–(aq) + 2e–
AgNO3 (aq)-Ag electrodes

Cathode: Ag+(aq) + e-→ Ag(s)
Anode: Ag(s) → Ag+( aq) + e-
AgNO3 (aq)- Pt electrodes

Cathode: Ag+(aq) + e-→ Ag(s)
Anode: 2H2O (l )→ O2(g) + 4H+( a q) + 4e–
BATTERIES
DRY CELL: Electrolyte used is ZnCl2 and NH4Cl
Anode: - Zinc rod

Zn(s) → Zn2++2e-
Cathode:-Carbon rod surrounded by MnO2

2MnO2 + 2NH4+ + 2e-→Mn2O3 +2NH3
19
Overall Reaction: -
Zn + 2MnO2 + 2NH4+ →Zn2++ Mn2O3 + 2 NH3
Voltage 1.5V
MERCURY CELL Electrolyte used is Paste of KOH &Zn (OH)2

Anode: - zinc-mercury amalgam
Zn (Hg) +2 OH- → Zn O (s) + H2 O +2e-
Cathode: - Hg O and carbon
Hg O+ H2 O+ 2e- → Hg(l) +2 OH-
Overall reaction: - Zn (Hg) + HgO → ZnO + H2
Voltage 1.35V
LEAD STORAGE BATTERY (SECONDARY BATTERY)
Electrolyte used is 38% H2SO4

Anode: - Pb grid
PbSO4 (s) +2 e- → Pb(s) + SO4-2 (aq)
Cathode: -Pb grid filled with PbO2

PbO2(S) + SO4 -2 + 4H+ (aq) +2e-→PbSO4(s) + 2H2O (l)
Overall Cell Reaction: -

Pb(s) +PbO2+2 H2SO4→2 PbSO4(S) +2H2O(l)
It can be recharged by reversing the electrodes. Reactant become products and products become
reactants.
FUEL CELL:
Electrolyte used is KOH solution
Anode: -
2 H2 (g)+ 4OH- →4H2 O +4 e −
Cathode: -
O2 (g) +2H2 O (l) +4 e- →4 OH- (aq)
Overall Reaction: -
2 H 2 (g)+ O2 (g)→2 H2 O (l)

Eco friendly
Efficiency 60-70%
CORROSION
Anode (oxidation): -
2 Fe(s)→ Fe+2(aq)
Cathode (Reduction): -
O2(g)+4 H+( aq)+4 e- → 2H2 O (l )
Atmospheric Oxidation: -
2Fe2+(aq) + 2H2O(l)+1/2O2→Fe2O3(s)+4H+(aq)
Formula of rust
Fe2O3. x H2O
20
PREVENTION OF CORROSION
By covering the surface with paint or by some chemicals (e.g. bisphenol).
Cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the object.
Galvanization.
IMPORTANT FORMULA
Nernst equation
E (M +n / M) = E0 (M +n / M) – RT ln 1
nF [M]+n
Relation between ∆ G0 and KC
∆G 0 = –RT ln KC.
MULTIPLE CHOICE QUESTIONS
1. Which of the following does not belong in the category of electrochemical cells?
a) Voltaic cell
b) Photovoltaic cell
c) Electrolytic cell
d) Fuel Cell
2. Which of the following statements about a lead storage cell (or a lead-acid battery) is false?
a) It is a primary cell
b) The cathode is made up of lead (IV) oxide
c) The anode is made up of lead
d) The electrolyte used is an aqueous solution of sulphuric acid
3. The conductivity of electrolytic conductors is due to __________

a) Flow of free mobile electrons
b) Movement of ions
c) Either movement of electrons or ions
d) Cannot be said
4. The process of transmitting electric current through an electrolyte’s solution to decompose it is known
as __________
a) Electrolyte
b) Electrode
c) Electrolysis
d) Electrochemical cell
5. In a fuel cell, which of the following can be utilized as a fuel?

a) Nitrogen
b) Argon
21
c) Hydrogen
d) Helium
6.Rust is a mixture of
(a) Fe O and Fe (OH)3
(b) Fe O and Fe (OH)2
(c) Fe2O3 and Fe (OH)3
(d) Fe3O4 and Fe (OH)3
7. The difference between the electrode potentials of two electrodes when no current is drawn through
the cell is called ___________.
(i) Cell potential
(ii) Cell emf
(iii) Potential difference
(iv) Cell voltage
8. Which of the following statement is not correct about an inert electrode in a cell?
(i) It does not participate in the cell reaction.

(ii) It provides surface either for oxidation or for reduction reaction.
(iii) It provides surface for conduction of electrons.
(iv) It provides surface for redox reaction.
9. Which of the statements about solutions of electrolytes is not correct?
(i) Conductivity of solution depends upon size of ions.

(ii) Conductivity depends upon viscosity of solution.
(iii) Conductivity does not depend upon solvation of ions present in solution.
(iv) Conductivity of solution increases with temperature.
10.While charging the lead storage battery ______________.

(i) PbSO4 anode is reduced to Pb.
(ii) PbSO4 cathode is reduced to Pb.
(iii) PbSO4 cathode is oxidised to Pb.
(iv) PbSO4 anode is oxidised to PbO2.
22
11. A current of 2.0 A passed for 5 hours through a molten metal salt deposits 22.2 g of metal (at. wt. =
177). The oxidation state of the metal in the metal salt is:
(a) +1
(b) +2
(c) +3
(d) +4
12. An electrochemical cell can behave like an electrolytic cell when ____________.
(i) Ecell = 0
(ii) E cell > E ext
(iii) E ext > E cell
(iv) E cell = E ext
13. The quantity of charge required to obtain one mole of aluminium from Al 2O3 is ___________.
(i) 1F
(ii) 6F
(iii) 3F
(iv) 2F
14. For the given cell, Mg/Mg2+|| Cu2+/Cu

(i) Mg is cathode
(ii) Cu is cathode
(iii) The cell reaction is Mg + Cu2+ → Mg2+ + Cu
(iv) Cu is the oxidizing agent
Assertion and reason type questions

Choose the answers from following options:
a) assertion is correct and reason is false

b) Both assertion and reason are true and the reason is the correct explanation of assertion.
c) Both assertion and reason are true and the reason is not the correct explanation of assertion.
d) Both assertion and reason are false.
15. Assertion: Current stops flowing when E Cell = 0.

Reason: Equilibrium of the cell reaction is attained.
16. Assertion: Ag+ /Ag E increases with increase in concentration of Ag+ ions.
Reason: Ag +/Ag E has a positive value.
17. Assertion: Copper sulphate can be stored in zinc vessel.
Reason: Zinc is less reactive than copper.
18. Match the items of Column I and Column II.
Column I Column II
(i) Lead storage battery (a) maximum efficiency
(ii) Mercury cell (b) prevented by galvanization

23
(iii) Fuel cell (c) gives steady potential
(iv) Rusting (d) Pb is anode, PbO2 is cathode
ANSWER. (i) → (d) (ii) → (c) (iii) → (a) (iv) → (b)

Column I Column II
(i) ∧m (a) S cm–1
(ii) E Cell (b) m–1
(iii) κ (c) S cm2 mol–1
(iv) G* (d) V
ANSWER. (i) → (C) (ii) → (d) (iii) → (a) (iv) → (b)
CASE BASED QUESTIONS

1. Read the given passage and answer the given questions:
Molar conductivity of an electrolyte is the conductance of all the ions produced by 1-gram mole of the
electrolyte in solution and is denoted as ∧m.
Λm= Κ X 1000
C
Here K is the specific conductance while c is the molar concentration of the electrolyte. The molar
conductance of the strong electrolyte at infinite dilution Λ m ∞ can be obtained graphically by
extrapolation while the same for weak electrolytes cannot be obtained graphically. It can be calculated
theoretically with the help of kohlrausch`s law .it can be mathematically represented as
Λ m ∞ (AxBy) = x λ∞m (Ay+) + Y λ∞m ( Bx- ).
1. 48250 C of electricity was required to deposit all the copper present in 0.5 litre of CuSO 4 solution using
inert electrodes. The molarity of solution was (assume volume constant).
a) 0.5 molar
(b) 2.5 molar
(c) 0.25 molar
(d) 1.0 molar
2. Which of the following solutions of K Cl will have the maximum value of specific conductance
a) 1.0 N
(b) 0.1 N
(c) 1.0 X 10-2 N
(d) 0.5 N
24
3. EQUIVALENT conductance of one molar methanoic acid solution is 10 Ω -1 cm2 equiv-1 and at infinite
dilution it is 200 ohm-1cm2 equiv-1. The pH of methanoic acid solution is
a) 7
(b) 3.3
(c) 1.3
(d) 6.8
4. The conductivity of 0.01 M NaCl solution is 0.00147 ohm-1 cm-1. what happens to the conductivity if
extra 100 ml is added to the above solution.
a) remains same
(b) First increase then decrease
(c) Increases
(d) Decreases
ANSWERS: 1. a) 0.5 molar

2. a) 1.0 N
3. (c) 1.3
4. (d) decreases
* FIGURE BASED QUESTIONS

1. Consider the following figure and answer the questions (i) to (vi) given below:
.
(i) Draw the diagram to show the direction of electron flow.
(ii) Is silver plate the anode or cathode?
(iii) What will happen if salt bridge is removed?
(iv) When will the cell stop functioning?
(v) How will concentration of Zn2+ ions and Ag+ ions be affected when the cell functions?
(vi) How will the concentration of Zn2+ ions and Ag+ ions be affected after the cell becomes ‘dead’?
25
ANSWER (i) Electrons move from Zn to Ag.
(ii) Ag is the cathode.
(iii) Cell will stop functioning.
(iv) When E Cell = 0.
(v) Concentration of Zn2+ ions will increase and concentration of Ag+ ions will decrease
(vi) When E cell = 0 equilibrium is reached and concentration of Zn2+ ions and Ag + ions will not change.
*VSA QUESTIONS
1. Why does the conductivity of a solution decreases with dilution.
ANSWER: The conductivity of a solution is the conductance of ions present in a unit volume of the
solution. The number of ions decreases when the solution is diluted. As a result, the conductivity of a
solution decreases with dilution.
2. Suggest two materials other than hydrogen that can be used as fuels in the fuel cells.
ANSWER: Methane and methanol can be used as fuels in fuel cells
3. Express the relation among the cell constant the resistance of the solution in the cell and the
conductivity.
ANSWER: K= 1/R X (L/A)
4. Write the expression for the molar conductivity if acetic acid at infinite dilution according to Kohlraush`s
law.
ANSWER: Λ∞ (CH3COOH) = λ∞ H+ + λ∞ CH3COO –
5. Name the type of fuel which was used in Apollo space program for providing electrical power.
ANSWER: H2-O2 fuel cell.
6. What is the name of the cell which is generally used in inverters?
ANSWER: LEAD STORAGE BATTERY
7. What is a primary cell?
ANSWER: A primary cell is an electrochemical cell which cannot be reached.
8. What will happen to the value of emf of the following cell if the concentration of the electrolyte in the
anode compartment increases?
Zn/Zn+2 (0.1 M) II Cu+2 (0.1 M)/Cu
ANSWER: if the concentration of Zn+2 is increased, emf of the cell will decrease.
9. Write the overall reaction occurring in dry cell.
ANSWER: Zn (s) + 2NH4+ (aq) + 2 Mn O2 (s) → Zn+2 (aq) + Mn2O3(s) + 2 NH3 ( aq) + H2O(l)
26
10. Which has greater Λ mc value: 0.1 K Cl or 0.01 M KCl solution?
ANSWER: 0.01 M K Cl solution because molar conductivity increases upon dilution
*SA TYPE I (TWO MARKS QUESTIONS)

1. Λ m ° for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol –1 respectively. Calculate Λ o for HAc.
ANSWER: Λm0 (H Ac) = λO H+ + λOAc- = λO H+ + λO Cl- + λOAc- + λONa+ - λO Cl- - λONa+
= (425.9 + 91.0 – 126.4) S cm2 mol –1 = 390.5 S cm2 mol–1
2. A solution of CuSO4 is electrolyzed for 10 minutes with a current of 1.5 amperes. What is the mass of
copper deposited at the cathode?
ANSWER: t = 600 s
Charge = current × time = 1.5 A × 600 s = 900 C
According to the reaction: Cu2+ (a q) + 2e– →Cu(s)
We require 2F or 2 × 96487 C to deposit 1 mol or 63 g of Cu.
For 900 C, the mass of Cu deposited = (63 g mol–1 × 900 C) / (2 × 96487 C mol–1) = 0.2938 g.
3. Write the difference between EMF and potential difference.

ANSWER:
EMF POTENTIAL DIFFERENCE

1. It is the difference in the electrode potentials It is the difference in the electrode potentials when
when no current flows through the cell. current is flowing through the cell.
2. It is the maximum voltage which can be It is less than the maximum voltage which can be
obtained from the cell. obtained from the cell
3.it is responsible for the flow of steady current it is not responsible for the flow of steady current
4. it can be measured by a potentiometer it can be measured by a potentiometer
4. Why are fuel cells regarded better than both primary and secondary batteries?
ANSWER: fuel cells work continuously as long as fuel is supplied. These do not cause any air pollution
problems like primary and secondary batteries.
27
5. Solutions of two electrolytes A and B are diluted. The limiting molar conductivity of B increases to a
smaller extent while that of A increases to a much larger extent comparatively. Which of two is a strong
electrolyte. justify your answer.
ANSWER: upon dilution limiting molar conductivity increases only to small extent for strong electrolytes
and to a large extent for weak electrolytes. Therefore, B is strong electrolyte and A is weak in nature.
6. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 Scm-1. Calculate its molar conductivity.
ANSWER:
Conductivity = 0.0248 S cm-1 = 0.0248 ohm-1 cm-1
Molar concentration = 0.20 M= 0.2 mol /l= 0.2 mol / 1000 cm3 = 2.0 x 10-4 mol cm-3
Molar conductivity = K/C= 0.0248 ohm-1 cm-1/ 2.0x 10-4 mol cm-3
= 124 ohm-1 mol-1cm2
=124 Smol-1 cm2
7. Calculate the equilibrium constant of the reaction:
Cu(s) + 2Ag+ (aq) → Cu2+ (aq) + 2Ag(s)
E0 cell = 0.46 V
ANSWER: E0 cell = (0 .059 /2) x log KC = 0.46 V
log KC = 0 .46 x2/ 0. 059 = 15.6
KC = 3.92 × 1015
8) The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the
reaction:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
ANSWER: ∆G 0 = – nFE 0 (cell) n = 2,
F = 96487 C mol –1
E0 cell = 1.1 V
Therefore, ∆G 0 = – 2 × 1.1V × 96487 C mol –1 = – 21227 J mol–1 = – 212.27 kJ mol–1
9) Write the chemistry of recharging the lead storage battery highlighting all the materials that are
involved during recharging.
ANSWER: A lead storage battery consists of a lead anode, a grid of lead packed with lead oxide (PbO2) as
the cathode, and a 38% solution of sulphuric acid (H2SO4) as an electrolyte.
During recharging:
2PbSO4+2H2O→Pb(s) +PbO2+4H++2SO42−
10) a) In a cell reaction , the equilibrium constant K is less than one. Is E0 for the cell positive or negative?
b) What will be the value of K if E0CELL = 0?
28
ANSWER: a) For a cell E0 =0.0591/n (log K)
Let the value of K be less than one
E0 = 0.0591/n (log 0.01)
0.0591/n (log 10-2) = - ve
b) If E0 cell= 0 then 0= 0.0591/n (log K)
Log K =0
K = antilog (0) =1
SA TYPE II (THREE MARKS QUESTIONS)
1. In the button cells widely used in watches and other devices the following reaction takes place:
Zn(s)+Ag2O(s)+H2O(l)→Zn2+(aq)+2Ag(s)+2OH−(aq)
Determine ΔGθ and Eθ for the reaction.
ANSWER: Given: E0 Ag+/Ag=+0.80 V, E0 Zn+2/Zn=-0.76 v
E0cell=E0cathode−E0anode= 0.80 − (−0.76)=1.56 V
ΔG0=−nFE0cell=−2×96500×1.56 =− 301080 J /mol =−301.08 kJ/mol
2. Calculate the emf of the cell in which following reaction takes place:
Ni (s) +2Ag+ (0.002 m) →Ni+2 (0.160 M) + 2 Ag(s)
Given: E0CELL =1.05 V
ANSWER: E (cell) = E0(cell ) – RT ln [Ni ]+2
2F [Ag+]2
E(cell) = E0(cell ) – 0.0591 log [Ni +2]

2 [Ag+]2
= 1.05 – 0.0591 log 0.16

2 (0.002)2
= 1.05 - 0.02955 log 4 × 104
= 1.05 - 0.02955 (log 10000 + log 4)
= 1.05 - 0.02955 (4 + 0.6021)
= 0.914 V
29
3. a) How would you determine the standard electrode potential of the system Mg2+/Mg?
b) Can you store copper sulphate solutions in a zinc pot?
Answer: a) To determine the standard electrode potential of the system Mg2+/Mg, connect it to the
standard hydrogen electrode (SHE). Keep the Mg2+/Mg system as cathode and SHE as anode
The standard electrode potential of Mg2+|Mg can be measured with respect to the standard hydrogen
electrode, represented by H+(aq,1 M)|Pt(s)|H2(g),1 bar.
Mg+2/ Mg (aq,1 M)||H+(aq,1 M)|Pt(s)|H2(g),1 bar
b) Zinc is more reactive than copper, so, zinc can displace copper from its salt solution.
Hence, the solution of copper sulphate cannot be stored in a zinc pot.
The reaction occurs is:
Zn+CuSO4→ZnSO4+Cu
4. a) Depict the galvanic cell in which the cell reaction is Cu + 2Ag+ → 2Ag + Cu2+
b) Consider a cell given below Cu|Cu2+|| Cl— |Cl2 ,Pt
Write the reactions that occur at anode and cathode
Answer: a) Cu|Cu2+|| Ag+|Ag
b) Anode: Cu → Cu2+ + 2e–
Cathode: Cl2 + 2e– → 2Cl–
Cu is anode as it is getting oxidized.
Cl2 is cathode as it is getting reduced.
5. Depict the galvanic cell in which the reaction

Zn(s) + 2Ag+ (aq) →Zn2+(aq) + 2Ag(s) takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
ANSWER: the galvanic cell in which the given reaction takes place is depicted as:
Zn)| Zn (aq) 2+||Ag (aq)+|Ag(s)
(i) The negatively charged electrode is the Zn electrode (anode).
(ii) The current carriers in the cell are ions. Current flows to zinc from silver in the external circuit.
(iii) Reaction at the anode is given by
Zn(s) →Zn (aq) 2+ +2e−
30
Reaction at the cathode is given by
Ag+ + e- → Ag
6.If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would flow
through the wire?
I = 0.5 A
t = 2 hours = 2 × 60 × 60 s = 7200 s
Thus, Q = It
= 0.5 A × 7200 s
= 3600 C
We know that 96487 C = 6.022 x 1023 number of electrons.

3600 C=6.022 x 1023 X 3600 /96487= 2.25X 1022 number of electrons
7. Calculate the equilibrium constant of the reaction: Cu(s) + 2Ag+ (aq) → Cu2+(aq) + 2Ag(s)
EOCELL = 0.46 V
ANSWER:
EOCELL = 0 059/ 2 log KC = 0.46 V
log KC = 15.6
KC= 3.92 × 1015
FIVE MARKS QUESTIONS
1. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation
with concentration.
ANSWER: Conductivity: The conductivity of a solution is defined as the conductance of a solution of 1 cm in

length and area of cross-section 1 sq. cm.
Specific conductance is the inverse of resistivity, and it is represented by the symbol κ. If ρ is resistivity,
then we can write K=1/ ρ
At any given concentration, the conductivity of a solution is defined as the unit volume of solution kept
between two platinum electrodes with the unit area of the cross-section at a distance of unit length.
31
Variation with concentration: When concentration decreases, there will be a decrease in Conductivity. It is
applicable for both weak and strong electrolytes. This is because the number of ions per unit volume that
carry the current in a solution decreases with a decrease in concentration.
Molar conductivity:
The molar conductivity of a solution at a given concentration is the conductance of volume V of a solution
containing 1 mole of the electrolyte, kept between two electrodes with the area of cross-section A and
distance of unit length.
Λm = K (A / l )
Now, l = 1 and A = V (volume containing 1 mole of the electrolyte)
Λm = K V
Variation with concentration: Molar conductivity increases with a decrease in concentration. This is
because the total volume V of the solution containing one mole of the electrolyte increases on dilution.
2. a) The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω. What is the cell
constant if the conductivity of 0.001M KCl solution at 298 K is 0.146 × 10 –3 S cm–1
b) How much charge is required for the following reductions?
1 mol of Al3+ to Al.
ANSWER: a) Given, Conductivity, k = 0.146 × 10−3 S cm−1
Resistance, R = 1500 Ω
Cell constant = k × R
= 0.146 × 10−3 × 1500
= 0.219 cm−1
b) Required charge = 3 F
= 3 × 96487 C
= 289461 C
3. Predict the products of electrolysis in each of the following.

(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution of AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes
Answer: (i) An aqueous solution of AgNO3 with silver electrodes
32
Cathode: the deposition of silver
Anode: silver electrode at the anode dissolves in the solution to form Ag+.
(ii) An aqueous solution of AgNO3 with platinum electrodes
Cathode: the deposition of silver
Anode: OH− ions have a lower discharge potential and get preference and decompose to liberate O2.
(iii) A dilute solution of H2SO4 with platinum electrodes

Cathode: H2 gas.
Anode: O2 gas
(iv) An aqueous solution of CuCl2 with platinum electrodes
Cathode: the deposition of copper will take place at the cathode.
Anode: Cl2 gas
* UNSOLVED QUESTIONS FOR PRACTICE

1. How much electricity in terms of Coulomb is required to reduce 1 mol of Cr2O72-to Cr3+.
2. What is Fuel Cell?
3. A solution of CuSO4 is electrolyzed using a current of 1.5 amperes for 10 minutes. What mass of Cu is
deposited at the cathode? (Atomic mass of Cu=63.7)
4. Calculate the equilibrium constant for the reaction Cu (s) + 2Ag+ →Cu +2 + 2Ag(s)
EoCu2+ /Cu = +0.34V, Eo Ag+/Ag = + 0.80V.
5. Write the Nernst equation and emf of the following cells at 298K:
Sn/Sn2+(0.050M)//H+(0.020M)/H2(g)/Pt(s)
Eo Sn 2+ /Sn= - 0.13V
6. Calculate the standard free energy change for the following reaction at 250C,
Au(s) +Ca+2 (1 M)→Au3+(1M) + Ca (s) ,
The electrode values are Ca2+ /Ca = –2.87V,Au3+ / Au = +1.50V.
Predict whether the reaction will be spontaneous or not at 250C.
7. How do you account for conductivity of strong and weak electrolyte with concentration? Plot the graphs
also.
8. State Kohlrausch’s law. Calculate Limiting molar conductivity of NaCl, HCl and NaAc are 126.4, 425.9 &91
SCm2 mol-1. Calculate Limiting molar conductivity of HAc.
33
9. Resistance of conductivity cell filled with 0.1molL-1 KCl solution is 100 ohm. If the resistance of the same
cell when filled with 0.02molL-1 KCl solution is 520 ohm. Calculate the conductivity & molar conductivity of
0.02mol L-1 KCl solution. The conductivity of 0.1 molL-1 solution of KCl is 1.29Sm-1.
10. A Copper – silver cell is set up. The copper ion concentration in it is 0.10 M.The concentration of silver
is not known. The cell potential measured 0.422 V. Determine the concentration of silver ion in the cell.
Eo Ag+/Ag = +0.80V, Eo Cu2+/Cu = +0.34V.
11.A voltaic cell is set up at 250C with the following half cells: Al(s)/Al3+ (0.001M) and Ni2+ (0.50)/Ni(s), Write
the equation for the cell reaction that occurs when the cell generates an electric current and determine
the cell potential (given EoNi2+ /Ni = -0.25V, Eo Al(s)/Al3+ =-1.66V)
12. Write the reaction involved in the following cells: (a) Fuel Cell (b) Lead Storage Battery.
13. Three electrolytic cells A, B, C containing solutions ZnSO4, AgNO3, and CuSO4respectively are connected
in series. a Steady current of 1.5 amperes was respectively are connected in series. A steady current of 1.5
amperes was passed through them until 1.45g of silver deposited at the cathode of cell B. How long did the
current flow? What mass of copper and zinc were deposited?
14. Conductivity of 0.00241M acetic acid is 7.896 X 10- S cm-1. Calculate its molar conductivity. If Λ0 for
acetic acid is 390.5 S cm2 mol-1. What is its dissociation constant?
15. (a) Two half-cell reactions of an electrochemical cell are given below:
MnO -4 + 8 H++ 5 e-→Mn2+ + 4H2O Eo =+1.51V
Sn2+ → Sn4+ + 2e- Eo = +0. 15V.Construct the redox reaction from the two-half-cell reaction and predict if
the reaction favors formation of reactants or product shown in the reaction.
(b). How much electricity in terms of Faraday is required to produce
(i) 20g of Ca from molten CaCl2
(ii) 40g of Al from molten AlCl3
* ANSWERS OF MCQ
1. Answer: b) Photovoltaic cell
2. Answer: a) It is a primary cell
3. Answer: b) Movement of ions
4. Answer: c) Electrolysis
5. ANSWER: c) Hydrogen
6. Answer: (c) Fe2O3 and Fe (OH) 3
7.ANSWER (ii) Cell emf
8. ANSWER (iv) It provides surface for redox reaction
9. ANSWER (iii) Conductivity does not depend upon solvation of ions present in solution.
10. ANSWER (i) PbSO4 anode is reduced to Pb
34
11. ANSWER: (c) +3
12. ANSWER (iii) E ext > E cell
13. ANSWER (iii) 3F
14. ANSWER: both (ii) and (iii)
(ii)Cu is cathode (iii) the cell reaction is Mg + Cu2+ → Mg2+ + Cu
15. ANSWER: Both assertion and reason are true and the reason is the correct explanation of assertion.
16. ANSWER: Both assertion and reason are true and the reason is not the correct explanation of assertion.
17. ANSWER: Both assertion and reason are false.
ANSWER. (i) → (d) (ii) → (c) (iii) → (a) (iv) → (b)
ANSWER. (i) → (C) (ii) → (d) (iii) → (a) (iv) → (b)
35
UNIT 3 - CHEMICAL KINETICS
Syllabus: Rate of a reaction (Average and instantaneous), factors affecting rate of reaction:
concentration, temperature, catalyst; order and molecularity of a reaction, rate law and
specific rate constant, integrated rate equations and half-life (only for zero and first order
reactions), concept of collision theory (elementary idea, no mathematical treatment),
activation energy, Arrhenius equation.
GIST OF THE LESSON
Rate of reaction, Average rate of reaction, Instantaneous rate of reaction
Units of rate of reaction, Rate law expression, Order of reaction, Molecularity of a
reaction, Rate constant and units of rate constant, Half-life of a reaction
Pseudo first order reaction, Factor effecting rate of reaction (temperature,
concentration and catalyst), Activation energy, Collosion theory.
MASTER CARD
RATE OF REACTION = -∆[R]/ ∆t = +∆[P]/ ∆t
INSTANTANEOUS RATE OF REACTION (rinst ) = -d[R]/dt = + d[P]/dt

RATE LAW EQUATION FOR REACTION
Aa +bB ------→ cC + dD
RATE = K [A]x[B]Y
Order of Units of K
reaction
0 mol L-1s-1
1 s-1
2 mol-1 L s-1
Order of Integrated rate half-life of a reaction

reaction equation
0 K= [R]0- [R]/t t ½ = 0.693/k
2.303
1 K= log [R] 0 /[R] t ½ = [R] 0 /2k
𝑡
Arrhenius equation k = A e-Ea/RT

Log k= logA - Ea/2.303RT
𝑘2 𝐸𝑎 𝑇2− 𝑇1
Log = [ ]
𝑘1 2.303 𝑇1𝑇2
Collision theory A +B ---→ AB
Rate = PZAB e-Ea/RT
36
One Mark Question
1. For several reactions an increase in temperature from 300 K to 310 increase the
rate increase approximately by
a. 3.3 %
b. 100 %
c. 10 %
d. 1000%
2. Fraction of molecules with energy equal to or greater than activation energy is equal to
a. Ea/RT
b. e-Ea/RT
c. Ea/2.303RT
d. –Ea/2.303RT
3. Collision theory assumes that the rate of a reaction depends on _______.
a. the energy of collisions.
b. the orientation of colliding molecules.
c. the energy of collisions and the orientation of colliding molecules.
d. the change in energy between the products and the reactants.
4. Which among the following is a false statement?
(a) Rate of zero order reaction is independent of initial concentration of reactant.
(b) Half-life of a third order reaction is inversely proportional to square of initial
concentration of the reactant.
(c) Molecularity of a reaction may be zero or fraction.
[𝑅]1 𝑘(𝑡2−𝑡1)
(d) For a first order reaction log =
[𝑅]2 2.303
5. Which of the following statements about the catalyst is true?

(a) A catalyst accelerates the rate of reaction by bringing down the activation energy.
(b) A catalyst does not participate in reaction mechanism.
(c) A catalyst makes the reaction feasible by making ∆G more negative.
(d) A catalyst makes equilibrium constant more favourable for forward reaction
6. The half-life of the first order reaction having rate constant K = 1.7 x 10-5s-1 is
(a) 12.1 h
(b) 9.7 h
(c) 11.3 h
(d) 1.8 h
7 The reaction of high molecularity is rare because
(a) Many body collisions have a low probability.
37
(b) Many body collisions are not favored energetically.
(c) Activation energy of many body collisions is very large
(d) Very high concentration is required for such reactions
8 The half-life period of any first order reaction
(a) is half the specific rate constant
(b) is always the same irrespective of the reaction
(c) is independent of initial concentration
(d) in directly proportional to initial concentration of reactants.
9 The unit of rate constant for the reaction
2H2 +2NO ---→ 2H2O + N2
Which has rate = k [H2][NO]2 is
(a) Mol L-1 s-1
(b) S-1
(c) Mol-2 L2 S-1
(d) Mol L-1
10. The order is decided by
(a) Temperature
(b). Mechanism of the reaction as well as concentration of reactants
(c ) Molecularity
(d)Pressure
11. The half-lives of two samples are 0.1 and 0.4 second. Their respective concentrations
are 200 and 50 respectively. What is the order of the reaction?
(a) 0
(b) 2
(c) 1
(d) 4
12 In a zero-order reaction, for every 10°C rise of
temperature, the rate is doubled. If the temperature is increased from 10∘C to 100∘C, the
rate of the
reaction will become
(a) 256 times
(b) 512 times
(c) 64 times
(d) 128 times
13. Which of the following observations is incorrect about the order of a reaction?
(a) Order of a reaction is always a whole number.
(b) The stoichiometric coefficient of the reactants doesn’t affect the order.
38
(c) Order of reaction is the sum of power to express the rate of reaction to the
concentration terms of the reactants.
(d) Order can only be assessed experimentally
14 A zero order reaction X --→Product; with an initial concentration 0.02M has a half-life of
10 min.
If one starts with concentration 0.04M, then the half-life is
a) 10 s
b) 5 min
c) 20 min
d) Cannot be predicted using the given information
15. In a reaction, when the concentration of reactant is increased two times, the increase in
rate of reaction was four times. Order of reaction is:
(a) Zero (b) 1 (c) 2 (d) 3
Read the statements given as assertion & reason both and choose the correct option as
per the following instructions.
(a) If both assertion & reason are correct statements and reason is the correct explanation
of assertion.
(b) If both assertion & reason are correct statements and reason is not the correct
explanation of assertion.
(c) If the assertion is the correct statement & the reason is an incorrect statement.
(d) If the assertion is incorrect statement and reason is the correct statement.
16. Assertion: The order of reaction can be zero or fractional.
Reason: The order of a reaction cannot be determined from a balanced chemical reaction.
17. Assertion: The order and molecularity of a reaction are always the same.
Reason: Order is determined experimentally whereas molecularity by a balanced elementary
reaction.
18. Assertion: Rate constant of a zero-order reaction has the same unit as the rate of a
reaction.
Reason: Rate constant of a zero-order reaction does not depend upon the concentration of
the reactant.
19. Assertion: In a first-order reaction, the concentration of the reactant is doubled; its half-
life is also doubled.
Reason: The half-life of a reaction does not depend upon the initial concentration of the
reactant in a first Order reaction.
39
20. Assertion: Average rate and instantaneous rate of a reaction have the same unit.
Reason: Average rate becomes an instantaneous rate when the time interval is too small.
ANSWERS MCQ
1 (b) 2 (b) 3 (c) 4 (c) 5 (a) 6 (c) 7 (a) 8 (c) 9 (c) 10 (b)
11 (b) 12 (b) 13 (a) 14(c) 15 (c) 16 (b) 17 (d) 18 (a) 19(d) 20(b)
Very Short answered questions (1 Marks)

Q1 what are the units of rate constant for first order reaction?
Ans: time-1
Q2 Give two important factors which affect the rate of reaction.
Ans (a) Concentration (b) Temperature
Q3 What is half-life period of a reaction?
Ans Time in which 50% reactants changed into products
Q4. Write Arrhenius equation.
Ans K = A e-Ea/RT
Q5. What is the rate determing step in a complex reaction?
Ans the slowest step in the reaction.
Short answered questions (2 Marks)
Q1 Define the following terms:
(a) Pseudo first order reaction.
(b) Half-life period of reaction (t1/2).
Answer:
(a) Those reactions which are not truly of the first order but under certain conditions
become first order reactions are called pseudo first order reaction.
(b) The time taken for half of the reaction to complete is called half-life period.
Q2 (a) For a reaction, A + B → Product, the rate law is given by, Rate = k[A]1[B]2. What is the
order of the reaction?
(b) Write the unit of rate constant ‘k’ for the first order reaction.
Answer:
(a) For a reaction, A + B----→ Product
Rate = k [A]1 [B]2
This is the third order of reaction.
(b) Unit of rate constant for first order reaction is sec-1
Q3 a reaction is of second order with respect to its reactant. How will its reaction rate be
affected if the concentration of the reactant is (i) doubled (ii) reduced to half?
Answer:
40
Since Rate = K[A]2
For second order reaction Let [A] = a then Rate = Ka2
(i) If [A] = 2a then Rate = K (2a)2 = 4 Ka2
∴Rate of reaction becomes 4 times
𝑎
(ii) If [A] = then Rate = K (a/2)2=k a2/4
2
∴ Rate of reaction will be 1/4 th .
Q4(a) Explain why H2(g) and O2(g) do not react at room temperature.
(b) Write the rate equation for the reaction A2 + 3B2 → 2C, if the overall order of the
reaction is zero.
Ans (a) H2(g) and O2(g) do not react at room temperature because they do not have enough
activation energy to overcome the exceptionally high activation energy barrier.
(b) A2 + 3B2 → 2C
𝑑𝑥
Rate = ( ) = K[A]0 [B]0 = K (rate constant)
𝑑𝑡
Q5. For the reaction in a closed vessel:

2NO (g) + O2(g) →2NO2(g); Rate = k [NO]2 [O2]
If the volume of the reaction vessel is doubled, how would it affect the rate of the
reaction?
Ans If volume is doubled conc. of each reactant will be halved so diminish to 1/8
volume of initial value
Short answered questions (3 Marks)

Q1 the reaction between A and B is first order with respect to A and zero order with respect
to B. Fill in the blanks in the following table:
Experiment [A]/mol L-1 [B]/mol L-1 Intial rate /mol L-1

min-1
I 0.1 0.1 2.0 x 10-2
II ----- 0.2 4.0 x 10-2
III 0.4 0.4 ------
IV ----- 0.2 2.0 x 10-2
Ans Rate expression will be

Rate = k [A]1{B]0 = k [A]
Exp I 2.0 x 10-2 = k [A] = k (0.1)
K = 2.0 x 10-2/0.1 =0.2 min-1
41
Exp II 4.0 x 10-2= k [A] = 0.2 [A]
[A] = 4.0 x 10-2/0.2 = 0.2 mol L-1
Exp III Rate = k [A]= 0.2 x 0.4 = 0.08 mol L-1 min-1
Exp IV 2.0 x 10-2 = 0.2 [A]
[A] = 2.0 x 10-2/0.2 = 0.1 mol L-1
Q2 The initial concentration of N2O5 in the following first order reaction N2O5(g) → 2 NO2(g)
+ 1/2O2 (g) was 1.24 × 10–2 mol L–1 at 318 K. The concentration of N2O5 after 60 minutes was
0.20 × 10–2 mol L–1. Calculate the rate constant of the reaction at 318 K.
Ans For a first order reaction
[𝑅]1 𝑘(𝑡2−𝑡1)
log =
[𝑅]2 2.303
2.303 [𝑅]1
k= log [𝑅]2
(𝑡2−𝑡1)
2.303
= log 1.24 × 10–2/0.20 × 10–2
(60−0)
2.303
= log 6.2 min–1
60
K = 0.0304 min–1
Q3 Match the statement in column I and column II
Column I Column II
a Catalyst alter the rate of p Cannot be fraction or zero
reaction
b molecularity q Proper orientation is not there
always
c 2nd half-life of first order r By lowering the Ea energy
reaction
d e-Ea/RT s Is same as the first
e Energetically favorable t Total probability is one
reactions are sometimes slow
f Area under Maxwell Boltzmann u Fraction of molecules with
curve is constant energy equal or greater than Ea
Ans (a—r), (b—P), (c—s), (d—u), (e—q), (f—t)

Q4 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact
containing wood had only 80% of the 14C found in a living tree. Estimate the age of the
sample.
Ans Radioactive decay follows first order reaction.
0.693
K = 0.693/t1/2= years-1
5730
2.303 [𝑅]0
t= log
𝑘 [𝑅]
2.303×5730 100
= log
0.693 80
42
2.303×5730
= log 1.25
0.693
2.303×5730
= × 0.0969
0.693
1845.18 years
Q5 For a general reaction R--→ P
Plot of concentration of R vs time is given
Answer the following questions on the basis of graph.

(i) What is the order of reaction?
(ii) What is the slope of the curve?
(iii) What are the units of rate constant?
Ans. (i)the order of reaction is zero
(ii) the slope of the curve = -k
(iii)the units of rate constant = mol L-1 s-1
CASE STUDY BASED QUESTIONS

1. Thermal decomposition of ammonia takes place as follows:
2NH3(g) ------→ N2(g) +3H2 (g)
Rate of formation of N2(g) is 2.4 X 10 -3 mol L-1 sec-1
𝑑[NH3]
− = k1[NH3]
𝑑𝑡
𝑑[N2]
+ = k2[NH3]
𝑑𝑡
𝑑[H2]
= k3[NH3]
𝑑𝑡
Read the passage and answer the following questions:

(a) Write down the expression for instantaneous rate of reaction
1 𝑑[𝑁𝐻3] 𝑑[N2] 1 𝑑[𝐻2]
Ans: - = + = = instantaneous rate of reaction
2 𝑑𝑡 𝑑𝑡 3 𝑑𝑡
(b) Give relation between k1, k2 and k3.
43
Ans: 2NH3(g) ------→ N2(g) +3H2 (g)
1 𝑑[𝑁𝐻3] 𝑑[N2] 1 𝑑[𝐻2]
- = + =
2 𝑑𝑡 𝑑𝑡 3 𝑑𝑡
1 1
k1 [NH3] = k2[NH3] = k3 [NH3]
2 3
3
k1 = 3 k2 = k3
2
𝑑[NH3]
(c) Give rate of decomposition of NH3(g) i; e −
𝑑𝑡
1 𝑑[𝑁𝐻3] 𝑑[N2]
Ans: - = + = 2.4 x 10-3
2 𝑑𝑡 𝑑𝑡
𝑑[𝑁𝐻3]
- = 4.8 x 10-3 mol L-1 sec-1
𝑑𝑡
+ 𝑑[H2]
(d) Give rate of formation of H2 (g) I;e
𝑑𝑡
𝑑[N2] 1 𝑑[𝐻2]
Ans: =
𝑑𝑡 3 𝑑𝑡
𝑑[𝐻2]
= 3 x 2.4 x 10-3
𝑑𝑡
= 7.2 x 10-3 mol L-1 sec-1
(e) What will be the instantaneous rate of reaction?

𝑑[N2]
Ans = 2.4 X 10 -3 mol L-1 sec-1
𝑑𝑡
2. Chemical kinetics deals with rate of chemical reactions, how fast reactants get used up or
how fast products are formed in the reaction. Differed chemical reactions have different
speed. Rate of reaction depends upon concentration of reactants, temperature, pressure
especially in gaseous reactions and presence of catalyst. Chemical reaction takes place as a
result of collision between reacting molecules. The rate of reaction does not depend upon
total number of collisions rather it depends upon number of effective collisions. In a redox
reaction, if E°cell is +ve, ∆G° will be –ve and ‘K’ equilibrium constant will be high i.e. products
formed will be more than the reactants.
(a)k (The rate constant), (Activation Energy) Ea and ‘A’ (Arrhenius constant) are 3 × 10–4
s–1, 104.4 kJ mol–1 and 6.0 × 1014 s–1 respectively. What is value of ‘k’ when T → ∞?
Ans. Arrhenius constant k = Ae–Ea/RT ⇒ k = Ae–Ea/∞ = Ae° = A = 6.0 × 1014 s–1
(b) What is meant by activation energy?
Ans. The extra energy which must be supplied to reactants in order to undergo
effective collision to form products.
(c) What does e–Ea/RT represent?
Ans. It represents fraction of molecules possessing activation energy (Ea) or more than
Ea.
(e) If Fe3+ + 2I– --→ Fe2+ + I2 has E° = 0.24V, what is the value of log K? What does value
of ‘K’ indicate?
44
𝑛𝐸0
Ans. log K = = 2 × 0.24V/0.0591 = 8.122 The value indicates that products are
0.0591
formed 108, times than reactants.
(d)What type of molecules undergoes effective collisions?

Ans. Those molecules which possess activation energy and collide in proper
orientation undergo effective collisions.
Long Answer Questions:

Q1. (a) Distinguish between order of a reaction and molecularity of a reaction.
(b) The rate of reaction increases four times when temperature changes from 300K to 320K
calculate the activation energy of reaction (R=8.314J K-1 mol-1 )
Ans (a) Order of a Reaction - 1. It is the sum of power of conc. Of reaction in the rate law
equation.
2. It can be zero or in fraction
Molecularity of a reaction - 1. It is the total no. of atoms, ions or molecules of the
reactants involved in the reaction.
2. It is always in whole no., cannot be zero and never more than 3.
𝑘2 𝐸𝑎 1 1
Ans (b) Log = ( - )
𝑘1 2.303𝑅 𝑇1 𝑇2
𝐸𝑎 1 1
Log 4 = ( − 320)
2.303 × 8.314 300
𝐸𝑎 320−300
2log2 = (
2.303 × 8.314 300×320
)
𝐸𝑎 20
2 × 0.301 = ×
2.303 × 8.314 300 × 320
2 × 0.301 × 2.301 × 8.314 × 300 × 320

𝐸𝑎 =
20
Ea = 55.336 KJ / mol
Q2. (a) For a reaction A + B-----→ P , the rate is given

Rate = K[A] [B]2
1. How is the rate of reaction effected if the Conc. Of B is doubled.
2. What is the overall order of reaction if a is present in large excess.
(b) A first order reaction takes 30 min for 50% completion. calculate the time required for
90% completion of this reaction.
45
[Log 2 = 0.301]
Ans. 1 R1 = K [A] [B]2
R2 = K [A] [2B]2 = 4K [A] [B]2
So, rate increasing 4 times.
2. When A is present in large amount, order with respect to A is zero.

Order = 0+2 = 2
(b) t1/2 = 30 min

0.693
t1/2 = min-1
30
K = 0.0231 min-1
2.303
𝑡1/2 = log[𝑅]0 /[𝑅]
0.0231
2.303 100
𝑡1/2 = log
0.0231 10
2.303
𝑡1/2 = min-1
0.0231
−1
𝑡1/2 = 99.7 𝑚𝑖𝑛
PREVIOUS YEARS QUESTIONS
1. Which of the following is affected by catalyst?

(a) ∆H (b)∆ G (c) Ea (d)∆ S
Ans (c)
ℎ𝑣
2. The order of the reaction H2 (g) + Cl2 (g) >2HCl (g) is
(a) 2 (b) 1 (c) 0 (d) 3
Ans (c)
3.A first order reaction takes 30 minutes for 50% completion. The value of rate constant k
would be:
(a) 2.5 × 10-3 min-1 (b) 2.75× 10-4 min-1 (c) 1.25×10-3 min-1 (d) 2.31× 10-2 min-1
Ans (d)
4. In the given reaction
A + 3 B -----→ 2C
The rate of formation of C is 2.5 × 10-4 mol L-1 s-1. Calculate the
46
(i)Rate of reaction
(ii) Rate of disappearance of B.
Ans: The rate of formation of C is 2.5 × 10-4 mol L-1 s-1
𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶]
Rate = - =- =
𝑑𝑡 3 𝑑𝑡 2 𝑑𝑡
1
(I ) Rate of reaction = ×2.5× 10-4 = 1.25× 10-4 mol L-1 s-1
2
1 𝑑[𝐵] 1 𝑑[𝐶]
(ii) Rate of disappearance of B = - =
3 𝑑𝑡 2 𝑑𝑡
1 𝑑[𝐵] 3
- = ×2.5× 10-4= 3.75× 10-4 mol L-1 s-1
3 𝑑𝑡 2
Q5 Answer the following questions:

(a) Identify the order of reaction from the unit of rate constant L mol-1 s-1
Ans the order of reaction=2
(b) The conversion of molecule A to B follows second order kinetics. If conc. Of A is
increased to three times, How will it affect the rate of formation of B ?
Ans. A--→ B
𝑑[𝐴] 𝑑[𝐵]
- = = Rate
𝑑𝑡 𝑑𝑡
𝑑[𝐴]
- = Rate of consumption of A
𝑑𝑡
𝑑[𝐵]
= Rate of formation of B
𝑑𝑡
Since given conversion follows second order
Rate = k[A]2
If conc. Of A is 3 times
Rate = k[3A]2 = 9k[A]2
Rate of formation of B is 9 times
(c) Write the expression of integrated rate equation for zero order reaction.
Ans. For zero order reaction
[R]t = [R]0- kt
1
K = {[R]0- [R]t}
𝑡
[R]t = conc.of R at time t

[R]0 = initial conc.of R
K = Rate constant
t = time taken
47
The following questions are case-based questions. Read the case carefully and answer the
questions that follow.
6. The rate of reaction is concerned with decrease in concentration of reactants or increase
in the concentration of products per unit time. It can be expressed as instantaneous rate at
a particular instant of time and average rate over a large interval of time. Mathematical
representation of rate of reaction is given by rate law. Rate constant and order of a reaction
can be determined from rate law or its integrated rate equation.
Answer the following questions:
(i)What is average rate of reaction?
Ans. Change in conc. Of reactant or product per unit time
(ii) Write two factors that affect the rate of reaction.
Ans. (a)Concentration (b) Temperature
(iii) (a) What happens to rate of reaction for zero order reaction?
(b) What is the unit of k for zero order reaction?
Ans (a) Rate is independent of conc. Of reactants and remain constant Rate = k
(b) mol L-1 s-1
OR
(iii) (a) For a reaction P + 2Q --→ Products Rate = k[P]1/2 [Q]1.
What is the order of the reaction?
(d)Define Pseudo first order reaction with example.
Ans. (a) 3/2 or 1.5
(b) A reaction appears to be of higher order but follows first order.
Example – hydrolysis of ester.
QUESTIONS FOR PRACTICE
Q1. Calculate the overall order of a reaction which has the rate expression
(a) Rate = k[A]1/2[B]3/2 (b) Rate = k[A]3/2 [B]-1
Q2. Write the rate law for a first order reaction. Justify the statement that half-life for a
first order reaction
is independent of initial conc. of the reactant.
Q3. A reaction is second order with respect to a reactant. How is the rate affected if conc.
of the reactant is reduced to half? What is the unit of rate constant for such a reaction?
48
Q4. The time required for 10% completion of a first order reaction at 298K is equal to that
required for its 25% completion at 308K. If the value of A is 4 × 1010s–1. Calculate k at 318K
and Ea.
Q5 For a first order reaction, show that time required for 99% completion is twice the time
required for the completion of 90% of reaction.
49
UNIT 4-The d- and f- Block Elements
SYLLABUS-
General introduction, electronic configuration, occurrence and characteristics of
transition metals, general trends in properties of the first row transition metals –
metallic character, ionization enthalpy, oxidation states, ionic radii, colour, catalytic
property, magnetic properties, interstitial compounds, alloy formation, preparation and
properties of K2Cr2O7 and KMnO4.
Lanthanoids - Electronic configuration, oxidation states, chemical reactivity and
lanthanoid contraction and its consequences.
Actinoids - Electronic configuration, oxidation states and comparison with lanthanoids.
GIST OF THE LESSON

1. The elements lying in the middle of Periodic table between s-block and p-block elements
(i.e. between group 2 and 13) are known as d-block or transition elements and have
electronic configuration of ns1-2 (n-1) d1-10
2. There are three transition series each of 10 elements:
(i) First transition series: It involves filling of 3d-orbitals. It starts from scandium (Z = 21)
and goes up to zinc (Z = 30).
(ii) Second transition series: It involves filling of 4d-orbitals. It starts from yttrium (Z=39)
to cadmium (Z = 48).
(iii) Third transition series: It involves filling of 5d-orbitals. The first element of this series
is lanthanum (Z = 57). It is followed by 14 elements called lanthanides which involve the
filling of 4f-orbitals. The next nine elements from Hafnium (Z = 72) to mercury (Z = 80)
belong to third transition series.
3. The f-block elements are called inner-transition elements.
4. All the transition elements are metallic in nature, good conductor of heat and
electricity; show a gradual decrease in electropositive character on moving across a
period. Due to strong metallic bonds, these metals are hard, possess high densities, high
enthalpies of atomisation, high melting and boiling points and form alloys with other
metals.
5. The melting point of these first increases to maximum and then gradually decreases
towards the end of the series due to decrease in the number of unpaired d-electrons.
6. The radii of ions in a given series decreases progressively with increase in atomic
number. This is because of poor shielding effect of d-electrons. Hence, not very large
difference in the sizes of d block elements is seen making them suitable to form alloys.
7. Ionisation energies generally increases from left to right in the series. The ionization
enthalpy of 5d transition series is higher than 3d and 4d transition series because of
lanthanoid contraction.
50
8. Transition metals exhibit a variety of oxidation states due to less energy difference in
ns and (n-1) d orbitals. O.S increases from left to right being max at the center (Mn with
+7) and then again decreases, however in d block Os shows max O.S of +8.
9. Most of the transition metals are sufficiently electropositive. They react with mineral
acids liberating H2 gas.
10. Transition elements and many of their compounds are paramagnetic due to
presence of unpaired e-
11. Formation of coloured compounds This is due to absorption of some radiation from
visible light to cause d-d transition of electrons in transition metal atom. The colour
exhibited is complimentary to the colour absorbed. However, the compounds of Zn in
3d series are colourless due to absence of unpaired electrons.
12. In contrast to s-and p-block elements, the transition elements have the ability to
form complexes. This is because these elements
(a) have small highly charged ions, and (b) contain vacant d-orbitals.
13. Many of transition metals and their compounds act as catalyst in variety of reactions
because of
(i) presence of incomplete or empty d-orbitals (ii) large surface area,
(iii) variable oxidation state (iv) ability to form complexes
14. Transition metals form large number of interstitial compounds.
15. A large number of alloys are formed by transition metals. It is due to almost similar
atomic radii
16. The oxides of transition metals in lower oxidation states are generally basic in nature
and those in, higher oxidation states are amphoteric or acidic in nature.
17. Potassium dichromate, K 2Cr2O7: It is prepared in the following steps:
FeCr2O4 + 8Na2CO3+7O2→8Na2CrO4 (yellow)+ 2Fe2O3 + 8CO2
2Na2CrO44 + 2H+ → Na2Cr2O7 + 2Na++ H2O
Na2Cr2O7 + 2KCl → K 2Cr 2O7 (orange)+ 2NaCl
The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution.
Sodium and potassium dichromates are strong oxidising agents. In acidic solution, its oxidising
action can be represented as follows:
51
2-
o Cr2 O7 + 14 H+ + 6 e- -------→ 2 Cr+3 + 7 H2 O
18. Potassium permanganate, KMnO4
• When finely powdered MnO2 is fused with KOH, K2MnO4 is obtained.

2MnO2+4 KOH+O2→2K 2MnO4+2H2O
• It is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation
of manganate (Vl).
• KMnO4 is deep purple in colour. On heating, it shows decomposition
2KMnO4 → K 2MnO 4 + MnO2 + O2
• The manganate and permanganate ions are tetrahedral. The green manganate is
paramagnetic because of one unpaired electron but the permanganate is diamagnetic due to
the absence of unpaired electron.
19. The f -block elements have been divided in two series depending upon the fact
whether the last electron (differentiating electron) enters 4f- orbitals or 5f-orbitals and
accordingly called lanthanides or actinides respectively.
20. Properties of the lanthanides:
(a) General electronic configuration is [Xe] 4f1-14 5d0-1 6s2.
(b) The metals are silvery-white in colour and possess high melting points.
(c) The lanthanides exhibit a O.S of + 3. However, some elements also exhibit + 2 (Eu2+)
and + 4 (Ce4+).
(d) Many of the lanthanide ions are coloured due to the electronic transition between
different 4 f-levels.
(f) The majority of the lanthanide ions exhibit paramagnetism due to the presence of
unpaired electrons. The lanthanoid ions that do not exhibit paramagnetism are those
with either no 4f-electrons, e. g., La3+ and Ce4+ or with a completed 4f-level, e.g.,
Yb2+ and Lu3+.
21. In lanthanide series with increasing atomic number there is a progressive decrease
in the atomic as well as ionic radii. This regular decrease is known as lanthanoid
contraction. This is due to the poor shielding of f-orbitals, which are unable to counter
balance the effect of increasing nuclear charge. Net result is contraction in size. This
52
gradual decrease in atomic size across the first f- transition element series is called
lanthanoid contraction because of which 4d elements and 5d elements have
comparable sizes.
22. Properties of actinides:

(a) General electronic configuration is [Rn] 5f0-14 6d0-1 7s2.
(b) The elements are all silvery-white metals with moderate m.pt.
(c) The ionic size of the actinides decreases gradually along the series.
(e) The actinides have the ability to exhibit several oxidation states. However, +4
oxidation state is preferred in actinides.
(f) Many actinoid elements are radioactive. The elements beyond uranium are man-
made.
MCQs
1.Which of the following has magnetic moment value of 5.9?

(a) Fe2+ (b) Fe3+ (c) Ni2+ (d) Cu2+
2. Anomalous electronic configuration in the 3d series are of
(a) Cr and Fe (b) Cu and Zn (c) Fe and Cu (d) Cr and Cu
3. Which of the following are d-block elements but not regarded as transition elements?
(a) Cu, Ag, Au (b) Zn, Cd, Hg (c) Fe, Co, Ni (d) Ru, Rh, Pd
4. CuSO4. 5H2O is blue is colour because
(a) It contains water of crystallization. (b) SO42- ions absorb red light.
(c) Cu2+ ions absorb orange red light. (d) Cu2+ ions absorb all colours except red from
the white light.
5. Transition elements form alloys easily because they have
(a) Same atomic number (b) Same electronic configuration
(c) Nearly same atomic size (d) None of the above
6. Which one of the following characteristics of the transition metals is associated with
higher catalytic activity?
(a) High enthalpy of atomization (b) Paramagnetic behaviour
(c) Colour of hydrate ions (d) Variable oxidation states
7. Which of the following has the maximum number of unpaired electrons?
(a) Mg2+ (b) Ti3+
(c) V3+ (d) Fe2+
8. The property which is not characteristic of transition metals is
(a) variable oxidation states. (b) tendency to form complexes.
(c) formation of coloured compounds. (d) natural radioactivity.
9. When manganese dioxide is fused with KOH in air. It gives
53
(a) potassium permanganate (b) potassium manganate
(c) manganese hydroxide (d) Mn3O4.
10.Which metal has highest melting point?
(a) Pt (b) W
(c) Pd (d) Au
ASSERTION REASON:
(a) If both Assertion and Reason are correct and the Reason is a correct explanation of the
Assertion.
(b) If both Assertion and Reason are correct but Reason is not a correct explanation of the
Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
11. Assertion: Cuprous ion (Cu+) has unpaired electrons while cupric ion (Cu++) does not.
Reason: Cuprous ion (Cu+) is colourless whereas cupric ion (Cu++) is blue in the aqueous
solution.
12. Assertion: Transition metals show variable valency.
Reason: Transition metals have a large energy difference between the ns2 and (n – 1) d
electrons
13.Read the passage given below and answer the following questions:
The transition elements have incompletely filled d-subshells in their ground state or in any of
their oxidation states. The transition elements occupy positions in-between s- and p-blocks
in groups 3-12 of the Periodic table. Starting from the fourth period, transition elements
consist of four complete series. In general, the electronic configuration of outer orbitals of
these elements is (n – 1) d1–10 ns0–2. The electronic configurations of outer orbitals of Zn, Cd,
Hg, and Cn are represented by the general formula (n – 1) d10 ns2. All the transition elements
have typical metallic properties such as high tensile strength, ductility, malleability. Except
for mercury, which is liquid at room temperature, other transition elements have typical
metallic structures. The transition metals and their compounds also exhibit catalytic property
and paramagnetic behaviour. Transition metal also forms alloys. Alloys may be homogeneous
solid solutions in which the atoms of one metal are distributed randomly among the atoms
of the other.
I)Which one of the following outer orbital configurations may exhibit the largest number of
oxidation states?
54
(a) 3d54s1 (b) 3d54s2
(c) 3d24s2 (d) 3d34s2
II)The correct statement(s) among the following is/are
(i) all d- and f-block elements are metals
(ii) all d- and f-block elements form coloured ions
(iii) all d- and f-block elements are paramagnetic.
(a) (i) only (b) (i) and (ii) only
(c) (ii) and (iii) only (d) (i), (ii) and (iii)
III). The oxidation state of vanadium in V2O5 is
(a) +5/2 (b) +7
(c) +5 (d) +6
IV)Transition elements form alloys easily because they have
(a) same atomic number (b) same electronic configuration
(c) nearly same atomic size (d) same oxidation states
14. Match the column:
SECTION B
Very Short answer questions:
Q 1 What is the general electronic configuration of d block elements?
Ans: (n-1) d1-10 ns1-2
Q 2 Why do transition elements show variable oxidation states?
Ans: The variability of oxidation state of transition elements is due to incompletely filled d-
orbitals and presence of unpaired electrons, i.e. (ns) and (n -1) d electrons have approximate
equal energies.
Q 3 Which elements are considered as pseudo d block elements?
Ans: Zn, Cd, Hg.
Q 4 Explain Why Transition elements generally form coloured compounds?
Ans: Because of presence of unpaired d electrons, which undergoes d-d transition by
absorption of energy from visible region and then the emitted light shows complementary
colours. This is how transition elements form coloured compounds
55
Q 5: Why transition metals show highest O.S only with Oxygen or halogens?
Ans: Because of their highly electronegative nature.
Q 6 Zinc is not regarded as a transition element. Why?
Ans. Zinc in its common oxidation state of +2 has completely filled d-orbitals. Hence
considered as non-transition element
Q 7. What is meant by ‘lanthanoid contraction’?
Ans: The steady decrease in the ionic radius from La3+ to Lu3+ is termed as lanthanoid
contraction.
Q 8 Write the formula of an oxo-anion of Manganese (Mn) in which it shows the oxidation
state equal to its group number.
Ans: Permanganate ion, i.e., MnO4– with oxidation number +7.
Short answer questions:
Q 9 How would you account for the following:
(i) Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an
oxidising agent.
(ii) In a transition series of metals, the metal
which exhibits the greatest number of oxidation states occurs in the middle of the series.
Ans: (i) Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half-filled t2g
orbitals. Therefore Cr2+ is reducing agent. While Mn2+ has stable half-filled d5 configuration.
Hence Mn3+ easily changes to Mn2+ and acts as oxidising agent.
(ii) Due to presence of more unpaired electrons and use of all 4s and 3d electrons in the
middle of series.
Q 10. (a) Which metal in the first transition series (3d series) exhibits +1 oxidation state most
frequency and why?
(b) Which of the following cations are coloured in aqueous solutions and why?
SC3+, V3+, Ti4+, Mn2+.
(At. No. Sc = 21, V = 23, Ti = 22, Mn = 25) (Delhi 2013)
+1
Ans :(a) Copper exhibits + 1 oxidation state more frequently i.e., Cu because of its electronic
configuration 3d104s1. It can easily lose 4s1 electron to give stable 3d10 configuration.
(b) Sc3+ = 4S0 3d0 = no unpaired electron
V3+ = 3d2 4s0 = 2 unpaired electrons
Ti4+ = 3d0 4s0 = no unpaired electron
Mn2+ = 3d5 4s0 = 5 unpaired electrons
Thus V3+ and Mn2+ are coloured in their aqueous solution due to presence of unpaired
electron.
Long answer questions:

Q 11 What is Lanthanoid contraction? What are its two consequences?
56
Ans: Lanthanoid contraction: The overall decrease in atomic and ionic radii with increasing
atomic number is known as lanthanoid contraction. In going from La+3 to Lu+3 in lanthanoid
series, the size of ion decreases. This decrease in size in the lanthanoid series is known as
lanthanoid contraction. The lanthanoid contraction arises due to imperfect shielding of one 4f
electron by another present in the same subshell.
Consequences:
(i) Similarity in properties: Due to lanthanoid contraction, the size of elements which follow (Hf
– Hg) are almost similar to the size of the elements, of previous row (Zr – Cd) and hence these
are difficult to separate. Due to small change in atomic radii, the chemical properties of
lanthanoids are very similar due to which separation of lanthanoid becomes very difficult.
(ii) Basicity difference: Due to lanthanoid contraction, the size decreases from La+3 to Lu+3.
Thus, covalent character increases. Hence basic character of hydroxides also decreases i.e.
why La (OH)3 is most basic while Lu (OH)3 is least basic.
Q 12. When chromite ore FeCr2O4 is fused with NaOH in presence of air, a yellow coloured
compound (A) is obtained which on acidification with dilute sulphuric acid gives a compound
(B). Compound (B) on reaction with KCl forms an orange coloured crystalline compound (C).
(i) Write the formulae of the compounds (A), (B) and (C).
(ii) Write one use of compound (C).
Ans: The chromite ore FeCr2O4 on fusion with NaOH in presence of air, forms a yellow
coloured compound (A) i.e. Sodium chromate.
Na2Cr2O7 + 2KCl → 2NaCl + K2Cr2O7 (C)

(i) Thus (A) → Sodium chromate Na2CrO4
(A) → Sodium dichromate Na2Cr2O7
(B) → Potassium dichromate K2Cr2O7
(ii) (C) is used as a strong oxidising agent in acidic medium in volumetric analysis.
UNSOLVED EXERCISE
1.Which transition metal can show highest oxidation state?

(a) Sc (b) Ti (c) Os (d) Zn
57
2. In K4{Fe(CN)6] oxidation number of Fe is
(a) +2 (b) + 4 (c) + 6 (d) + 7
3. When KMn04 acts as oxidising agent in alkaline medium, the oxidation number of Mn
decreases by
(a) 1 (b) 2 (c) 3 (d) 5.
4.The transition element with lowest atomic number is
(a) Scandium (b) Titanium (c) Zinc ( d) Lanthanum.
5.Which of the following oxides is amphoteric in nature?
(a) NiO (b) ZnO (c) CoO (d) FeO
6.The equivalent mass of K2Cr2O7, when it acts as oxidising agent in acidic medium, is equal to
(a) M (b) M/2 (c) M/6 (d) M/5
7. Which of the following would be diamagnetic?
(a) Cu2+ (b) Ni2+ (c) Cd2+ (d) Ti3+.
8. Least paramagnetic property is shown by
(a) Fe (b) Mn (c) Ni (d) Cu
9. The aqueous solution containing which one of the following ions will be colourless?
(a) Fe2+ (b) Mn2+ (c) Ti3+ (d) Sc3+
10.The value of’spin only’ magnetic moment for one of the following configurations is 2.84
BM. The correct one is
(a) d4 (in strong ligand field) (b) d4 (in weak ligand field)
(c) d³ (in weak as well as strong fields) (d) d5 (in strong ligand field)
11.Which of the following factor may be regarded as the main cause of lanthanide
contraction?
(a) Poor shielding of one of the 4f-electrons by another in the subshell.
(b) Effective shielding of one of the 4f-electrons by another in the subshell.
(c) Poorer shielding of 5d electrons by 4f electrons.
(d) Greater shielding of 5d electrons by 4f electrons.
12.Lanthanides and actinides resemble in
(a) electronic configuration (b) oxidation state
(c) ionization energy (d) formation of complexes.
2-
13.MnO4 (1 mole) in neutral solution (aqueous) disproportionate to
(a) 23 mole of MnO4– and 13 mole of MnO2
(b) 13 mole of MnO4– and 23 mole of MnO2
(c) 13 mole of Mn2O7 and 13 mole of MnO2
(d) 23 mole of Mn2O7 and 13 mole of MnO2
14.Which of the following oxides in acidic in nature?
(a) CrO ` (b) Cr2O3 (c) CrO3 (d) CrO2
15.Which of the following would be paramagnetic?
(a) Zn2+ (b) Cu+ (c) Sc3+ (d) Mn2+
58
16.In a given shell, The order of screening effect is
(a) s > p > d > f (b) f > d > p > s (c) p < d < s < f (d) f > p > s > d
17. MATCH the column
Very Short answer questions:

1. Why d block elements are called transition elements? [CBSE 2021]
2. Why the compounds of d block are mostly coloured?
3. Why Zn has lowest enthalpy of atomization? [CBSE 2023]
4. Which has max no.of unpaired electrons Fe+3 , Sc+3 , Mn+2 , Zn+2 and Co+2 ?
Short answer questions:

5. Why transition elements form alloys?
6. Why melting point of Cr and W is higher than expected?
7. Cr2+ is a strong reducing agent. Why?
8. Why Zr and Hf have similar sizes? [CBSE 2020]
9. Why transition elements forms complexes?
10. Draw the structure of chromate and dichromate ion.
11. How would you account for the following:
(i) Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an
oxidising agent.
(ii) In a transition series of metals, the metal which exhibits the greatest number of oxidation
states occurs in the middle of the series.
[CBSE 2023]
Long answer questions:
12. How would you account for the following:
(i) Many of the transition elements and their compounds can act as good catalysts.
(ii) The metallic radii of the third (5d) series of transition elements are virtually the same as
those of the corresponding members of the second series.
(iii) There is a greater range of oxidation states among the actinoids than among the
lanthanoids. [CBSE 2023]
59
Answers of objective questions of solved exercise:
1) B 5) C 9 )B 13 (i) B
2 )D 6 )D 10) B (ii) A
3 )B 7 )D 11 )B (iii) C
4 )C 8 )D 12 )C (iv) C
14. 1 –C ,2- D ,3-B , 4-E,
5-A
Answers of objective questions of Unsolved exercise
1) C 2 )A 3) C 4) A 5)B 6)C 7)C 8)D
9)D 10)A 11)A 12)B 13)A 14)C 15)D 16)A
17) 1-C ,2-A,
3-B
60
UNIT 5 - COORDINATION COMPOUNDS
SYLLABUS
Double Salts
Coordination Compound
IMPORTANT TERMS
Writing Formula of Coordination Complex
Werner Theory
Isomerism in Coordination Compounds
Valence bond theory
Crystal Field Theory
Metal Carbonyls
Application of Coordination Complexes
GIST OF THE LESSON
Double Salts Coordination Compound

Double salts are the addition A molecular compound resulting from
compounds which are stable in solid the combination of two or more stable
state but break up into constituent molecular compounds and retains its
ions when dissolved in water or any identity in the solid state as well as in
other solvent. e.g solution e.g
Mohr’s salt FeSO4. (NH4)2SO4.6H2O [Co (NH3)6]Cl2 , K4[Fe(CN)6]
Potash alum K2SO4.Al2(SO4)3.24H2O
IMPORTANT TERMS:
Coordination entity or sphere
Counter ion Ligand ( Lewis base )

K4 [ Fe (CN) 6
]
Coordination number
Central metal atom or ion( Lewis acid )
1. Complex ion or Coordination Entity: - It is an electrically charged species in

which central metal atom or ion is surrounded by number of ions or neutral
molecules.
61
(i) Cationic complex entity It is the complex ion which carries positive charge. e.g.,
[Pt (NH3)4]2+
(ii) Anionic complex entity It is the complex ion which carries negative charge.
e.g., [Fe (CN)6]4-
2. Central Atom or Ion: - The atom or ion to which a fixed number of ions or
groups are bonded. It is also referred as Lewis acid. e.g., in [NiCI2(H2O)4]. Ni is
central metal atom.
3. Ligands: - Ligands is electron donating species (ions or molecules) bonded to
the Central atom. These may be charged or neutral. Ligands are of the following
types:
(i) Unidentate: - It is a ligand, which has one donor atom e.g F- -Fluorido, Cl- -
Chlorido, Br- –Bromido
I - - Iodido, H- -Hydrido, OH- – Hydroxido, CN- -Cyanido, SCN- - Thiocyanato NCS- -
Isothiocyanato, CH3COO- -Acetato SO42- - Sulphato, CO32- - Carbonato, C2O42- -
Oxalato (ox), NO31- - Nitrato NO21- - Nitrito(N), PO43- - Phosphato, H2O- Aqua , NH3
– Ammine
(ii) Bidentate: - The ligands which have two donor sites. e.g. C2O42- - Oxalato (ox),
ethylenediamine (en)
(iii) Polydentate: - The ligands which have several donor sites. e.g., [EDTA]4- is
hexadentate.
Ambidentate ligands: - These are the monodentate ligand which can ligate
through two different sites, e.g. – SCN- thiocyanato - NCS-1 isothiocyanato
- NO2- nitrito (N) - ONO- nitrito (O)
-CN- cyano -NC- isocyano
(v) Chelating ligand: - When a bidentate or a polydentate ligand uses

its two or more donor atoms to bind a single metal ion, then a ring-
like structure is obtained. It is called chelate and the ligand is known
as chelating ligand. The chelating ligands form more stable complexes than the
unidentate ligands
62
(vi) Coordination Number: - It is defined as the number of coordinate bonds
formed by central metal atom, with the ligands.
(vii) Coordination Sphere: - The central ion and the ligands attached to it are
enclosed in square bracket which is known as coordination sphere.
(viii) Homoleptic complex: -The central metal atom is bonded with only one kind
of donor groups. [Co (NH3)6]Cl2
(ix) Heteroleptic complex: -The central metal bonded with more than one kind of
donor groups. [Co (NH3)4Cl2]Cl
Writing Formula of Coordination Complex: -
1. Cation is written first followed by anion.
2. In coordination sphere central metal atom is written first followed by ligands.
3. If more than one type of ligands is present then alphabet is followed.
Na2[Fe (H2O)4(NO)Br]
Nomenclature of Coordination Compounds: -

1) Cation is written first followed by anion.
2) While writing name of coordination sphere ligands are named first followed by
central metal atom.
3) To indicate number of ligands, prefix di, tri, tetra, penta, hexa, hepta etc are
used. If ligands itself involve such prefixes in its name then prefix bis, tris, tetrakis,
and so on are used to indicate number of ligands.
4) While writing name of central metal atom: -
a. If coordination sphere is cation name of metal atoms written as such: Fe – Iron,
Au – Gold, Cu – Copper, Cr – Chromium, Ag – Silver.
b. If, coordination sphere is anion suffix ‘ate’ is used to write name of central
metal atom. Such as: Fe – Ferrate, Hg – Mercurate, Cu – Cuperate, Ag – Argentate,
Au – Aurate, Pd – Peladate, Cr - Chromate
5) After writing name of central metal atom its oxidation number is indicated in
perantheses’()’ in Roman numerals.
(1) Na2[Fe(H2O)Br4(NO)] Sodium tetrabromidonitrosylferrate(II)
(2) [Fe(H2O)4Br(NO)]SO4 Tetraquabromidonitrosyliron(III) sulphate
(3) K4[Fe(CN)6] Potassium hexacyanoferrate(II)
(4) [Cr(NH3)3(H2O)3]Cl3 Triamminetriaquachromium(III) Chloride
(5) [Pt(NH3)2Cl(NO2)] Diamminechloridonitritoplatinum(II)
63
(6) [Ni(CO)4] Tetracarbonylnickel (O)
(7) [CO(NH3)5CO3]Cl Pentamminecarbonatocobalt(III) chloride
(8) K3[Cr(C2O4)3] Potassium trioxalatechromate(III)
Werner Theory
Metal in a complex shows two type of valences – Primary & Secondary
Primary Valency Secondary Valency
• It is oxidation no, of metal • It is co-ordination number.
• It is variable • It is non-variable.
• Satisfied by anions (in co-ordination • Satisfied by ligands (in co-ordination
sphere) sphere)
• Ionisable. • Non-ionisable
• Ionic: Nondirectional. • Directional: Decide geometry of
• Represented by dotted line in complex ion.
Werner structure. • Represented by solid lines in Werner
Structure.
Isomerism in Coordination Compounds

(a) Structural isomerism
(i) Linkage isomerism: - This type of isomerism arises due to the presence of an
ambidentate ligand in a coordination compound. e.g [Co (NH3)5NO2]Cl2 and
[Co(NH3)5ONO]Cl2
(ii) Coordination isomerism: - : This type of isomerism is observed in the
coordination compounds having both cationic and anionic complex ions. The
64
ligands are interchanged in both the cationic and anionic ions to form isomers. An
examples is: [Co(NH3)6][Cr(CN)6] & [Cr(NH3)6][Co(CN)6]
(iii) Ionisation isomerism: - This type of isomerism arises when the coordination
compounds give different ions in solution. For example, there are two isomers of
the formula Co (NH3)5BrSO4 . [Co (NH3)5(SO4)]Br & [Co(NH3)5Br]SO4 .
(iv) Hydrate Isomerism: - This type of isomerism arises when different number of
water molecules are present inside and outside the coordination sphere.
[Cr(H2O)6]Cl3 & [Cr(H2O)5Cl]Cl2.H2O
(b) Stereoisomerism
(i) Geometrical isomerism- The complex compounds which have the same ligands
in the co-ordination sphere but the relative position of the ligands around the
central metal atom is different are called geometrical isomerism. If same ligands
are on same side – Cis isomer. If same ligands are on opposite side – trans isomer.
NOTE: - [Mabcd]-complex give three isomers
65
NOTE: -Tetrahedral complexes does not exhibit geometrical isomerism due to
same relative position of ligands around central metal atom.
(ii) Optical isomerism: - Optical isomers are mirror images that cannot be
superimposed on one another. These are called as enantiomers and rotate the
plane of polarised light equally but in opposite directions. The isomer which
rotates the plane of polarised light towards left is called laevorotatory (l) while
which rotates the plane towards right is called dextrorotatory (d).
Valence bond theory: -

(i) The number of metals–ligand coordinate bonds which can be formed in case of
given metal ion depends upon the number of vacant orbitals for bonding in metal
ion and is known as the coordination number of metal ion.
(ii) The metal atom or ion under the influence of ligands uses its (n – 1) d, ns, np
or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of
definite geometry.
66
(iii) The empty hybrid orbitals of the central metal atom or ion overlap with the
filled orbitals of the ligand containing the lone pair of electrons. In this way a
metal–ligand coordinate bond is formed.
(iv) The inner orbital (low spin) or the outer orbital (high spin) complexes are
formed depending upon whether the d-orbitals of inner shell or d-orbitals of
outer shell are used in hybridisation.
(v) The complex will be diamagnetic if all electrons are paired. If unpaired
electrons are present then the complex will be paramagnetic
High spin complex.• Unpaired electron present (weak field ligand doesn’t pair
the electrons)
Low spin complex.• Unpaired electron absent (strong field ligand does pairing
of electrons)
Coordination Type of Distribution of Hybrid Orbitals

Number Hybridisation in Space
3
4 sp Tetrahedral
4 dsp2 Square planar
3
5 sp d Trigonal bipyramidal
3 2
6 sp d Octahedral
2 3
6 d sp Octahedral
Limitation: -
• It couldn’t explain why pairing occurs in S.F.L. and no pairing in W.F.L.
• It couldn’t explain colour of compound.
• It doesn’t distinguish between strong and weak ligands.
Explain the diamagnetic nature of [Co(NH3)6]3+ on the basis of VBT
NH3 is strong field ligand and will do pairing of electrons.
3+
Co [Ar] 3d6 3d6 4S 4P
In absence of ligands
With the approach of ligands
These orbitals undergo d2sp3 hybridisation

x x x x x x
After hybridisation x x x x x x
Six NH3 will form six M L coordinate bonds NH 3 NH 3 NH 3 NH 3 NH 3 NH 3

Geometry - Octahedral Diamagnetic due to absence of unpaired electrons
67
Explain the paramagnetic nature of [CoF6]3- on the basis of VBT.
F- is weak ligand and cannot cause pairing of electrons.
Co 3+ [Ar] 3d6
In absence of ligands 3d6 4S 4P 4d
With the approach of ligands there is no pairing of electrons
These orbitals undergo sp3d2 hybridisation

After hybridisation
x x x x x x
x x x x x x
−
Six F - form six coordinate bonds. F F −
F −
F −
F −
F −
Paramagnetic due to presence of four unpaired electrons Geometry - Octahedral
Crystal Field Theory

• It assumes the ligands to be point charges and there is electrostatic force of
attraction between ligands and metal atom or ion.
• The splitting of five degenerate d-orbital of the metal into different sets of
orbitals having different energies in the presence of electrostatic field of
ligands is called crystal field splitting.
eg set: - dx2–y2 , dz2 t2g set :- dxy, dyz, dxz.
• Weak field ligands which cause a small degree of crystal field splitting e.g.
I– , Br– , Cl– , F– , OH– , C2O42–, H2O etc.
• Strong field ligands are those ligands which cause a high degree of splitting
e.g. CO, CN, NO. etc.
• Spectrochemical series I– < Br– < SCN– < Cl– < S2– < N3 – < F- < OH– < ox2– <
H2O < NCS– < EDTA4– < NH3 < py ~ en < dipy < o-phen < N2– < CN– < CO.
• For the same metal, the same ligands and metal-ligand distances, the
difference in energy between eg and t2g level is
68
Crystal Field splitting in Octahedral and tetrahedral
Case – 1 : d4 ion in strong field o > P Electrons will be paired , Electronic

configuration : t2g4 eg0
Case- 2: d4 ion in weak field o <P Electrons will jump to 'eg' orbital Electronic
configuration : t2g3 eg1
NOTE: - ( P- Pairing energy, energy required for pairing electrons in an orbital )
Strong field - Low spin which is known as spin paired.
Weak field - High spin which is known as spin free
Metal Carbonyls: Metal carbonyls are the organometallic compounds in which
carbon monoxide acts as the ligand.
Synergic bonding in metal carbonyl:- The metal carbon
bond in the metal carbonyl possess both sigma and pi
character.
[1] Metal-carbon  -bond is formed by the donation of
the lone pair of electrons on the carbonyl carbon into a vacant orbital of the
metal.
[2] Metal-carbon  -bond is formed by the donation of a pair of electrons from
a filled d-orbital of the metal into the vacant antibonding  * orbital of carbon
monoxide.
Application of Coordination Complexes: -
69
a) Biological System: Chlorophyll – complex of Mg, Haemoglobin – complex of Fe,
Vit. B-12 – complex of Co
b) Metallurgy: Extraction of Au, Ag, by cyanide process, Refining of Ni by Mond’s
process, Refining of Zr by Van Arkel process.
c) Quantitative Analysis: Estimation of hardness of water Ca2+ and Mg2+ are
estimated by complexomatric titration using EDTA.
d) Qualitative Analysis: Cu2+, Fe2+, Zn2+, Ni2+ etc ions are confirmed by reactions
involving complex formation.
e) As medicines: Cisplatin [Cancer Treatment], EDTA [Used to remove heavy metal
poison using chelate therap

1. The oxidation state of nickel in [Ni(CO)4] is
(a) 0 (b) 1 (c) 2 (d) 3
2. When 1 mol CrCl3.6H2O is treated with excess of AgNO3, 3 mol of AgCl are
obtained. The formula of the complex is:
(a) [CrCl3(H2O)3].3H2O (b) [CrCl2(H2O)4]Cl.2H2O
(c) [CrCl(H2O)5]Cl2.H2O (d) [Cr(H2O)6]Cl3
3. Which of the following is a hexadentate ligand?
(a) EDTA4- (b) (COO)22-- (c) en (d) NH3
4. The primary and secondary valency of copper in the complex [Cu(NH3)4]SO4
are
(a) 2, 4 (b) 4, 2 (c) 0, 4 (d) 1, 4
5. Which of the following statement is correct?
(a) [Cu(NH3)4]2+ is diamagnetic while [Fe(CN)6]4- is paramagnetic
(b) [Cu(NH3)4]2+ is paramagnetic while [Fe(CN)6]4- is diamagnetic
(c) both are paramagnetic
(d) both are diamagnetic
6. The monodentate ligands which can coordinate with the central atom
through more than one site are called:
(a) bidentate ligands (b) ambidentate ligand
(c) Chelate ligand (d) none of these
7. Which of the following is not ambidentate ligand?
(a) CN- (b) NO2- (c) SCN- (d) NH3
8. Which of the following is incorrect:
70
(a) [CoBr(NH3)5]SO4 - shows ionization isomerism
(b) [Co(NH3)5(NO2)]Cl2 - linkage isomerism
(c) [Co(NH3)6][Cr(CN)6] - coordination isomerism
(d) trans-[Co(en)2Cl2]+ - optical isomerism
9. IUPAC name of [Pt(NH3)3Br(NO2)Cl]Cl is:
(a) triamminechlorodibromidoplatinum(IV) chloride
(b) triamminechloridobromidonitrochlorideplatinum(IV) chloride
(c) triamminebromidochloridonitroplatinum(IV) chloride
(d) triamminenitrochlorobromoplatinum(IV) chloride
10. Which of the following compounds can exhibit linkage isomerism?
(a) [Co(en)3]Cl3
(b) [Co(en)2Cl2]Cl
(c) [Co(en)2(NO2)Cl]Br
(d) [Co(NH3)5Cl]Br2.
11. How many ions are produced from [Co(NH3)5Cl]Cl2 in solution?
(a) 3 (b) 4 (c) 2 (d) 5
12. Which one of the following is expected to exihibit optical isomerism (en =
ethylene diammine).
(a) cis-[Pt (NH3)2Cl2) (b) cis-[Co(en)2Cl2]
(c) trans-[Co(en)2 Cl2] (d) trans-[Pt (NH3)2Cl2]
13. Which of the following cyano complexes would exihibit the highest value of
paramagnetic character?
(a) [Cr(CN)6]3- (b) [Mn(CN)6]3-
(c) [Fe(H2O)6]3- (d) [Co(CN)6]3-
14. The diamagnetic species is
(a) [Ni(NH3)4]2+ (b) [NICl4]2-
(c) [CoCl4]2- (d) [CoF6]2-
15. Denticity of dien
(a) 3 (b) 4 (c) 5 (d) 6
16. Assertion Reason Type questions Directions:
These questions consist of two statements, each printed as Assertion and
Reason. While answering these questions, you are required to choose any
one of the following four responses.
(a) If both Assertion and Reason are correct and the Reason is a correct
explanation of the Assertion
71
(b) If both Assertion and Reason are correct but Reason is not a correct
explanation of the Assertion.
(d) If the Assertion is incorrect but Reason is correct
(i) Assertion (A) : Oxalate ion is a bidentate ligand.

Reason (R) : Oxalate ion has two donor atoms
(ii) Assertion (A) : [FeF6]3– is a low spin complex.
Reason (R) : Low spin complexes have lesser number of unpaired electrons.
(iii) Assertion(A): [Fe (H2O)6]2+ is sp3d2 hybridized and paramagnetic complex ion.
Reason(R) : It has four unpaired electrons.
(iv) Assertion :CO is stronger ligand than NH3 for many metals
Reason : CO can form pi bonds by back bonding
(v) Assertion : F- ion is a weak ligand and forms outer orbital complex.
Reason : F- ion cannot force the electrons of dz2 and d x 2-y2 orbitals of the inner
shells to occupy dxy ,dyz and dxz orbitals of the same subshell
TWO MARKS QUESTIONS

17. (i) Write the IUPAC name of the isomer of the complex: [Pt(NH3)2Cl2]
(ii) Write the formula for : Tetraammineaquachloridocobalt (III) nitrate
Ans (i) cis-diamminedichloridoplatinum (II) and trans-
diamminedichloridoplatinum (II)
(ii) [Co(NH3)4(H2O)Cl](NO3)2
18. When a coordination compound CrCl3.6H2O is mixed with AgNO3, 2 moles
of AgCl are precipitated per mole of the compound. Write
(i) structural formula of the complex.
(ii) IUPAC name of the complex.
Ans. (i) [Cr(H2O)5Cl]Cl2.H2O
(ii) pentaaquachloridochromium (III) chloride monohydrate
19. For the complex [Fe(CN)6]3–, write the hybridisation type, magnetic
character and spin nature of the complex. (At. Number : Fe = 26).
Ans. d2sp3 hybridisation , Paramagnetic and low spin complex.
72
20. Explain why [Fe(H2O)6]3+ has magnetic moment value of 5.92 BM whereas
[Fe(CN)6]3– has a value of only 1.74 BM.
Ans. [Fe(CN)6]3– involves d2sp3 hybridisation with one unpaired electron and
[Fe(H2O)6]3+ involves sp3d2 hybridisation with five unpaired electrons.
21. Draw all the isomers (geometrical and optical) of: (i) [CoCl2(en)2]+
Ans.
22. What is meant by chelate effect?

Ans. Chelate effect : When a bidentate or a polydentate ligand contains donor
atoms positioned in such a way that when they coordinate with the central
metal ion, a five or a six membered ring is formed. This effect is called
Chelate effect. As a result, the stability of the complex increases.
23. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are
tetrahedral. Why?
Ans. Because In the presence of strong ligand CO, the unpaired d-electrons of Ni
pair up but Cl– being a weak ligand is unable to pair up the unpaired
electrons.
24. What is meant by ambidentate ligands? Give two examples.
Ans. A molecule or an ion which contains two donor atoms but only one of them
forms a coordinate bond at a time with the central metal atom is called
ambidentate ligand, e.g., CN– or NC– and NO2– or ONO–
25. What are the primary and secondary valency of [Co(NH3)6]Cl3 & K4[Fe(CN)6] ?
Ans. [Co(NH3)6]Cl3 –primary valency= +3, secondary valency=6
K4[Fe(CN)6] –primary valency= +2, secondary valency=6
26. Draw the optical isomers of [Co(en)3]3+
Ans.
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THREE MARKS QUESTIONS
27. (i) For the complex [Fe(H2O)6]3+, write the hybridisation, magnetic character
and spin of the complex. (At. number: Fe = 26)
(ii) Draw one of the geometrical isomers of the complex [Pt(en)2Cl2]2+
which is optically inactive.
Ans. (i) ii)
28.
A
solution
of
[Ni(H2O)6] 2+ is green but a solution of[Ni(CN)4]2– is colourless. Explain.

Ans. In [Ni(H2O)6]2+, Ni is in +2 state with the configuration 3d8 , i.e., it has two
unpaired electrons which do not pair up in the presence of the weak H2O
ligand. So, it is coloured..
In case of [Ni(CN)4]2–, Ni is again in +2 state with the configuration 3d8 but
in presence of the strong CN– ligand, the two unpaired electrons in the 3d
orbitals pair up. Hence, there is no unpaired electron present. Hence, it is
colourless.
29. A metal ion Mn+ having d5 valence electronic configuration combines with
three didentate ligands to form a complex compound. Assuming ∆o > P ,
(i)Write the coordination number of the metal ion.
(ii)What type of hybridisation will Mn+ have?
(iii)Write the electronic configuration of the metal
Ans. (i) 6 (ii) d2sp3 (iv)t2g5 eg0
30. What is crystal field splitting energy? Write electronic configuration for d4
in case of strong field and weak field ligand?
Ans. When ligands approach a transition metal ion, the d-orbitals split into two
sets, one with lower energy and the other with higher energy. The
difference of energy between the two sets of orbitals is called crystal field
splitting energy (∆o) in case of octahedral field.
If ∆o < P (pairing energy), the 4th electron enters one of the eg orbitals
giving the configuration t2g3 eg1 , thereby forming high spin complexes.
If ∆o > P, the 4th electron pairs up in one of the t2g orbitals giving the
configuration t2g4 eg0, thus forming low spin complexes.
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31. Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with square
planar structure and the [NiCl4]2– ion with tetrahedral geometry explain?
Ans. In [NiCl4]2- , Cl– is a weak field ligand. It is, therefore, unable to pair up the
unpaired electrons of the 3d orbital. Hence, the hybridisation involved is
sp3 and the shape is tetrahedral.
In [Ni(CN)4]2– , CN- is a strong field ligand which pair up the unpaired
electrons of the 3d orbital. Hence, the hybridisation involved is dsp2 and the
shape is square planar.
FIVE MARKS QUESTIONS

32. For the complex [Fe(en)2Cl2]Cl, (en = ethylene diamine), identify
(i) the oxidation number of iron,
(ii) the coordination number hybrid orbitals and the shape of the complex,
(iii)the magnetic behaviour of the complex,
(iv)the number of geometrical isomers,
(v) name of the complex. (At. no. of Fe = 26)
Ans. (i) Oxidation number of iron, x = + 3
(ii)The complex has two bidentate ligands and two monodentate ligands.
Therefore, the coordination number is 6 and hybridization will be d2sp3 and
shape will be octahedral.
(iii) Due to presence of one unpaired electrons in d orbitals the complex is
paramagnetic.
(iv) The number of geometrical isomers are two, cis and trans
(v) Name of complex: Dichloridobis (ethane-1, 2- diamine) Iron (III) chloride.
33. CoSO4Cl.5NH3 exists in two isomeric forms ‘A’ and ‘B’. Isomer ‘A’ reacts with
AgNO3 to give white precipitate, but does not react with BaCl2. Isomer ‘B’
gives white precipitate with BaCl2 but does not react with AgNO3. Answer
the following questions:
(i) Identify ‘A’ and ‘B’ and write their structural formulae.
(ii) Name the type of isomerism involved.
(iii) Give the IUPAC name of ‘A’ and ‘B’.
Ans. (i) A-[Co(NH3)5SO4]Cl, B- [Co(NH3)5Cl]SO4
(ii) ionization isomerism
(iv) A-pantaamminesulphatocobalt(III) chloride
B- pantaamminechloridocobalt(III) sulphate
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CASE BASED QUESTIONS
34. Read the passage given below and answer the following questions: (1+1+2)
Valence bond theory considers the bonding between the metal ion and the
ligands as purely covalent. On the other hand, crystal field theory considers
the metal -ligand bond to be ionic arising from electrostatic interaction
between the metal ion and the ligands.In coordination compounds, the
interaction between the ligand and the metal ion causes the five d -orbitals
to split -up.This is called crystal field splitting and the energy difference
between the two sets of energy level is called crystal field splitting
energy.The crystal field splitting energy (Δo) depends upon the nature of
the ligand. The actual configuration of complexes is divided by the relative
values of Δo and P (pairing energy). If Δo < P, then complex will be high spin.
If Δo > P, then complex will be low spin.
(i) CO is a stronger ligand than NH3 why?
Ans. because in case of CO back bonding takes place in which central
atom uses its filled d orbital with empty π * molecular orbital of CO
(ii) How the crystal field splitting energy for octahedral (Δo ) and
tetrahedral (Δt ) complex is related.
Ans.
(iii)On the basis of crystal field theory, what will be the electronic
configuration of d5 in the given two situations: (a) Δo > P and (b) Δo <
P
Ans. If ∆o > P = t2g5 eg0 If ∆o < P= t2g3 eg2
OR
Using crystal field theory, calculate magnetic moment of central
metal of [FeF6]4 -.
Ans. √4(4 + 2)=4.9 BM
35. Read the following paragraph and answer the questions. (1+1+2)
Isomerism is a phenomenon in which compounds have the same molecular
formula but different physical and chemical properties on account of
different structures. The two major types of isomerism are structural and
stereo isomerism. The structural isomerism is further divided into four
types. Linkage, coordination, ionisation and solvate isomerism while the
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stereo isomerism is divided into two types: Geometrical and optical
isomerism.
(i)Name the type of isomerism exhibited by [Co(NH3)5CN]+2
Ans. Linkage isomerism
(ii)The complexes [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]are the
examples of which type of isomerism?
Ans. Coordination isomerism
(iii) Why is geometrical isomerism not possible in tetrahedral complexes
having two different types of unidentate ligands coordinated with the
central metal ion ?
Ans. Tetrahedral complexes do not show geometrical isomerism because the
relative positions of the unidentate ligands attached to the central metal
atom are the same with respect to each other.
OR
Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of
these will exhibit optical isomerism?
Ans. Three isomer are possible
CBSE BOARD QUESTIONS

Q.1 The magnetic moment of [𝑁𝑖𝐶𝑙4]2− [CBSE 2023]
A. 1.82 𝐵𝑀 B. 2.82 𝐵𝑀 C. 4.42 𝐵𝑀 D. 5.46 𝐵
Ans. B. 2.82 𝐵𝑀
Q.2 Write the electronic configuration of Fe(III) (d5) on the basis of crystal field
theory when it forms an octahedral complex in the presence of (i) strong
field ligand, and (ii) weak field ligand. (Atomic no. of Fe = 26) [CBSE 2023]
Ans. (i) t2g5eg0 (ii) t2g3eg2
Q.3 [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are
tetrahedral. Why? [CBSE 2019 ,2022 ]
Ans. In [Ni(CO)4], Ni is in zero oxidation state whereas in [NiCl4]2– it is in +2
oxidation state. In the presence of strong ligand, CO, the unpaired d-
electrons of Ni pair up but Cl– being a weak ligand is unable to pair up the
unpaired electrons.
77
Q.4 When a coordination compound CrCl3.6H2O is mixed with AgNO3, 2 moles
of AgCl are precipitated per mole of the compound. Write
(i) structural formula of the complex. (ii) IUPAC name of the complex.
[CBSE 2016; 2019 ]
Ans. (i) [Cr(H2O)5Cl]Cl2.H2O
(ii) pentaaquachloridochromium(III) chloride monohydrate.
Q.5 Using IUPAC norms,write the formulae for the following complexes:
[CBSE 2019 ]
(i) hexaaquachromium(III) chloride (ii) sodium trioxalatoferrate(III)
Ans. (i) [Cr(H2O)6]Cl3 (ii) Na3[Fe(C2O4)3]
Q.6 (a) Which of the following species cannot act as a ligand? Give reason. 𝑂𝐻−,
𝑁𝐻4+, 𝐶𝐻3𝑁𝐻2 , 𝐻2𝑂 [CBSE 2023]
(b) The complex [(𝑁𝐻3)5(𝑁𝑂2)]𝑙2 is red in colour. Give IUPAC name of its
linkage isomer.
Ans. (a) Usually, species having lone pairs can acts as a ligand. Here, 𝑁𝐻4+
ion cannot act as ligand because it does not possess any lone pairs of
electrons
(b) [(𝑁𝐻3)5(𝑁𝑂2)]𝑙2 Its linkage isomer: [𝐶𝑜(𝑁𝐻3)5(𝑂𝑁𝑂)]𝐶𝑙2
IUPAC name of linkage isomer: Pentaamminenitrito-O-cobalt (III) chloride
Q.7 Using valence bond theory, predict the hybridisation and magnetic
character of the following: (i) [CoF6]3– (ii) [Ni(CN)4]2– [Atomic number:
Co = 27, Ni = 28] [CBSE 2019 ]
Ans. (i) sp3d2 , paramagnetic (ii) dsp2 , diamagnetic
Q.8 (i) What type of isomerism is shown by the complex [Cr(H2O)6]Cl3?
(ii) On the basis of crystal field theory, write the electronic configuration for
d4 ion if ∆o > P.
(iii) Write the hybridisation and shape of [CoF6] 3–. [CBSE 2015,2022]
Ans. (i) Hydration isomerism is shown by complex [Cr(H2O)6]Cl3.
(ii) If ∆o > P, electronic configuration becomes t2g4 eg0.
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Q.9 What is meant by chelate effect? Give an example. [CBSE
2020]
Ans. When a bidentate or a polydentate ligand contains
donor atoms positioned in such a way that when they
coordinate with the central metal ion, a five or a six-membered ring is
formed, the effect is called chelate effect. Example, [PtCl2(en)].
Q.10 (b) Explain [Fe(𝐶𝑁)6]3− is an inner orbital complex whereas [𝐹𝑒𝐹6]3− is an
outer orbital complex. [Atomic number: 𝐹𝑒 = 26 ][CBSE 2023]
Ans. [(Fe𝐶𝑁)6]3−
𝐹𝑒 ⇒ +3
oxidation state i.e., E. C. = 3𝑑 5

𝐶𝑁− ⇒ strong field ligand i.e., Δ0 > 𝑃 ⇒ Pairing will take place Electronic
configuration of
𝐹𝑒 3+: 3𝑑5 i.e., Hybridisation will be: 𝑑2𝑠𝑝3 i.e., Inner orbital complex
[𝐹𝑒𝐹6]3− 𝐹𝑒 ⇒ +3 oxidation state i.e., E.C. ⇒ 3𝑑5
𝐹 − ⇒ weak field ligand i.e., Δ0 < 𝑃 ⇒ Pairing will not take place Electronic
configuration of
𝐹𝑒 3+ ∶ 3𝑑5
i.e., Hybridisation will be: 𝑠𝑝3𝑑2 i.e., Outer orbital complex
ASSIGNEMENT
1 Marks questions
i. Arrange the following complexes in the increasing order of conductivity of
their solution: [Co(NH3)3Cl3], [Co(NH3)4Cl2]CI, [Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2
ii. Explain why [Fe(H2O)6] 3+ has a magnetic moment value of 5.92 BM whereas
[Fe(CN)6]3- has a value of only 1.74 BM.
iii. Arrange the following complex ions in increasing order of crystal field
splitting energy (Δo) : [Cr(Cl)6] 3– , [Cr(CN)6] 3– , [Cr(NH3)6] 3+
iv. Draw isomers for [Co(NH3)3Cl3]
v. The IUPAC name of complex ion ,[Fe(CN)6] 3- is
79
2 Marks questions
vi. What is the coordination number of central metal ion in [Fe(C2O4)3] 3– ?
vii. Write the formula of pentamminechloridoplatinum(IV).
viii. When 1 mol CrCl3.6H2O is treated with an excess of AgNO3, 3 mol of AgCl
are obtained. Write structural formula & IUPAC name of the complex.
ix. Draw structures of geometrical isomers of [Fe(NH3)2(CN)4] –
x. What is meant by denticity of a ligand?
3 Marks questions
xi. Explain the following with example:
a)Chelating ligand b) ambidentate ligand c) bidentate or Didentate
ligand
xii. How many geometrical isomers are possible in the following coordination
entities? (i) [Cr(C2O4)3] 3– (ii) [Co(NH3)3Cl3]
xiii. Write the name & Using VBT Predict the Magnetic behaviour,
Hybridization, Shape of following. Also predict whether it is inner or outer
orbital complex in case of octahedral complexes.
(i) [Fe(H2O)6] 3+ (ii) [Fe(CN)6] 3 –
xiv. Describe the type of hybridisation,shape and magnetic property: (i)
[Fe(H2O)6] 2+ (ii) [Co (NH3)6] 3+ (iii) [NiCl4] 2–
Answer Key
1-A 2-D 3-A 4-A 5-B 6-B 7-D 8-D 9-C 10-C
11-A 12-B 13-C 14-A 15-A 16(i)-A 16(ii)- 16(iii)- 16(iv)- 16(v)-
D A A A
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UNIT 6. HALOALKANES AND HALOARENES ( 6 Marks)
Haloalkanes: Nomenclature, nature of C–X bond, physical and chemical properties, optical
rotation, mechanism of substitution reactions.
Haloarenes: Nature of C–X bond, substitution reactions (Directive influence of halogen in
monosubstituted compounds only).
Uses and environmental effects of - dichloromethane, trichloromethane, tetrachloromethane,
Iodoform, freons, DDT.
Mind mapping
(1) Primary or 10 haloalkanes: In this case, X – atom is bonded to the 10 C –atom. CH3 – CH2 – Cl
(2) Secondary or 20 haloalkanes: Here, X – atom is bonded to 20 C – atom. CH3 – CH (Br) – CH3
(3) Tertiary or 30 haloalkanes: Here, the X atom is bonded to 30 C – atom. CH3 C (Cl) (CH3)2
1. The decreasing order of reactivity of different halogen acids towards alcohols is as
follows: H – I > H – Br > H – Cl > H – F.
The decreasing order of reactivity of different alcohols towards HX is as follows:
30 alcohol > 20 alcohol > 10 alcohol > CH3 – OH.
2. 10 and 20 alcohols react with HCl gas in the presence of anhydrous ZnCl2 to form 10 and
20 chloro-alkanes respectively. It is known as Grove’s process.
𝐴𝑛ℎ𝑦 𝐴𝑙𝐶𝑙3
CH3 – CH2 – OH + HCl → CH3 – CH2 – Cl + H2O
3. The reaction of alcohols with thionyl chloride in the presence of pyridine to give chloro-
alkanes is known as Darzen’s process.
𝑝𝑦𝑟𝑖𝑑𝑖𝑛𝑒
CH3CH2OH + SOCl2 → CH3CH2Cl + SO2 + HCl
4. Alkenes on reaction halogen acids, HX give haloalkanes.
>C = C< + H – X → >CH – CX<
It is an example of electrophilic addition reaction. The reaction proceeds as follows:
𝑟𝑒𝑎𝑟𝑟𝑎𝑛𝑔𝑒𝑚𝑒𝑛𝑡 𝑖𝑓 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒
Alkene 𝐻+ → Carbocation → Carbocation 𝑋− →
haloalkane. For example, CH3 – CH = CH2 + HCl → CH3 –
CH(Cl) – CH3
5. Markovnikoff’s rule and anti Markovnikoff’s rule: According to M rule, during the
addition of unsymmetrical reagents to the unsymmetrical alkenes, the negative part is
bonded to that doubly bonded carbon atom which has lesser number of H-atom and the
positive part is attached to other doubly bonded carbon atom.
For example, CH3 – CH = CH2 + HBr → CH3 – CH (Br) – CH3
𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒
Using anit M rule, CH3 – CH = CH2 + H – Br → CH3 – CH2 – CH2 - Br
81
6. Finkelstein reaction: In this reaction, chloro-alkanes or bromo-alkanes are treated with
NaI or KI in acetone as solvent to give corresponding iodo-alkanes.
𝑎𝑐𝑒𝑡𝑜𝑛𝑒
For example, CH3 – CH2 – Cl + KI → CH3 – CH2 – I + KCl
7. Borodine Hunsdicker’s reaction: In this reaction, the silver salt of carboxylic acid is
treated with Br2 in CCl4 as solvent to give bromoalkane. Here, bromoalkane formed,
contains one carbon atom less than in silver salt of carboxylic acid.
𝐶𝐶𝑙4
For example, R – COOAg + Br2 → R – Br + AgBr + CO2
8. Swart’s reaction: In this reaction, chloro-alkanes or bromoalkanes are treated with
inorganic fluoride such as SbF3, SbF5, AgF, HgF2 etc. to give corresponding fluoroalkanes.
For example, 3 CH3 – CH2 – Cl + SbF3 → 3 CH3 – CH2 – F + SbCl3
9. Alkyl halides are insoluble in water due to their inability to form H-bonds with water
molecules.
10. Differences between SN1 reactions and SN2 reactions:
S. No. SN2 reactions SN1 reactions

1 Rate = k [substrate][nucleophile] Rate = k [substrate]
2 Second order reactions First order reactions
3 One step reaction Two step reactions
4 Involves transition state Involve carbocation as intermediate
5 Always back side attack favours Both back as well as front side is possible
6 Walden inversion if substrate is Partial racemisation, if substrate is optically
optically active active
7 No rearrangement Rearrangement if possible
8 10 > 2 0 > 3 0 30 > 20 > 10
11. Substitution by –OH and formation of alcohols: R – X + KOH (aq.) → R – OH + KX

12. Substitution by –OR and formation of ethers, Williamson’s synthesis:
R – X + KO – R → R – O – R + KX
13. Substitution by NC- and formation of alkyl cyanides:
R – X + KCN (or NaCN) → R – CN + KX
-
14. Substitution by CN and formation of isocyanides: R - X + AgCN → R – NC + AgX
15. Substitution by O2N- and formation of nitroalkanes: R – X + AgNO2 → R – NO2 + AgX
16. Substitution by ONO- and formation of alkyl nitrites:
R –X + KNO2 (or NaNO2) → R ON =O + KX
17. Saytzeff’s rule: During dehydrohalogenation or 𝛽 elimination of haloalkanes, if two or
more alkenes are possible as the products, then more alkylated alkene will be the major
product.
CH3 – CH2 – CH(Cl) – CH3 + alk. KOH → CH3 – CH2 – CH = CH2 + CH3 – CH = CH – CH3
Minor product Major product
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
18. Reaction with Na metal: Wurtz’s reaction: R -X + 2 Na + X-R → R – R + 2 NaX
82
19. By halogenations of benzene: It is an example of electrophilic substitution reaction.
𝑎𝑛ℎ𝑦. 𝐴𝑙𝐶𝑙3
C6H6 + Cl2 → C6H5Cl + HCl
𝐶𝑢𝐶𝑙/𝐻𝐶𝑙
20. By Sandmeyer’s reaction: C6H5 - 𝑁2+ 𝐶𝑙 − → C6H5 – Cl + N2 + HCl
𝐶𝑢/𝐻𝐶𝑙
21. By Gatterman’s reaction: C6H5 - 𝑁2+ 𝐶𝑙 − → C6H5 – Cl + N2 + HCl
22. By Balz’s Schiemann’s reaction:
𝐻𝐵𝐹4
C6H5 - 𝑁2+ 𝐶𝑙 − → C6H5 - 𝑁2+ 𝐵𝐹4− + HCl
𝐻𝑒𝑎𝑡
C6H5 - 𝑁2+ 𝐵𝐹4− → C6H5 – F + N2 + BF3
23. Preparation of iodobenzene:
𝑊𝑎𝑟𝑚
C6H5 - 𝑁2+ 𝐶𝑙 − + KI → C6H5 – I + N2 + KCl
24. Comparison of reactivity of haloalkanes and haloarenes towards nucleophilic
substitution reactions: The low reactivity of haloarenes is due to resonance in
haloarenes. Due to resonance, there is partial double bond character in C – X bond. As a
result, its cleavage is very difficult. In haloalkanes, there is no resonance and there is
pure single C – X bond which undergo cleavage more easily.
623 𝐾 𝑎𝑛𝑑 60 𝑎𝑡𝑚
25. Dow’s process: C6H5Cl + NaOH → C6H5 - OH + NaCl
476 𝐾 𝑎𝑛𝑑 𝑝𝑦𝑟𝑖𝑑𝑖𝑛𝑒
26. C6H5Cl + CuCN → C6H5 - CN + CuCl
27. 2 C6H5Cl + 2 NH3 + Cu2O → 2 C6H5 – NH2 + 2 CuCl + H2O
28. Reduction: C6H5Cl + 2 [H] → C6H6 + HCl.
Reducing agent: LiAlH4, Na-Al/NaOH, H2/Pd-C
𝑇𝐻𝐹
29. Reaction with Mg: C6H5Cl + Mg → C6H5MgCl [Grignard reagent]
30. Fittig reaction: C6H5Cl + 2 Na + ClH5C6 → C6H5 – C6H5 + 2 NaCl
31. Wurtz Fittig reaction:
C6H5Cl + 2 Na + Cl – CH3 → C6H5 – CH3 + 2 NaCl
MCQ [Only one option is correct]

Level – 1
1. Which of the following can be used for the preparation of 1-chloropropane?
(a) Propene and HCl in the presence of peroxide
(b) Propene and HCl in the absence of peroxide
(c) Propene and Cl2 followed by treatment with aqueous KOH
(d) Propan-1-ol and SOCl2/pyridine
2. Groove’s process is used for the preparation of
(a) CH3CH2Cl (b) CH3CH2F (c) CH3CH2Br (d) CH3CH2I
83
3. Alkyl halides can be prepared by all the following methods except
𝑍𝑛𝐶𝑙2 𝑆𝑂2 𝐶𝑙2 , 475𝐾
(a) CH3CH2OH + HCl (g) → (b) CH3CH = CH2 →
𝐶𝐶𝑙4 , 𝑅𝑒𝑓𝑙𝑢𝑥
(c) CH3CH2OH + NaCl → (d) CH3COOAg + Br2 →
4. For the preparation of n-propyl bromide from n-propyl alcohol, which of the following
reagent is most preferred?
(a) Red P and Br2 (b) Br2 and CH3COOH (c) HBr and H2SO4 (d) NaBr
5. The method to prepare fluoro-ethane is
𝐻2 𝑆𝑂4 𝑎𝑛𝑑 ℎ𝑒𝑎𝑡 𝑆𝑏𝐹5
(a) CH3CH2OH + HF → (b) CH3CH2OH + HF →
ℎ𝑒𝑎𝑡 𝑙𝑖𝑔ℎ𝑡
(c) CH3CH2Cl + Hg2F2 → (d) CH3CH3 + F2 →
6. The allylic bromination can be carried out with
(a) HBr/H2O2 (b) HOBr (c) Br2/CS2 (d) NBS
𝑎𝑙𝑐.𝐾𝑂𝐻 𝑎𝑛𝑑 ℎ𝑒𝑎𝑡 𝑆𝑂2 𝐶𝑙2 ,475𝐾
7. (CH3)3CCl → “A” → “B”. Compound “B” in the sequence is
(a) 3-chloro-2-methylpropene (b) 1-chloro-2-methylpropene
(c) 1, 2-chloro-2-methylpropene (d) 1, 2-chloro-2-methylpropane
8. Neopentyl alcohol on treatment with HBr gives
(a) neopentyl bromide (b) 2-bromo-2-methylbutane
(c) 2-methylbut-2-ene (d) 2-methylbut-1-ene
9. Which of the following cannot be prepared by direct halogenations of benzene?
(a) Iodobenzene (b) Chlorobenzene (c) Bromobenzene (d) Fluorobenzene
10. The carbon atom holding halogen in haloarenes is
(a) sp2 hybridized (b) sp3 hybridized (c) sp hybridized (d) dsp2 hybridized
Level – 2
1. The I.U.P.A.C. name of β-phenylethylbromide is
(a) 2-bromo-1-phenylethane (b) 1-bromo-2-phenylethane
(c) 2-bromo-1-phenylethylene (d) 2-bromo-2-phenylethane
2. For the preparation of chloro-ethane,
(a) HCl gas is passed through ethanol (b) ethanol is treated with thionyl chloride
(c) ethyl sulfide is treated with NaCl (d) all the above are correct
3. The alkyl halides that can be made by free radical halogenations of alkanes are
(a) RCl and RBr but not RF and RI (b) RF and RCl but not RBr and RI
(c) RF, RCl, RBr and RI (d) RF, RCl, RBr but not RI
4. Which of the following alkyl halide has maximum density?
(a) CH3CH2CH2I (b) CH3CH2I (c) CH3Br (d) CH3I
5. Among the following, which one has highest boiling point?
(a) CH3CH2F (b) CH3CH2Cl (c) CH3CH2Br (d) CH3CH2I
6. Which of the following cannot be used to prepare an alkyl chloride from an alcohol?
(a) HCl and anhy. ZnCl2 (b) NaCl (c) PCl5 (d) SOCl2
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7. Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl3 to form
(a) 3-propyl-1-chlorobenzene (b) n-propyl benzene
(c) isopropyl benzene (d) Mixture of a, b and c
8. HCl gas on passing through propene in the presence of benzoyl peroxide gives
(a) 2-chloropropane (b) allyl chloride (c) 1-chloropropane (d) both a and c
9. Silver benzoate reacts with bromine in the presence of carbon tetrachloride to form
(a) C6H6 (b) C6H5COBr (c) m-BrC6H5COOAg (d) C6H5Br
10. Toluene on reaction with N-bromosuccinimide gives
(a) p-bromoethylbenzene (b) o-bromoethylbenzene
(c) phenyl bromomethane (d) m-bromoethylbenzene
Level – 3
𝑋 𝑌
1. CH3 – CH2 – CH2Br → Product → CH3 – CH(Br) – CH3. In the sequence X and Y
are (a) dilute aqueous NaOH and HBr (b) conc. alc.
NaOH and HBr (c) dilute aqueous NaOH and Br2/CCl4 (d)
conc. alc. NaOH and Br2/CCl4
2. Which of the following will have maximum dipole moment?
(a) CH3F (b) CH3Cl (c) CH3Br (d) CH3I
2
3. Which of the following is an example of SN reaction?
(a) CH3 – CH(Br) – CH3 + OH- → CH3 – CH(OH) – CH3 + Br-
(b) CH3 Br + OH- → CH3 OH
𝐻2 𝑆𝑂4
(c) CH3CH2OH → CH2 = CH2 + H2O
(d) CH3 C(Br)(CH3)2 + OH- → CH3 C(OH)(CH3)2 + Br-
4. Butane Nitrile is formed by the reaction of KCN with
(a) propyl alcohol (b) butyl chloride (c) butyl alcohol (d) propyl chloride
𝑎𝑙𝑐 𝐾𝑂𝐻 𝐵𝑟2 𝐾𝐶𝑁
5. CH3CH2Br → “X” → “Y” → “Z”. The compound “Z” is
(a) CH3CH2CN (b) NC CH2CH2 CN (c) Br CH2CH2 CN (d) Br CH = CH Br
6. The reaction of benzyl chloride with NaCN followed by reduction with Na/C 2H5OH gives
(a) β-phenyl ethylamine (b) N-isobutyl aniline
(c) benzyl amine (d) aniline
7. R – OH + HX → R – X + H2O. The order of reactivity of different R –OH is
0 0
(a) 3 > 2 < 1 0 (b) 10 > 20 > 30
(c) 30 > 20 > 10 (d) 30 < 20 > 10
𝐾𝐶𝑁 𝑑𝑖𝑙 𝐻𝐶𝑙
8. CH3Cl → “A” → “B”. The compound “B” is
(a) HCOOH (b) CH3COOH (c) CH3NH2 (d) CH3COCH3
2
9. The SN mechanism proceeds through the intervention of
(a) carbanion (b) carbocation (c) transition state (d) carbene
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𝑎𝑙𝑐 𝐾𝑂𝐻 𝑁𝐵𝑆 𝐾𝐶𝑁
10. CH3CH2CH2Cl → “X” → “Y” → “Z”. The compound “Z” is
(a) (CH3)2 CH - CN (b) Br CH = CH CN
(c) CH2 = CH CH2CN (d) CH2 = CH CH(Br)CN
Answer Key
Level – 1
1 2 3 4 5 6 7 8 9 10
d a c a c d a b d a
Level -2
1 2 3 4 5 6 7 8 9 10
b b a d d b c a d c
Level – 3
1 2 3 4 5 6 7 8 9 10
b b b d b a c b c c
Assertion Reason Type Questions:

Instructions: The following question consist two statements as Assertion and Reason.
While answering these questions, choose correctly any one of the following responses.
(a) If both Assertion and Reason are true and Reason is the correct explanation of
Assertion.
(b) If both Assertion and Reason are true and Reason is not the correct explanation of
Assertion.
(c) If Assertion is true and Reason is false. (d) If both Assertion and Reason is false.
1. Assertion: Iodoalkanes undergo nucleophilic substitution more readily than
bromoalkanes.
Reason: Iodine is a better leaving group due to its larger size which makes the covalent
bond weaker.
2. Assertion: SN2 mechanism leads to racemisation.
Reason: The incoming nucleophile attacks the compounds from the side opposite to the
outgoing nucleophle in SN2 mechanism.
3. Assertion: Haloalkanes react with KCN to form cyanoalkanes.
Reason: KCN completely ionises in solution.
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4. Assertion: Chlorobenzene is less polar than chloro methane.
Reason: Chlorobenzene has a longer C-Cl bond due to resonance.
5. Assertion: Presence of nitro group at ortho or para position makes nucleophilic
substitution in chlorobenzene easier.
Reason: Nitro group donates electrons to stabilize the intermediate ion formed by the
addition of the incoming nucleophile.
6. Assertion: Chloroform must be stored in dark coloured bottles.
Reason: Chloroform reacts with air to form phosgene.
7. Assertion: Chlorobutane has lower boiling point than 2-Chloro-2-methylpropane.
Reason: The intermolecular forces in straight chain compounds are stronger than in
branched compounds.
8. Assertion: Benzyl chloride undergoes nucleophilic substitution through SN1 mechanism.
Reason: Benzyl carbocation is resonance stabilized.
9. Assertion: Haloalkanes are only sparingly soluble in water.
Reason: Haloalkanes cannot form hydrogen bonds with water molecules.
10. Assertion: Propene reacts with HBr to form 2-bromopropane.
Reason: The intermediate carbocation formed will be secondary since it is more stable
than primary.
Answer Key
1 2 3 4 5 6 7 8 9 10
a d a c c b a a b a
Case study
The polarity of carbon-halogen bond of alkyl halides is responsible for their nucleophilic
substitution, elimination and their reaction with metal atoms to form organometallic
compounds. Nucleophilic substitution reactions are categorized into SN1 and SN2 on
the basis of their kinetic properties. Chirality has a profound role in understanding the
reaction mechanisms of SN1 and SN2 reactions. SN2 reactions of chiral alkyl halides are
characterized by the inversion of configuration while SN1 reactions are characterized by
racemisation.
(a) What is Saytzef’s rule? Explain with one example.
(b) What are ambident nucleophiles? Explain with an example.
(c) What happens when
(i) n-butyl chloride is treated with alcoholic KOH
(ii) methyl chloride is treated with KCN?
OR
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Identify A, B, C and D in the following:
𝑃𝐵𝑟3 𝑎𝑙𝑐.𝐾𝑂𝐻 𝐻𝐵𝑟 𝑁𝐻3
CH3CH2CH2OH → A → B → C → D
CBSE questions
1. Alkyl halides, though polar in nature, are immiscible in water. Explain why?
2. Arrange the following compounds in the increasing order of reactivity towards SN 2
reactions: 1-Bromo-3-methylbutane, 2-bromo-2-methylbutane, 3 - bromo -2-
methylbutane.
3. How will you convert ethanol to fluoroethane?
4. Why vinyl chloride is less reactive than ethyl chloride towards nucleophilic substitution
reactions?
5. The p-isomer of dichlorobenzene has higher melting point than its m-isomer and o-
isomer. Why?
6. How does chlorobenzene react with sodium metal in dry ether? What is the name of
reaction?
7. How is chloroform prepared form acetone? Write all the reactions involved.
8. Write one chemical test to distinguish between CH3CH2Br and C6H5Br.
9. A small amount of ethyl alcohol is always added to chloroform bottles during the
storage. Why?
10. (a) The dipole moment of chlorobenzene is lower than that of chloro cyclo hexane.
Why?
(b) Grignard reagent should be prepared under anhydrous conditions. Explain why?
11. Among the C6H5CH2Cl and C6H5CH(Cl)CHC6H5, which is more easily hydrolyzed by
aqueous KOH?
12. Which one in the following pairs of compounds undergoes SN2 reaction faster and why?
(a) -CH2Cl and -Cl (b) CH3CH2CH2CH2CH2I and CH3CH2CH2CH2CH2Cl
13. Haloalkanes give cyanides on reaction with KCN but isocyanides with AgCN. Explain
why?
14. Differentiate between SN1 and SN2 reactions?
15. Arrange following the decreasing order of reactivity towards SN1 reactions:
(a) CH3(Br)CHCH3, CH3CH2Br, CH2 = CH – Br, CH2 = CH – CH(Br)CH3
(b) ClCH2 – CH = CH – CH2CH3, CH3 – C(Cl) = CH CH2CH3,
CH3CH = CH – CH2CH2Cl, CH3CH = CHCH(Cl)CH3
16. How will the products differ when ethyl bromide reacts separately with
(a) aqueous KOH and alcoholic KOH (b) KNO2 and AgNO2?
17. Complete the following:
(a) C6H5 -Cl + NH3 + Cu2O → ………………….
(b) CH3CH2I + KCN → …………………………..
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18. When propene is heated with chlorine at 773 K, then product is substituted and not
addition in nature. Explain.
19. Which of the following has higher boiling point: 1-chloropentane and 2-chloro-2-
methylbutane?
20. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols
but in the presence of alcoholic KOH, alkenes are major products. Explain.
21. Explain why (i) alkyl halides though polar, are insoluble in water?
22. How the following conversions are carried out?
(i) toluene to benzyl alcohol (ii) but-1-ene to 1-iodobutane
(iii) tert-butyl bromide to isobutyl bromide (iv) ethanol to fluoro-ethane
23. Write short note on following:
(i) Balz Scheimann’s reaction (ii) mechanism of SN2 reaction
(iii) stereochemistry of SN1 reaction (iv) Grove’s process
24. Complete the following:
(i) C6H5CH2CH3 + Br2 ℎ𝜈 → ………………………………………………..
+
(ii) C6H5𝑁2 Cl + Cu/HCl → ………………………………………………..
(iii) (CH3)2CHCl 𝑁𝑎, 𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 → …………………………………………………..
25. Identify A, B, C and D in the following:
(i) CH3CH2CH2OH 𝑃𝐵𝑟3 → A 𝑎𝑙𝑐. 𝐾𝑂𝐻 → B 𝐻𝐵𝑟 → C 𝑁𝐻3 → D
(ii) CH3CH(Br)CH3 𝑎𝑙𝑐. 𝐾𝑂𝐻 → A 𝐻𝐵𝑟, 𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒 → B 𝑁𝑎𝐼, 𝑎𝑐𝑒𝑡𝑜𝑛𝑒 → C
𝑀𝑔, 𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 → D.
26. Explain why Haloarenes are much less reactive towards nucleophilic substitution
reactions than haloalkanes?
27. Discuss the preparation and uses of following:
(a) D.D.T. (b) Freon (c) CCl4
Subjective assignment
1. Write structures of the following compounds:
(a) 2-Chloro-3-methylpentane (b) 1-Chloro-4-ethylcyclohexane
(c) 4-tert. Butyl-3-iodoheptane (d) 1, 4-Dibromobut-2-ene
(e) 1-Bromo-4-sec. butyl-2-methylbenzene.
2. Identify all the monochloro structural isomers formed on free radical monochlorination
of (CH3)2CHCH2CH3.
3. Write the products of the following reactions:
(a) C6H5 CH = CH2 + HBr →
(b) CH3 CH2 CH = CH2 + HCl →
(c) C6H5 CH2 CH = CH2 + HBr 𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒 →
4. Why is sulphuric acid not used during the reaction of alcohols with KI?
89
5. Write structures of different dihalogen derivatives of propane.
6. Among the isomeric alkanes of molecular formula C5H12, identify the one that on
photochemical chlorination yields (a) A single monochloride.
(b) Three isomeric monochlorides. (c) Four isomeric monochlorides.
7. Draw the structures of major monohalo products in each of the following reactions:
(a) cyclohexanol + SOCl2 → (b) CH3 CH2 Br + NaI →
(c) cyclohexene + Br2 𝑈. 𝑉. 𝑙𝑖𝑔ℎ𝑡 →
8. Arrange each set of compounds in order of increasing boiling points:
(a) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(b) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.
9. Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the main product. Explain.
10. In the following pairs of halogen compounds, which would undergo SN 2 reaction faster?
(a) CH3 -CH2 -CH2 -CH2 -Cl and CH3 -CH2 -CH2 -CH2 –I
(b) cyclohexylchloromethane and chlorocyclohexane
11. Predict the order of reactivity of the following compounds in SN 1 and SN2 reactions:
(a) The four isomeric bromobutanes
(b) C6H5CH2Br, C6H5CH(Br)C6H5, C6H5CH(Br)CH3, C6H5C(Br)(CH3)C6H5
12. Identify chiral and achiral molecules in each of the following pair of compounds:
(a) CH3CH(Br)(OH) and CH3CHBr2 (b) CH3CH(OH)CH2CH2CH3 and CH3CH2CH(OH)CH2CH3
(c) CH3CH(Br)CH2CH3 and CH3CH2CH2CH2Br
13. Although chlorine is an electron withdrawing group, yet it is ortho-, para - directing in
electrophilic aromatic substitution reactions. Why?
14. Which alkyl halide from the following pairs would you expect to react more rapidly by
an SN2 mechanism? Explain your answer.
(a) CH3CH2CH2CH2Br or CH3CH2CHBrCH3 (b) CH3CH2CHBrCH3 and (CH3)3CBr
(c) (CH3)2CHCH2CH2Br or CH3CH2CH(CH3)CH2Br
15. In the following pairs of halogen compounds, which compound undergoes faster SN 1
reaction? (a) (CH3)3CCl or CH3CH2CHClCH2CH3
(b) CH3CH2CH2CH2CH2CHClCH3 or CH3CH2CH2CH2CH2CH2Cl
16. Which compound in each of the following pairs will react faster in SN 2 reaction with –
OH? (a) CH3Br or CH3I (b) (CH3)3CCl or CH3Cl
17. Predict all the alkenes that would be formed by dehydrohalogenation of the following
halides with sodium ethoxide in ethanol and identify the major alkene: (a) 1-Bromo-1-
methylcyclohexane (b) 2-Chloro-2-methylbutane (c) 2,2,3-Trimethyl-3-bromopentane.
18. Explain why
(a) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(b) alkyl halides, though polar, are immiscible with water?
(c) Grignard reagents should be prepared under anhydrous conditions?
19. Arrange the compounds of each set in order of reactivity towards SN 2:
(a) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
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(b) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane
(c) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-
3-methylbutane.
20. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolyzed by aqueous KOH?
21. p-Dichlorobenzene has higher m.eling poin and solubility than those of o- and m-
isomers. Discuss.
22. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols
but in the presence of alcoholic KOH, alkenes are major products. Explain.
23. What happens when
(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN?
24. Primary alkyl halide C4H9Br “A” reacted with alcoholic KOH to give compound “B”.
Compound “bb” is reacted with HBr to give (c) which is an isomer of (a). When (a) is
reacted with sodium metal it gives compound (d), C8H18 which is different from the
compound formed when n-butyl bromide is reacted with sodium. Give the structural
formula of (a) and write the equations for all the reactions.
Hint and solution:

Solution 2: In the given molecule, there are four different types of hydrogen atoms.
Replacement of these hydrogen atoms will give the following
(CH3)2CHCH2CH2Cl (CH3)2CHCH(Cl)CH3 (CH3)2C(Cl)CH2CH3 CH3CH(CH2Cl)CH2CH3
Solution 3: (a) C6H5 CH(Br) – CH3 (b) CH3 CH2 CH(Cl) – CH3 (c) C6H5 CH2 CH2 CH2Br
Solution 9: KCN is ionic in nature and provides cyanide ions in solution. Although both
carbon and nitrogen atoms are in a position to donate electron pairs, the attack takes
place mainly through carbon atom and not through nitrogen atom since C—C bond is
more stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen
is free to donate electron pair forming isocyanide as the main product.
Solution: 11.
(a) CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1)
CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2)
(b) C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br (SN1)
C6H5C(CH3)(C6H5)Br < C6H5CH(C6H5)Br < C6H5CH(CH3)Br < C6H5CH2Br (SN2)
Solution 12: (a) CH3CH(Br)(OH) (b) CH3CH(OH)CH2CH2CH3 (c) CH3CH(Br)CH2CH3
Solution 13: Chlorine withdraws electrons through inductive effect and releases
electrons through resonance. Through inductive effect, chlorine destabilises the
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intermediate carbocation formed during the electrophilic substitution.
Through resonance, halogen tends to stabilise the carbocation and the effect is more
pronounced at ortho- and para- positions. The inductive effect is stronger than
resonance and causes net electron withdrawal and thus causes net deactivation. The
resonance effect tends to oppose the inductive effect for the attack at ortho- and para
positions and hence makes the deactivation less for ortho- and para attack. Reactivity is
thus controlled by the stronger inductive effect and orientation is controlled by
resonance effect.
92
UNIT 7 - ALCOHOLS, PHENOLS AND ETHERS
Syllabus: 06 marks
Alcohols: Nomenclature, methods of preparation, physical and chemical properties (of primary alcohols only),
identification of primary, secondary and tertiary alcohols, mechanism of dehydration, uses with special reference to
methanol and ethanol.
Phenols: Nomenclature, methods of preparation, physical and chemical properties, acidic nature of phenol,
electrophillic substitution reactions, uses of phenols.
Ethers: Nomenclature, methods of preparation, physical and chemical properties, uses.
Short Notes
Organic Compound Structure of Functional group IUPAC name
Alcohols R-O-H Alkanol
Phenols C6H5-O-H Phenol
Ethers R-O-R Alkoxyalkane
Classification Alcohols Phenols

MONOHYDRIC CH3CH2OH
(Contain one -OH
group) ETHANOL
ETHYL ALCOHOL
DIHYDRIC CH2OH-CH2OH
(Contain two -OH
group) ETHANE-1,2 DIOL
ETHYLENE GLYCOL Catechol

TRIHYDRIC CH2OH-CHOH-CH2OH
(Contain three -
OH group) PROPANE1,2,3 TRIOL
GLYCEROL Phloroglucinol
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B. On the basis of hybridization of carbon atom to which-OH group is attached
Csp3-OH Alkanols (1○,2○,3○) CH3CH2CH2-OH, (CH3)2CH-OH,

(CH3)3C-OH
Propyl alcohol Isopropyl
alcohol tertiary butyl alcohol
Allylic alcohols CH2=CH-CH2OH Prop-2-enol
Benzylic alcohols C6H5CH2OH Benzyl
alcohol(Phenylmethanol)
Csp2-OH Phenols C6H5OH
Vinylic alcohol CH2=CH-OH Vinyl alcohol
(Ethenol)
PREPARATION OF ALCOHOLS
I By Hydration of
Alkenes
Ii Reduction of
Aldehyde
Iii Reduction of
ketones
Iv Reduction of
Carboxylic Acids
V Reduction of Esters
vi From Grignard
reagent ( number
of carbon atom
increases)
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PREPARATION OF PHENOLS
I From Haloarenes
Ii From Benzene
sulphonic acid
Iii From Aniline
iv From Cumene
{Commercial
manufacture)
PHYSICAL PROPERTIES
1. BOILING POINTS
S.NO FACT ABOUT BOILING POINTS REASON

1 Increases with increase in the number Due to increase in strength of Vander
of carbon atoms Waal’s forces
2 Decrease with increase in branching of Decrease in Vander Waal’s forces due
carbon chain to decrease in surface area
3 Alcohols and phenols have higher Due to the presence of intermolecular
boiling points compared to ethers, hydrogen bonding in alcohols and
halo compounds and carbonyl phenols.
compounds of comparable masses.
2. SOLUBILITY
1 Alcohols and Phenols are miscible in Due to formation of H-bonds with water
water in all proportions. molecules extensively
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2 Solubility decreases with increase in Due to hydrophobic interactions of the
size of alkyl /aryl group large -R group
A. Chemical properties of alcohols and phenols I. Reactions involving cleavage of O–H bond: Alcohols react as
nucleophiles:
a. Reaction with metals (acidic character) 2RO-H+ 2Na-→2RO-Na + H2(g)

sodium alkoxide
C6H5O-H +NaOH-→C6H5O-Na +H2O
Sodium phenoxide
b. Esterification H+
RO-H + HO-COR’-----→RCOOR’ + H2O
H+
RO-H + (RCO)2O---→RCOOR’ + R’COOH
H+
RO-H +Cl-COR---→ RCOOR’ +HCl
Note: comparison of Acidic nature
1 For Isomeric alcohols,10 >20 >30 Due to electron releasing effect of R groups
that stabilise the carbocation
2 ROH>H2O>C6H5OH Due to relative stability of phenoxide ion via
resonance
3 In Substituted phenols, o-Cresol<Phenol< Electron- withdrawing group(-NO2) enhance
o-nitrophenol the ease of cleavage of O-H bond
II. Reactions of alcohols involving cleavage of carbon – oxygen (C–O) bond:
A With Hydrogen
halide(HX)
B With Phosphorus
trihalide (PX3)
C Dehydration
D Oxidation
E Dehydrogenation
Note: The relative ease of reaction of alcohols with HX follows the order:30 >20 >10 . This is due to the relative stability
of tertiary carbocations compared to secondary and primary carbocation.
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ETHERS(R-O-R)
Classification:
Symmetrical Ethers (R-O-R) Unsymmetrical ethers(R-O-R’)
CH3-O-CH3 Methoxymethane (Dimethyl CH3-O-C2H5 Methoxyethane
ether)
CH2CH3-O-CH2CH3 (CH3O)CH(CH3)CH2CH3
Ethoxyethane (diethylether) 2-Methoxybutane
(sec-Butylmethyl ether
Preparation of Ethers
1. By dehydration of primary alcohols at 413 K
2. Williamson’s synthesis
(note: to prepare ethers containing secondary or tertiary alkyl/aryl group must be a part of alkoxide ,
primary alkyl halide is most suitable in all cases.)
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Chemical properties:
A. Reaction i. ROR + 2HI-→2RX +H2O Cleavage of C-O bond on

with HI either side of etheral
oxygen takes place.
ii. ROR’ +HI →RI + R’-OH If R’ is 20 or 30 , it forms the
alkyl halide preferably
(stable carbocation)
iii. C6H5-O-R+ HI -→C6H5OH + RX The cleavage of C-O bond is
difficult due to partial
double bond character
iv.R3C-O-R’ +HI-→R’OH + R3C-I Due to formation of stable
30 Carbocation
Note: the order of reactivity of hydrogen halides follows the order: HI> HBr>HCl
B. Electrophilic substitution:
The Alkoxy(-OR) group in aromatic ethers is o-/p- directing and activates the benzene ring towards electrophilic
substitution.
I Halogenations
II Nitration
III Friedal craft

alkylation
IV Friedal craft
acetylation
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ALCOHOLS, PHENOLS AND ETHERS
LEVEL 1
1. When phenol is treated with CHCl3 and NaOH, the product formed is
(a) benzaldehyde ( b) salicylaldehyde (c) salicylic acid (d) benzoic acid
2. The major product obtained on iteraction of phenol with NaOH and CO2 is
(a) benzoic acid (b) salicylaldehyde (c) salicylic acid (d) phthalic acid
3. Ethers are isomeric with (a) aldehydes (b) vinyl alcohols (c) alcohols (d) ketones
4. Ethanol on warming with conc H2SO4 at 413 K gives
(a) ethene (b) diethyl ether (c) dimethyl ether (d) ethyl hydrogen sulphate
5. Conversion of chloromethane into Methanol involves :
(a) SN1 mechanism (b) SN2 mechanism
(c) both (a) and (b) (d)elimination –addition mechanisn
6. Phenol on treatment with excess of conc. HNO3 gives
(a) o-nitrophenol (b) p-nitrophenol (c) o and p nitrophenol (d) 2,4,6 trinitrophenol
7. Ethene reacts with alkaline KMnO4 solution to form which substance also used as an Antifreeze.
(a) Glycerol (b) Glycol (c) Propanol (d) Ethanol
LEVEL 2
8. Which of the following will not form a yellow precipitate on heating with an alkaline solution of iodine ?
(a) butan-2-ol (b) methanol (c) ethanol (d) propan-2-ol
9. Propan-1-ol and propan-2-ol can be distinguished by
(a) oxidation with alkaline KMnO4 followed by reaction with Fehling’s solution
(b) oxidation with acidic dichromate followed by reaction with Fehling’s solution
(c) oxidation by heating with copper followed by reaction with Fehling’s solution
(d) oxidation with conc H2SO4 followed by reaction with Fehling’s solution
10. The best reagent to convert pent-3-en-2-ol into pent-3-en-2-one is
(a) acidic permanganate (b) acidic dichromate
(c) chromic anhydride in glacial acetic acid (d) pyridinium chlorochromate
11. Which of the following alcohols undergoes acid catalysed dehydration to alkenes most readily?
(a) (CH3)2CHCH2OH (b) (CH3)3COH (c) CH3CHOHCH3 (d) CH3CH2CH2OH
12. Which of the following Grignard reagent is suitable for the preparation of 3-Methyl-butan-2-ol?
(a) butanone + methyl magnesium bromide (b) acetone + ethyl magnesium bromide
(c)acetaldehyde + isopropyl magnesium bromide (d) ethyl propionate + methyl magnesium bromide
LEVEL 3
13. The products obtained when benzyl phenyl ether is heated with HI in the mole ratio 1:1 are
(1)phenol (2) benzyl alcohol (3)benzyl iodide (4) iodobenzene
(a) 1 and 3 only (b) 3 and 4 only (c)1 and 4 (d)2 and 4 only
14. Anisole reacts with HI at 373K to give
(a) C6H5I + CH3OH (b) CH3I + C6H5OH
(c) C6H5CH2OH + CH3I (d) CH3CH2I + C6H5OH
15. The correct order of acidic strength of the following compounds :
I. Phenol II. P-cresol III. M-nitrophenol IV. P-Nitrophenol
(a) IV>III>I>II (b) II>IV>I>III (c) I>II>IV>III (d) III>II>I>IV
99
16. Match the compounds in column I with the properties in column II
(a) (A)- (p) (B)- (r) (C)- (p), (s) (D) - (p), (q) (b) (A)- (q) (B)- (r) (C)-(p) (D)- (s)
(c) (A)- (p) (B)- (r) (C)- (p) (D)- (s) (d) (A)- (q) (B) -(p) (C) -(s) (D)- (r)
Column I Column II
(A)Butan-2-ol (p) less acidic than phenol
(B)3 -nitrophenol (q) gives alkene with Cu at 573 k
17. Which is
(C) P-cresol (r) more acidic than ethanol
the best reagent
(D) 2-methyl propan-2-ol (s) gives toluene on reduction with zinc dust
to convert
cyclohexanol with cyclohexene? a. Conc.HCl b.
Conc. HBr c. Conc. H3PO4 d. Conc. HCl with ZnCl2
ASSERTION-REASON TYPE QUESTIONS
In the following questions a statement of assertion followed by a statement of reason is given. Choose the correct answer
from the following choices:
a. Assertion and reason both are correct statements and the reason is the correct explanation of the assertion
b. Assertion and reason both are correct statements but the reason is not the correct explanation of the assertion.
c. Assertion is correct statement but reason is wrong statement.
d. Assertion is a wrong statement but reason is correct statement.
18. Assertion: the boiling points of alcohols are higher than those of hydrocarbons of comparable molecular mass
Reason: alcohols show intramolecular hydrogen bonding
19. Assertion : phenol undergoes Kolbe’s reaction but ethanol doesnot.
Reason: phenol is more acidic than ethanol
20. Assertion: the ease of dehydration of alcohols follows the order : primary> secondary > tertiary
Reason: dehydration proceeds through the formation of carbocations .
21. Assertion: Phenol is more acidic than alcohol
Reason: phenoxide ion is resonance stabilized
22. Assertion: O- and p- nitrophenols can be separated by steam distillation
Reason: o- isomer is steam volatile due to chelation by intramolecular H-bonding while p isomer is not steam volatile due
to association of molecules by intermolecular H-bonding
23. Assertion: Equimolar mixture of conc HCl and anhydrous ZnCl2 is called Lucas reagent
Reason: lucas reagent can be used to distinguish between methanol and ethanol.
24. Assertion: tert. Butyl methyl ether is not prepared by the reaction of tert. butyl bromide with Sodium methoxide.
Reason: Sodium methoxide is a strong nucleophile
25. Assertion: Reaction of CH3OH with phenyl magnesium bromide yields benzene.
Reason:CH3OH is stronger acid than Benzene
26. Assertion: During acid- catalysed esterification, oxygen atom of alcohol is present in ester molecule.
Reason: Esterification is an irreversible process.
27. CASE BASED QUESTION
Both alcohols and phenols are acidic in nature but phenols are more acidic than alcohols. Acidic strength of alcohols are
mainly depends upon the inductive effect. Acidic strength of phenols depends upon a combination of both inductive and
resonance effects of the substituents and its position on the benzene ring. Electron withdrawing groups increases the
acidic strength of phenols whereas electron donating groups decreases the acidic strength of phenols. Phenol is a weaker
acid than carboxylic acid.
Following questions are multiple choice questions . choose the most appropriate answer:
100
(i) phenols are highly acidic as compared to alcohols due to
(a) the higher molecular mass of phenols (b) the stronger hydrogen bonds in phenols
(c)alkoxide ion is a strong conjugate base (d) phenoxide ion is resonance stabilized
(ii)The correct order of acidic strength among the following is
(I) H2O (II) CH3CH2OH (III) C6H5OH (IV) p- Cl C6H4OH
(a) (III>(IV)>(II)>(I) (b) (IV)> (III)> (I)> (II) (c) (IV)>(III)>(II)>(I) (d) (I)>(II)>(IV)>(III)
OR
The correct decreasing order of pKa value is
(I) 3-Methoxy phenol (II) 4-Methyl phenol (III) 4-nitrophenol (IV) 3-chlorophenol
(a) (II)>(IV)>(I)>(III) (b) (IV)>(II)>(III)>(I) (c ) (III)>(II)>(IV)>(I) (d) (IV)>(I)>(II)>(III)
(iii) The compound that doesnot liberate CO2 on treatment with aqueous sodium bicarbonate solution is (a) benzoic acid
(b)benzenesulphonic acid (c)salicylic acid (d) carbolic acid
(iv) Most acidic among the following is
(a) o-nitrophenol (b)m-nitrophenol (c) p-nitrophenol (d) phenol
ONE MARK QUESTION
1. How would you obtain phenol from benzene ?
2. ortho-nitrophenol has lower boiling point than p-nitrophenol. Why ?
3. Out of CH3OH and C6H5OH , which one is more acidic ?
4. Why is (+--)Butan-2-ol optically inactive?
5. Give a chemical test to distinguish between Pentan-2-ol and Pentan-3-ol.
6. How can propan-2-one be converted into tert-butyl alcohol?
7. Explain how an –OH group attached to carbon atom in the benzene ring activates benzene towards substitution?
8. How would you obtain acetophenone from phenol ?
9. Write the structure and IUPAC name of Glycerol.
10. Suggest a reagent for conversion of ethanol to ethanal.
11. Suggest a reagent for conversion of ethanol to ethanoic acid
12. Dehydration of ethanol with conc H2SO4 at 413 K gives ______________.
13. Tertiary alcohols when passed over heated copper at 573 K gives ____________.
14. Ortho and para nitrophenols can be separated by _____________.
15. 100% pure ethanol is called __________.
16. Phenol has smaller/larger dipole moment than methanol
17. Ketones are reduced to primary /secondary alcohols.
18. Bond angle in dimethyl ether is more than in water. (true/false)
19. Phenols turn blue litmus red ( true or false)
TWO MARK QUESTION
20. Describe the mechanism of acid dehydration of ethanol to yield ethene
21. What happens when phenol is treated with (i) dil HNO3 (ii) conc HNO3
22. Explain the following behaviours :
(i) Alcohols are more soluble in water than the hydrocarbons of comparable molecular masses.
(ii) ortho-nitrophenol is more acidic than orthomethoxyphenol
23. How are the following conversions carried out ?
(i) Propene to propane-2-ol (ii) Benzyl chloride to Benzyl alcohol
24. Write the reactions involved a) phenol with Bromine water b) phenol with Bromine in CS2
25. Write the structural formula of a) di-isopropyl ether b) anisole
26. Give chemical tests to distinguish between compounds in each of the following pairs
a) phenol and benzyl alcohol b) butan-2-ol and 2-methyl propan-2-ol
27. Why Di-tert butyl ether cannot be prepared by williamson’s synthesis? Explain.
101
THREE MARK QUESTION
28. Explain the following with an example in each :
(i) Kolbe's reaction (ii) Reimer-Tiemann reaction (iii) Williamson ether synthesis
29. State the products of the following reactions : (i) CH3CH2CH2OCH3 + HBr →
(ii) C6H5OC2H5 + HBr -→ (iii) (CH3)3C — O C2H5 +HI -→
30. Name the reagent used in the following conversions:
(a) primary alcohol to aldehyde (b) butan-2-one to butan-2-ol
(c) phenol to 2,4,6 tribromophenol
31. How will you convert phenol into the following compounds?
(a) Benzoquinone (b) Salicylic acid (c) Anisole
32. Write a short note on
( a). Hydroboration-oxidation (b). Williamson’s synthesis (c). Riemer-Tiemann reaction
FIVE MARK QUESTION

33. Give a chemical test to distinguish between
(a). Propan-1-ol and Propan-2-ol (b). Ethanol and Phenol (c). Methanol and ethanol
(d). Tert.butyl alcohol and butyl alcohol (e). Anisole and Benzyl alcohol
34. (a). Compound A (C7H8O) is insoluble in aqueous sodium bicarbonate but dissolves in aqueous sodium hydroxide. It gives
characteristic colour with ferric chloride solution. When treated with bromine water it form a compound B(C7H5OBr3).
( i) Give the structure of (A) and (B).(ii) What would be the structure of (A) if it neither dissolves in aqueous sodium
hydroxide nor gives a characteristic colour with FeCl3?
(b).Draw the resonance structures of phenoxide ion
35. An organic compound(A) with molecular formula C8H16O2 was hydrolysed with dilute sulphuric acid to give carboxylic acid
(B) and an alcohol(C). Oxidation of (C) with chromic acid also produced (B). On dehydration (C) gives but-1-ene. a. Identify
A, B and C. b. Write the chemical equations involved.
36. Ethanol, C2H5OH is obtained commercially by Fermentation from sugars. The Yeast added to molasses, sugarcane or
grapes converts sugars present in them into alcohol gradually. The enzymes released by yeast help in the process. Most
brewers and wineries use the biological method to manufacture the colourless and pleasant -smelling compound.
Commercial alcohol is blue, foul-smelling, poisonous and thus unfit for drinking.
(i) Write the chemical equations involved in the biochemical conversion of sugars into alcohol.
(ii) How is denatured alcohol obtained?
(iii) What is the maximum purity achieved for ethanolic solution during fractional distillation? Why?
ANSWER KEY
1 B 9 C 17 C 25 C
2 C 10 D 18 C 26 D
3 A 11 B 19 B 27 i D
4 B 12 C 20 D OR 27 i B
5 B 13 A 21 A 27ii A
6 D 14 B 22 A 27 iii D
7 B 15 A 23 C 27 iv C
8 B 16 A 24 B
102
SOLUTIONS
1. Chlorobenzene reacts with NaOH at high temp and pressure forms Sodium phenoxide which reacts with H+ ion to form
phenol.
2. Orthonitrophenol undergoes intramolecular H-bonding
3. C6H5OH
4. It’s a racemic mixture
5. Iodoform test is given by pentan-2-ol
6. Propan-2-one treated with CH3MgBr followed by hydrolysis
7. –OH is +R group and increases electron density at ortho and para position
8. Phenol with zinc dust gives benzene . Acetylation of benzene gives acetophenone
9. Propan-1,2,3 triol
10. PCC
11. Alk KMnO4 or Acid K2Cr2O7
12. Ethoxy ethane
13. Alkene
14. Steam distillation
15. Absolute alcohol
16. Smaller
17. Secondary
18. True
19. True
20.
21. I) with dilute HNO3 mixture of ortho and para nitrophenol ii) with conc HNO3 2,4,6 trinitrophenol
22. I) alcohols have intermolecular H-bonding ii) –NO2 is electron withdrawing group
23. I) hydration of alkene ii) aq KOH
24.
25. Correct structure

26. I) Phenol form white precipitate with Br2 water ii) butan-2-ol gives yellow ppt with NaOH /I2
27. Tert butyl forms alkene
103
28. Correct reactions
29. I) CH3CH2CH2OH + CH3Br ii) C6H5OH + C2H5Br iii) (CH3)3C-I + CH3CH2OH

30. (a) PCC or CrO3 (b) LiAlH4 (c) Conc HNO3
31. (a) Oxidation with acidified potassium dichromate (b) Treatment with carbon tetrachloride in presence of NaOH (see
RiemerTiemann reaction) (c) NaOH CH3Br
Phenol--------→ Sodium phenoxide--------→ Anisole [Write equations]
32. Refer NCERT
33. (a) With Lucas reagent (Conc.HCl/ Anhyd. ZnCl2), in Propan-2-ol turbidity will appear after 5minutes in cold but not in
Propan -1-ol. (b). Phenol gives violet colouration with FeCl3 solution (c). Ethanol will form a yellow ppt. of Iodoform with
iodine in Sodium hydroxide solution, not methanol. (d). With Lucas reagent Tert.butyl alcohol yields turbidity immediately
in cold butyl alcohol gives turbidity only on heating. (e). Benzyl alcohol will evolve H2 gas on treatment with sodium metal
not anisole. Hint:[Write chemical equation for the positive test only]
34. (a) The compound A has a phenolic group, moreover the methyl group should be present at the meta position. On
bromination 2,4,6-Tribromo-3-methyl phenol(B) is obtained. [write the chemical equation] (b). The compound (A) which is
insoluble in aqueous sodium hydroxide nor gives a characteristic colour with FeCl3 can be Anisole or Benzyl alcohol.
[Draw their structures]
35. (A)-Butyl butanoate (B)-Butanoic acid (C) – n- Butyl alcohol [Draw the structural formula and write the chemical
equations for the stated reactions]
36. (i). (a) The enzyme Invertase converts sucrose to Glucose and Fructose.
Invertase
C12H22O11 + H2O---------------------→ C6H12O6 + C6H12O6
Sucrose Glucose Fructose
(b) Then zymase causes fermentation of conversion of Glucose and Fructose into ethanol.
Zymase
2C2H5OH + 2CO2------------→C6H12O6
(ii). Addition of copper sulphate(blue) and Pyridine (foul-smelling liquid) to commercial alcohol to make it unfit for drinking
is referred to as denatured alcohol. (iii).During fractional distillation ethanol-water mixture form a minimum boiling azeotrope
at 95% (by Volume) composition and cannot be further separated.
WORKSHEET 1
1. Name the reagents used in the following reactions:
(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
104
2. Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol.
(iii) Treating phenol wih chloroform in presence of aqueous NaOH
3. Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with that of ethanol.
4. Write the equations involved in the following reactions:
(i) Reimer - Tiemann reaction (ii) Kolbe’s reaction
5. Arrange the following compounds in increasing order of their acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol.
6. Arrange the following sets of compounds in order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
7. What happens when ethanol is heated at 443 K? write the mechanism.
105
WORKSHEET 2
106
WORKSHEET 3
107
--------X-------X---------
108
UNIT 8 - ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
(GIST OF THE LESSON)
Syllabus / Curriculum
➔Nomenclature and structure of carbonyl Group
➔Preparation of Aldehydes and Ketones
➔Physical properties of Aldehydes and Ketones
➔Chemical reactions of Aldehydes and Ketones
➔Uses of Aldehydes and Ketones
➔Nomenclature and structure of carboxyl group
➔Methods of Preparation of carboxylic Acids
➔Physical properties & chemical reactions of Carboxylic acids
➔Uses of carboxylic acids
109
➔IMPORTANT TERMS AND DEFINITIONS IN CHAPTER:
1. Carbonyl compounds - The organic compounds having carbonyl group -C=O as the functional unit are called
carbonyl compounds. These include Carbonyl compounds. I
Carbonyl compounds General Formula Examples
HCHO formaldehyde (methanal), CH3CHO acetaldehyde

(Ethanal), C6H5CHO Benzaldehyde
O
Aldehydes II
R - |C - H
O CH3 COCH3 Acetone (Propanone), C6 H5 COCH3

II acetophenone.
Ketones
R - |C - R'
CH3COOH acetic acid (ethanoic acid), C6H5 COOH benzoic

O
II acid
Carboxylic acids C| - OH
R -R-C-OH
2. Nucleophilic addition reaction: Addition reaction which are initiated by nucleophiles are called nucleophilic addition
reaction. Nucleophiles are CN-, Cl-, OH- etc.
Mechanism - Nucleophile attacks electrophilic sp2 hybridised carbon and the hybridization changes to sp3 and a
tetrahedral alkoxide intermediate is formed which reacts with proton to form addition product.
110
3. Structure of Carbonyl group –
Carbonyl carbon atom is sp2 hybridised and form 3--() bonds and one  - bonds with oxygen by overlapping with p-
orbital of oxygen. The bond angles in 120o and structure is trigonal planar.
4. Aldol Condensation -
The compounds having alcoholic group and aldehyde / ketone group
Aldehyde and ketone having at least one  hydrogen atom undergo aldol condensation in presence of dil. NaOH as
catalyst to form β-hydroxy aldehydes (aldol) or β-hydroxy ketones (ketol).
111
5. Cross Aldol condensation -
When aldol condensation is carried out between two different aldehydes and / or ketones, it is called cross aldol
condensation. If both of them contain α-hydrogen atoms, it gives a mixture of four products. This is illustrated below
by aldol reaction of a mixture of ethanal and propanal.
6. Acetals & Ketals - Aldehydes react with one equivalent of monohydric alcohol in the presence of dry hydrogen chloride
to yield alkoxy alcohol intermediate, known as hemiacetals, which further react with one more molecule of alcohol
to give a gem–dialkoxy compound known as acetal as shown in the reaction. Similar reactipons taks place with
ketones to form ketals.
7. Rosenmund Reaction
8. Friedel - crafts acetylation -
9. Hell-volhard Zelinsky reaction - Reaction of carboxylic acids having an  H. atom with Cl2 / Br2 in presence of red P to
form  - Chloro / Bromo acids.
112
- C=O
10. Clemmensen reduction - Reduction of group of Aldehydes and ketones to CH2 by Zn - Hg and HCl (Conc.)
ǀ
11. Wolf - Kishner reduction of C = 0 group of Aldehydes and ketones to CH2 by hydrazine followed by pot. Hydroxide
and ethylene glycol.
12. Cannizzaro - reaction: Aldehyde which do not have an -hydrogen atom, undergo self oxidation and reduction
(disproportion) reaction with cone. Alkali.
13. Structure of carboxyl group :
O O- O-
-C -C -C
: O : O
.. - H
O
.. - H
.. - H
I II III
All bonds lie in one plane and separated by about 1200 C is Sp2 hybridised
structure is trigonal planar.
14. Decarboxylation - Sodium salts of acids when heated with soda lime, alkanes are formed.
113
CH3 COONa + NaOH (CaO) → CH4 + Na2CO3
Sodium acetate Sodium lime Methane

15. Esterification - When acids are warmed with alcohol in presence of conc. H2SO4, pleasant fruity smelling esters are
formed. Conc. H2SO4, acts as dehydrating agent.
CH3 CO OH + C2H5O H Conc. H2SO4 CH3COOC2H5

-H2O Ethyl acetate
Mechanism of esterification
Tetrahedral intermediate
Protonated carboxylic acid
Protonated ester
16. Trans-esterification : The process in which esters react with alcohols in presence of mineral acids to form new alcohol
and ester.
R - COOR' + R" OH H+ R - COOR" + R' OH
17. Boiling points and solubility of aldehydes, ketones and carboxylic acids.
Carboxylic acids have higher boiling points than aldehydes, ketones and alcohols of comparable molecular masses
because it exists as dimmer through intermolecular hydrogen bonding.
Lower carboxylic acids, aldehyde and ketones are quite miscible with water due to hydrogen bonding.
18. Effect of substituents on the acidity of carboxylic acids.
114
e- Withdrawing group increases acidity of carboxylic acids by stabilizing its conjugate base through delocalization of
negative charge by Inductive or Resonance effects.
O O
EWG C EDG C
O O
EWG stabilises carboxylate anion and EDG destabilises the carboxylate anion and
strengthens the acid weakens the acid
115
MIND MAPPING--MEMORY MAPS
Figure -2
116
Figure-3
117
118
119
MCQ
Level -1
1. The oxidation of toluene to benzaldehyde by chromyl chloride is called

(a) Etard reaction
(b) Riemer–Tiemann reaction
(c) Wurtz reaction
(d) Cannizzaro’s reaction
2. The addition of HCN to carbonyl compounds is an example of
(a) Electrophilic addition
(b) Nucleophilic addition
(c) Nucleophilic substitution
(d) Electrophilic substitution
3. CH3CHO and C6H5CH2CHO can be distinguished chemically by
(a) Benedict’s test
(b) Iodoform test
(c) Tollens’ reagent test
(d) Fehling’s solution test
4. Substance X is heated with soda lime and gives ethane ,the substance X is
(a) ethanol
(b) ethanoic acid
(c) propanoic acid
(d) methanoic acid
5. Electrolysis of an aqueous solution of CH3 –COONa gives
a) methane
b) ethane
c) ethene
d) butane
6. Formic acid and acetic acid can be distinguished chemically by
(a) Reaction with HCl
(b) Iodoform test
(c) Reaction with NH3
(d) Tollens’ test
7. Which of the following will give Cannizzaro reaction ?
(a) CH3CHO
(b) CH3COCH3
(c) (CH3)3CCHO
(d) CH3CH2CHO
8. (A)Both Assertion and reason are true and reason is correct explanation of assertion
(B)Both Assertion and reason are true and reason is not correct explanation of assertion
(C)Assertion is true, reason is false
(D)Assertion is false, reason is true.
Assertion : Acetic acid in vapours state shows a molecular mass of 120.
Reason : CH3COOH typically undergoes dimeric intermolecular hydrogen bonding. It exists as a dimer in
the vapour state
9. Assertion : Aromatic carboxylic acids do not undergo Friedel-Crafts reaction
Reason :The carboxyl group is deactivating and the catalyst aluminium chloride (Lewis acid) gets
bonded to the carboxyl group).
120
10. Benedict solution provides
(a) Cu+2
(b) Cu+
(c) Ca+2
(d) Ba+2
Level-2
11. Which of the following reactions are ways to synthesize carboxylic acids?
I. Oxidation of an aldehyde
II. Hydrolysis of an anhydride
III. Hydrolysis of a ketone
A) I & II B) I C) II & III D) I & III
12. Toluene is oxidized to benzaldehyde by

a. alkaline KMnO4
b. PCC
c. acidified K2Cr2O7
d. CrO2Cl2
13. When Ethanal is heated with Fehling’s solution it gives a precipitate of
(a) CuO
(b) Cu
(c) Cu + Cu2O + CuO
(d) Cu2O
14. Which of the following have the highest Ka value
a. Formic acid
b. Acetic acid
c. Chloroacetic acid
d. Fluroacetic acid
15. The product formed in aldol condensation is
(a) a beta-hydroxy aldehyde or a beta-hydroxyketone
(b) an alpha-hydroxy aldehyde or ketone
(c) an alpha, beta unsaturated ester
(d) a beta-hydroxy acid
16. The reagent which can be used to distinguish acetophenone from benzophenone is
(a) 2,4-dinitrophenylhydrazine
(b) aqueous solution of NaHSO3
(c) Benedict reagent
(d) I2 and NaOH
17. The major product of nitration of benzoic acid is,
(a) 2-nitrobenzoic acid
(b) 4-nitrobenzoic acid
(c) 3-nitrobenzoic acid
(d) 2,4- dinitro benzoic acid
18. Oxidation of cyclohexene using acidified KMnO4 will give ………
(a) Adipic acid
(b) Hexane -1,6-dial
(c) Cyclohexane carboxylic acid
(d) Cyclopentane carboxylic acid
121
19. Assertion: Acetic acid is stronger acid than CH3CH2COOH
Reason: Acetic acid is resonance stabilized.
(A) Both Assertion and reason are true and reason is correct explanation of assertion.
(B) Both Assertion and reason are true and reason is not correct explanation of assertion.
(C) Assertion is true, reason is false.
(D) Assertion is false, reason is true.
20. Assertion: The pKa of acetic acid is lower than that of phenol.
Reason: Phenoxide ion is more resonance stabilized than acetate ion.
(A) Both Assertion and reason are true and reason is correct explanation of assertion.
(B) Both Assertion and reason are true and reason is not correct explanation of assertion.
(C) Assertion is true, reason is false.
(D) Assertion is false, reason is true.
LEVEL-3
21. Which is not true about acetophenone ?

(a) It reacts with 2,4-dinitrophenylhydrazine to form 2, 4-dinitrophenylhydrazone
(b) It reacts with Tollen’s reagent to form silver mirror.
(c) It reacts with I2/NaOH to form iodoform
(d) On oxidation with alkaline KMnO4 followed by hydrolysis it gives benzoic acid
22. An organic compound ‘X’ having molecular formula C5H10O yields phenylhydrazone and gives negative
response to iodoform test and Tollen’s test. It produces n-pentane on reduction. ‘X’ could be
(A) 3-pentanone (B)n-amyl alcohol (C)pentanal (D)2-pentanon
23. Which of the following products is formed when benzaldehyde is treated with CH3MgBr and the
additionproduct so obtained is subjected to acid hydrolysis ?
(a) A secondary alcohol
(b) A primary alcohol
(c) Phenol
(d) tert-Butyl alcohol
24. Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally
known
(a) an amine
(b) an imine
(c) an enamine
(d) a Schiff’s base
25. The increasing order of the rate of HCN addition to compound A – D is
(A) HCHO (B) CH3COCH3 (C) PhCOCH3 (D) PhCOPh

(a) D < C < B < A
(b) C < D < B < A
(c) A < B < C < D
(d) D < B < C < A
26. Oxidation of acetone using HNO3 will give
(a) two molecules of acetic acid
(b) one molecule of propionic acid
(c) CH3COOH + H2O + CO2
(d) two molecules of formic acid
122
27. Consider the reactions,
Identify A, X, Y and Z.
(a) A-Methoxymethane, X-Ethanol, Y-Ethanoic acid, Z-Semicarbazide.
(b) A-Ethanal, X-Ethanol, Y-But-2-enal, Z-Semicarbazone.
(c) A-Ethanol, X-Acetaldehyde,Y-Butanone, Z-Hydrazone.
(d) A-Methoxymethane, X-Ethanoic acid,Y-Acetate ion, Z-Hydrazine
28. Arrange the following molecules in the increasing order of Pka values
a)Dichloro acetic acid< Trichloroacetic acid < Chloroacetic acid < Acetic acid
b)Trichloro acetic acid< Dichloroacetic acid < Chloroacetic acid < Acetic acid
c)Trichloro acetic acid > Dichloroacetic acid > Chloroacetic acid > Acetic acid
d)Dichloro acetic acid< Trichloroacetic acid < Chloroacetic acid < Acetic acid
29. Assertion : Compounds containing –CHO group are easily oxidised to corresponding carboxylic acids.
Reason : Carboxylic acids can be reduced to alcohols by treatment with LiAlH4
If both Assertion and Reason are correct and the Reason is a correct explanation of the Assertion.
If both Assertion and Reason are correct but Reason is not a correct explanation of the Assertion.
If the Assertion is correct but Reason is incorrect.
If both the Assertion and Reason are incorrect
30. Assertion : The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular masses.
Reason : There is a weak molecular association in aldehydes and ketones arising out of the dipole-
dipoleinteractions.
If both Assertion and Reason are correct and the Reason is a correct explanation of the Assertion.
If both Assertion and Reason are correct but Reason is not a correct explanation of the Assertion.
If the Assertion is correct but Reason is incorrect.
If both the Assertion and Reason are incorrect.
Answer key
1 A 11 A 21 B
2 B 12 D 22 A
3 B 13 D 23 A
4 C 14 D 24 D
5 B 15 A 25 A
6 B 16 D 26 C
7 C 17 C 27 B
8 A 18 A 28 B
9 A 19 C 29 B
10 A 20 C 30 A
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CASE STUDY BASED QUESTIONS
1. The carbonyl group of aldehydes and ketones is reduced to -CH2- group on treatment with zinc amalgam and
concentrated hydrochloric acid [Clemmensen reduction] or with hydrazine followed by heating with sodium or
potassium hydroxide in high boiling solvent such as ethylene glycol (Wolff-Kishner reduction).
Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxidised to carboxylic
acidson treatment with common oxidising agents like nitric acid, potassium permanganate, potassium
dichromate,etc. Even mild oxidising agents, mainly Tollens’ reagent and Fehlings’ reagent also oxidise
aldehydes.
Ketones are generally oxidised under vigorous conditions, i.e., strong oxidising agents and at elevated
temperatures. Their oxidation involves carbon-carbon bond cleavage to afford a mixture of
carboxylic acidshaving lesser number of carbon atoms than the parent ketone.
1. Which of the following cannot be made by reduction of ketone or aldehyde with NaBH4 in methanol?
(a) 1-Butanol
(b) 2-Butanol
(c) 2-Methyl-1-propanol
(d) 2-Methyl-2-propanol
2. The carbonyl compound producing an optically active product by reaction with LiAlH4 is:
(a) Propanone
(b) Butanone
(c) 3-Pentanone
(d) Benzophenone.
3. A substance C4H10O (X) yields on oxidation a compound C4H8O which gives an oxime and a positive
Iodoform test. The substance X on treatment with cons. H2SO4 gives C4H8. The structure of the
compound X is:
(a) CH3CH2CH2CH2OH
(b) CH3CH(OH)CH2CH3
(c) (CH3)3 COH
(d) CH3CH2-O-CH2CH3
4. An organic compound (A) with molecular formula C8H8O forms an
orange-red precipitate with 2,4-DNP reagent and gives yellow precipitate on heating with iodine in
the presence of sodium hydroxide. It neither reduces Tollens’ or Fehlings’ reagent, nor does it
decolourise bromine water or Baeyer’s reagent. On drastic oxidation with chromic acid, it gives a
carboxylic acid (B)having molecular formula C7H6O2. compounds (A) and (B) are respectively :
(a) Acetophenone and Benzoic acid

(b) Benzophenone and Benzoic acid
(c) Benzaldehyde and Benzophenone
(d) Benzyalaldehyde and 1-phenylethanoic acid
ANSWERS
1.D 2.B 3.B 4.A
5. Read the passage given below and answer the following questions :
Carboxylic acids dissociate in water to give carboxylate ion and hydronium ion.
124
RCOOH + H2O ⟶ RCOO- + H3O+
The acidity of carboxyl group is due to the presence of positive charge on oxygen which liberates
proton. The carboxylate ion formed is resonance stabilised.
Carboxylic acids are stronger acids than phenols. Electron withdrawing groups (EWG) increase
the acidity of carboxylic acids by stabilising the conjugate base through delocalisation of negative
charge by inductive and/or resonance effects. Electron donating group (EDG) decrease the acidity by
destabilising the conjugate base.The following questions are multiple choice questions. Choose the
most appropriate answer :
1. Which of the following statement is not true about the acidic nature of carboxylic acids.
a. Smaller the pKa, the stronger the acid.
b. The presence of electron donating group on the phenyl of aromatic carboxylic acid increases
theiracidity.
c. The presence of electron withdrawing group on the phenyl of aromatic carboxylic acid increases
their acidity.
d. Carboxylic acids are weaker than mineral acids
2. Which one of the following is the correct order of acidic strength?

(a) CF3COOH > CHCl2COOH > HCOOH > C6H5CH2COOH > CH3COOH
(b) CH3COOH > HCOOH > CF3COOH > CHCl2COOH > C6H5CH2COOH
(c) HCOOH > C6H5CH2COOH > CF3COOH > CHCl2COOH > CH3COOH
(d) CF3COOH > CH3COOH > HCOOH > CHCl2COOH > C6H5CH2COOH3
3. Which of the following acids has the smallest acid dissociation constant?
(a) CH3CHFCOOH (b) FCH2CH2COOH (c) BrCH2CH2COOH (d) CH3CHBrCOOH
4. The correct order of acidity for the following compounds is
(a) I > II > III > IV (b) III > I > II > IV (c) III> IV > II> I (d) I > III > IV > II
ANSWERS
1.B 2.A 3.C 4.A
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VSA TYPE QUESTIONS - 1 Marks Questions
1. Aldehydes and Ketones have lower boiling points than corresponding alcohols. Why?
Ans. The boiling points of aldehydes and ketones are lower than that of corresponding alcohols due
to absence of intermolecular H–bonding in aldehydes and ketones.
2. Account for the following : Cl-CH2COOH is a stronger acid than CH3COOH.
Ans. Chloroacetic acid has lower pKa value than acetic acid; ‘Cl’ in chloroacetic acid shows –I effect,
it creates less electron density on oxygen of carboxylic acid. thus, release of proton becomes easier.
In case of acetic acid, the state of affair is just opposite. Hence, chloroacetic acid is stronger than
acetic.
3. Monochloro ethanoic acid has a higher pKa value than dichloroethane acid. Why?
ANS: The strength of an acid is indicated by pKa value, where, pKa = – log Ka. Since
monochloroethanoic acid is weaker than dichloroethanoic acid due to presence of only one Cl
(EWG), it has lower value ofdissociation constant Ka. , therefore, it has higher value of pKa.
4. The aldehydes and ketones undergo a number of addition reactions. Explain.
Ans. Aldehydes and ketones undergo a number of addition reactions as both possess the carbonyl functional
group which reacts with a number of nucleophiles such as HCN, NaHSO3, Alcohols, ammonia derivatives and
Grignard reagents.
5. Ethanoic acid is a weaker acid than benzoic acid. Explain.
ANS: The —COOH group in benzoic acid is attached to sp2 - carbon of the phenyl ring and is more
acidicthan acetic acid in which —COOH group is attached to sp3 – carbon atom of CH3 group. So,
benzoic acidis stronger than acetic or acetic acid is weaker acid than benzoic acid.
6. Lower aldehydes and ketones are quite miscible with water why?
Ans. Due to easy Formation of H-bondings with water.
7. Why 2,4 dinitrophenol is more acidic than phenol?
Ans. Nitro (-NO2) group is electron withdrawing so it facilitates to release H+.
8. Complete the reaction equation -
C6H6+ RCOCl AlCl3 -----------

Anhyd
O
Ans. C6H6+ RCOCl AlCl3 + HCl
||
Anhyd
i. Aromatic C-R
Ketone
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9. Why is the boiling point of an acid anhydride higher than the acid from which it is derived?
Ans. Acid anhydrides are bigger in size than corresponding acids and have more surface area and more Van
der waal’s force of attraction and hence have higher boiling point.
10. Why the oxidation of toluene to benzaldehyde with CrO3 is carried out in the presence of acetic anhydride.
Ans. If acetic anhydride is not used we will get benzoic acid. Acetic anhydride is used to prevent oxidation
of benzaldehyde to benzoic acid.
11. Mention a Chemical property in which Ethanal differs from acetic acid
Ans. Ethanal reduces Tollen's reagent and Fehlings solution whereas ethanoic acid does not.
12. Give one chemical test to distinguish between acetaldehyde and benzaldhyde.
Ans. Acetaldehde gives iodoform test whereas benzaldhyde does not.
13. Convert Toluene to Benzaldehyde.
Ans.
14. Compare the strength of following acids formic acid, acetic, Benzoic acid.
Ans. HCOOH > C6H5COOH > CH3COOH
15. Why is oxidation of alcohols to get aldehydes carried out under controlled conditions?
Ans. It is because aldehydes can get further oxidised to acids, so oxidation of alcohols toaldehydes
needs to be controlled.
16. Why formic acid is stronger than acetic acid?
Ans. Due to +I effect, CH3- group in acetic acid increases e-density on carbon atom which makes it weak acid.
While in formic acid no such group is present, hence is more stronger than acetic acid.
127
17. Why is oxidation of alcohols to get aldehydes carried out under controlled conditions?
Ans. It is because aldehydes can get further oxidised to acids, so oxidation of alcohols toaldehydes
needs to be controlled.
18. Why do aldehydes have lower boiling point than corresponding alcohols?
Ans. Aldehydes have lower boiling point as they are not associated with intermolecular H-bonding whereas
alcohols are associated with intermolecular H-bonding. So, Aldehydes have lower b.p.
19. Why do Carboxylic acids not give the characteristic reactions of a carbonyl group?
Ans. Due to resonance, It doesn’t give the characteristics reactions of carbonyl group. It does not have free
20. Most aromatic acids are solids while acetic acid and others of this series are liquids. Explain why?
Ans. Aromatic acids have higher molecular weight, More van-der waals force of attraction as
compared to aliphatic acids, Hence they are solids.
21. Suggest a reason for the large difference in the boiling points of butanol and butanal, although they have
same solubility in water.
Ans. The b.p. of butanol is higher than that of butanal because butanol has strong intermolecular H-
bonding while butanal has weak dipole-dipole interaction. However both of them form H-bonds with water
and hence are soluble.
22. Which of the aldehydes undergo canizzaro's reaction?
Ans. Those aldehydes which not have -H atoms undergo canizzaro's reaction e.g. HCHO,
C6H5CHO
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2 Marks Questions
1. Write a test do distinguish between Phenol and Benzoic acid.
Ans. Add neutral FeCl3 to each.
Violet colouration appearance with phenol
No violet colouration with Benzoic acid.
OR
Add NaHCO3 solution to each:-
With phenol no reaction, but with benzoic acid CO2 gas is evolved.
2. Give chemical tests to distinguish between the following pairs of compounds:
(i) Propanal and propanone
(ii) Benzaldehyde and benzoic acid.
Ans. (i) Add Tollen's reagent. Propanal will give silver mirror whereas propanone will not react.
b. (ii) Add NaHCO3 solution. Benzaldehyde will not react whereas benzoic acid will give brisk
effervescence due to CO2.
3. Give chemical tests to distinguish between the following pairs of compounds :
(i) Phenol and Benzoic acid,
(ii) Benzaldehyde and Acetophenone
Ans. (i) Add neutral ferric chloride. Phenol will give violet colur whereas benzoic acid not react.
(ii) Add I2 and NaOH. Acetophenone give yellow ppt. of iodoform whereas benzaldehyde will
not react.
4. Account for the following :
(i) Most aromatic acids are solids while acetic acid and others of this series are liquids.
(ii) Explain why ketones are less reactive towards nucleophiles than aldehydes.
Ans. (i) Aromatic acids have higher molecular weight, therefore they have more van der Waals' force of
attraction as compared to aliphatic acids, therefore, they are solids.
129
(ii) Ketones are less reactive towards nucleophiles than aldehydes because in ketones there are two
alkyl groups which decrease positive charge on carbonyl group due to electron repelling nature
(electron releasing nature) whereas in aldehyde there is one alkyl group which is electron releasing.
5. Complete the following reaction equations:

Zn/HCl
(i) RCHO
Zn/HCl
(ii) CH3CONH2 + HNO2
Ans. (i) RCHO R - CH3 + H2O
(ii) CH3CONH2 + HNO2 CH3COOH + N2 + H2O
6. There are two-NH2 groups in semicarbazide. However only one is involved in formation of semicarbazones.
Explain
Ans: Due to resonance one NH2 group is involved in resonance and hence can’t participate in the formation
of semicarbazone.
Lone pair of other NH2 group is not involved in resonance and is available for nucleophillic attack
7. CH3CHO is more reactive than CH3COCH3 towards reaction with HCN. Explain
Ans. It is a nucleophilic addition reaction, in which CN– acts as a nucleophile. CH3CHO undergoes
nucleophilic addition reactions faster than CH3COCH3 as in CH3COCH3 there are two electron
releasing methyl groups attached to the carbonyl carbon that hinders the approach of nucleophile
to carbonyl carbon and reduce the electrophilicity of the carbonyl group (+I Inductive
effect of methyl group) while in CH3CHO, there is only one methyl group attached to carbonyl
carbon.
8. What is Tollens’ reagent? Write one usefulness of this reagent.
ANS. Tollens’ reagent is an ammoniacal silver nitrate solution. Tollens’ reagent is used to test an
aldehyde.Both aliphatic and aromatic aldehydes reduce Tollens ’reagent and give silver mirror.
130
9. Why are aldehydes more reactive than ketones when they undergo nucleophillic addition reaction?
Ans.
a. + I effect:- The alkyl group in Ketones due to their e-releasing character decrease the +ve charge on
C-Atom and thus reduce its reactivity.
b. Steric hindrance:- Due to steric hindrance in ketones they are less reactive.
10. Treatment of Benzaldehyde with HCN gives a mixture of two isomers which cannot be separated even by
careful fractional distillation. Explain why?
Ans. It is because we get two optical isomers which have same physical Properties and cannotbe separated by
Fractional distillation
11. Explain why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is a
high melting solid.
Ans. Due to intramolecular H-bonding in o-hydroxy benzaldehyde exists as discrete molecule whereas due to
intermolecular H-bonding p-hydroxy benzaldehyde exist as associated molecules. To break this intermolecular
H-bonds a large amount of energy is needed. Consequently P-isomer has a much higher m.p. and b.p. than that
of o-isomer. As a result o-hydroxy benzaldehyde is liquid.
131
12. Describe the following:
(i) Cannizzaro reaction (ii) Decarboxylation
Ans. (i) Cannizzaro reaction. Aldehydes which do not have -hydrogen atom (HCHO, C6H5CHO),(CH3)3 CHO
undergo auto-oxidation and reduction (disproportionation) on treatment with conc. Alkali, in this one
molecule of aldehyde is oxidized and other molecule gets reduced.
NaOH
2HCHO CH3OH + HCOONa
(ii) Decarboxylation. Carboxylic acid lose carbon dioxide, when their sodium salts are heated with
sodalime (NaOH + Cao).
13. Account for the following:
(a) Cyclohexanone forms cyanohydrin in good yield but 2,2,6 trimethyl cyclo-hexanone
does not. Why?
Ans. In 2,2,6 trimethyl cyclohexanone there is steric hinderance of 3 methyl groups, It does not form
cyanohydrin in good yield.
(b) Melting point of an acid with even no. of carbon atoms is higher than those of its neighbour
with odd no. of carbon atoms.
Ans. They fit into crystal lattice more readily than odd ones being more symmetrical that is why they have
higher lattice energy and higher melting point
132
3 Marks Questions
1. Write one chemical equation fro each, to illustrate the following reactions :
(i) Rosenmund reduction
(ii) Cannizzaro reaction
(iii) Fischer esterification
O O
Pd-BaSO4
Ans. i Rosenmund reduction : CH3-C-Cl
| + H2 CH3-C-H + HCl |
quinoline,S
| |
50%KOH
(ii) Cannizzaro reaction : 2HCHO HCOOK + CH3OH
(iii) Fischer esterification:

Conc.H2SO4
CH3COOH + C2H5OH CH3COOC2H5 + H2O
2. Account for the Following:
(i)Higher carboxylic acid are insoluble in water. Why?

(ii)Why p-nitro benzoic acid has higher Ka value than benzoic acid?
(iii) The boiling points of aldehydes and ketones are lower than that of the corresponding acids.
Ans: (i)Due to increased hydrophobic part, H-bonding does not take place. So higher carboxylic acid
areinsoluble in water.
Ans(ii): Higher the Ka value, stronger is the acid. Nitro group has –R as well as –I effect which makes the
O-H more polar hence p-nitro benzoic acid is stronger acid. (The conjugate base gets stabilised
through delocalisation of the negative charge by inductive and /or resonance effects). So it has higher
Ka value
Ans(iii) The boiling points of aldehydes and ketones are lower than that of the corresponding acids
due tointermolecular hydrogen bonding in carboxylic acids
3. Write the chemical tests to distinguish between:
(i) Acetaldehyde and Benzaldehyde
(ii) Phenol and Acetic acid
(iii) Pentanal and Pentan-2-one

133
Ans. (i) Add Fehling's solution to each of them separately. Acetaldehyde will give brick red precipitate
whereas benzaldehyde will not react.
Or
Acetaldehyde will give iodoform positive test.
(ii) Acetic acid gives effervescence with NaHCO3 due to CO2
Or
Phenol with neutral ferric chloride gives violet colour.
(iii) Pentanal will form silver mirror with Tollen's reagent.
Or
Pentan-2-one will give iodoform test with I2 and NaOH.
4. Account for the following:
(i) Oxidation of toluene to C6H5CHO with CrO3 is carried out in presence of acetic anhydride.
(ii)Melting point of an acid with even number is higher than those of its neighbours with odd number ofcarbon
atoms.
(iii)Aromatic acids are solid while most of aliphatic acids are liquids.
Ans. (i) Oxidation of toluene to C6H5CHO with CrO3 is carried out in presence of acetic anhydride. to
prevent further oxidation of C6H5CHO to benzoic acid.
(ii) Acids with even number of carbon atoms fit into crystal lattice and have higher lattice energy and
higher melting point.
(iii)Aromatic acidshave higher molecular weight and strong Van der Waals force of attraction as
compared to aliphatic acidsso they are solids
5. Two moles of organic compound A on treatment with a strong base gives two compounds B and C.
Compound B on dehydration with Cu gives A while acidification of C yields carboxylic acid D having molecular
formula of CH2O2. Identify the compounds A, B, C, D
134
6. An organic compound ‘A’ is resistant to oxidation forms on oxidation a compound 'B(C3H8O) on reduction.
‘B' reacts with HBr to form a bromide C’which on treatment with alcoholic KOH forms an alkene ‘D’ (C3H6).
Deduce A, B, C, D.
7. Arrange the following compounds in increasing order of their reactivity towards HCN. Explain it with
proper reasoning. Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone.
Ans. Addition of HCN to the carbonyl compounds is a nucleophilic addition reaction.The reactivity towards
HCN addition decreases as the + I effect of the alkyl groups increases and/or the steric hindrance to the
nucleophilic attack by CN– at the carboxyl carbon increases. Thus the reactivity decreases in the order:
In other words, reactivity increases in the reverse order, i. e. Ditert-butyl Ketone < tert-Butyl methyl Ketone
< Acetone < Acetaldehyde
8. Arrange the following compounds in increasing order of their boiling points.
135
Explain by giving reasons.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3.
Ans. The molecular masses of all these compounds are comparable:
CH3CHO (44), CH3CH2OH (46), CH3COCH3 (46), CH3CH2CH3 (44).
CH3CH2OH exists as associated molecule due to extensive intermolecular hydrogen bonding and hence its boiling
point is the highest (351 K). Since dipole dipole interactions are stronger in CH3CHO than in CH3OCH3, hence boiling
point of CH3CHO (293 K) is much higher than that of CH3OCH3 (249 K). Further, molecules of CH3CH2CH3 have only
weak Vander Waals forces while the molecules of CH3OCH3 have little stronger dipole-dipole interactions and
hence the boiling point of CH3OCH3 is higher (249 K) than that of CH3CH2CH3 (231 K).
Thus the overall increasing order of boiling points is : CH3CH2CH3<

CH3OCH3< CH3CHO < CH3CH2OH
9. Complete the following equations :
COOH
(i) SO3/H2SO4
(ii) CH3CONH2 + HNO2
(iii) CH3CHO + C6H5NHNH2
COOH COOH
SO3/H2SO4
Ans. (i) +H2O
SO3H
(ii) CH3CONH2 + HNO2 CH3COOH+N2+H2O
(iii) CH3CHO + C6H5NHNH2 CH3-CH=N-NHC6H5+H2O
136
5 Marks Questions
1. Which of the following compounds would undergo Aldol condensation, which the Cannizzaro reaction and
which neither? Write the structures of the expected products of Aldol condensation and Cannizzaro reaction.
1. Methanal
2. 2-Methypentanal
3. Benzaldehyde
4. Benzophenone
5. Cyclohexanone
6. 1-Phenylpropanone
7. Phenylacetaldehyde
8. Butan-1-ol
9. 2,2-Dimethylbutanal.
Ans. (a) Methanal, (c) benzaldehyde and (i) 2,2-dimethylbutanal will give Cannizzaro reaction because they
do not have -hydrogen atoms.
(b) 2-Methylpentanal (e) cyclohexanone (f) 1- phenypropanone (g) pheylacetaldehyde will give aldol
condensation because they -hydrogen atoms.
(d) Benzophenone and (h) butan-1-ol will neither undergo Cannizzaro reaction nor aldol condensation.
2. Give reasons for the following :

(i) C6H5COOH is weaker than formic acid.
(ii) HCOOH and CH3COOH are differentiated by Tollen’s reagent.
(iii) R – COOH do not give characteristic reaction of > C = O.
(iv) Carboxylic acids are stronger acids than phenols.
(v) Acid amides are weakly basic in nature.
Ans. (i) Due to instability of carboxylate anion due to conjugation, C6H5COOH is weaker than formic
acid
(ii) CH3COOH do not give Tollens’s test.

(iii) > C = O group is sterically hindered in carboxylic acid, hence do not give characteristic reaction of
>C = O.
(iv) Carboxylic acids are stronger acids than phenols due to the dispersal of –ve charge on carboxylate
ions than phenoxide ion.
(v) Acid amides are basic due to lone pair of electrons on nitrogen atom.
137
3. (i) Arrange the following in the property indicated:
a. Acetaldehyde, Acetone, di-tert-butyl ketone, Methyl tert-butyl ketone in (increasing

reactivity towards HCN)
Ans: di-tert-butyl ketone < Methyl tert-butyl ketone <Acetone <Acetaldehyde
(b) CH3CH2CHBrCOOH, CH3CHBrCH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (in increasing

order of acid strength)
(CH3)2CHCOOH<CH3CH2CH2COOH<CH3CHBrCH2COOH< CH3CH2CHBrCOOH
(ii) An aliphatic compound 'A' with a molecular formula of C3H6O reacts with phenylhydrazine to give
compound 'B'. Reaction of 'A' with I2 in alkaline medium on warming, gives yellow precipitate 'C'. Indentify
the compounds A,B and C.
Ans. CH3-C-CH
| 3+C6H5NHNH2 CH3-C=N-NH-C6H5+H2O
CH3
|
'A' 'B'
Acetone Acetone phenylhydrazone

O
CH3-C-CH
| 3+ 3I2 + 4NaOH CHI3 + CH3COONa+ 3NaI + 3H2O
|
Acetone C “Iodoform"
4. What is meant by the following terms? Give an example in each case.
1. Cyanohydrin
2. Semicarbazone
3. Hemiacetal
4. Ketal
5. 2,4-DNPderivative
Ans. (a) Cyanohydrin: When -CN and -OH groups areOHattached to same carbon atom it is called cyanohydrin
e.g. , CH3-CH-CN
138
(b) Semicarbazone: When aldehyde or ketone reacts with semicarbazide, the product formed is
semicarbazone e.g., CH3-CH=NHCONH2
(c) Hemiacetal: When aldehyde reacts with one mole of alcohol in

OH
presence of HCI gas, hemiacetal is formed e.g., CH3-CH-OCH3
(d) Ketal : When ketone reacts with two moles of alcohols in presence
of HCI gas, ketal formed e.g.,
(e) 2,4-DNP derivative: When aldeydeos or ketones react with 2,4- DNP, orange ppt is formed.
Questions for Practice
1. Write chemical reaction for getting
a. 2-propanol from ethanal
Draw structure of compound
b. 4-methyl pent-3-en-2-one.
Write a chemical test to distinguish between
c. Formic acid and acetic acid.
2. Distinguish between formic acid and acetic acid by a suitable chemical test.
3. Arrange the following compounds in increasing order of their property ,
(i) CH3CHO, CH3CH2OH, CH3CH2CH3 (boiling point)
(ii) CH3COCH3, C6H5COCH3, CH3CHO ( towards nucleophilic addition reaction)
(iii) Cl-CH2-COOH, F-CH2-COOH, CH3-COOH (acidic character)
.
4. Give reasons for the following:
(i) Aldehydes are more reactive than ketones in nucleophilic reactions.
(ii) Most aromatic acids are solids but acids of acetic acid group are mostly liquids.
5. Write the complete reaction for each of the following conversions stating the conditions necessary:
a. Toluene to Benzaldehyde (ii) Benzoyl chloride to Benzaldehyde
Suggest a test for distinguishing between the following pairs:
139
b. Aqueous solutions of phenol and benzoic acid
6. Convert (i) Propanoic acid to 1- propanol (ii) Toluene to benzoic acid.
7. Write reactions and conditions for the following conversions:
(i) Ethanol to propanone
(ii) Benzoyl chloride to Benzaldehyde
(iii) Acetaldehyde to crotonaldehyde
8. (a) Give reasons for the following:
(i) Ethanal is more reactive than acetone towards nucleophilic addition reaction.
(ii) (CH3)3C—CHO does not undergo aldol condensation.
(iii) Carboxylic acids are higher boiling liquids than alcohols.
9. Illustrate the following reactions giving a chemical equation for each:
a) Rosenmund reduction (b) Wolff kishner reduction.
10. Convert:
a. Reaction of An aldehyde to an acetal
b. Benzoic acid to m-nitrobenzoic acid
c. Benzoic acid to 3-bromobenzoic acid
11. (a) Give chemical tests to distinguish between
(i) Propanol and propanone
(ii) Benzaldehyde andacetophenone
(iii) Acetophenone and Benzophenone
(b) Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) Benzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid strength)
(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acid strength)
140
12. A component ‘A’ with molecular formula C5H10O gave a positive 2, 4 DNP test but a negative tollen’s reagents
test . It was oxidised to carboxylic acid B’ with molecular formula C3H6O2 when treated with alkaline KMnO4
under vigorous conditions . Sodium salt of B gave hydrocarbon C’ on Kolbe electrolysis reaction. Identify A , B,
C and D.
13. An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate with 2,4 DNP
reagent and gives yellow precipitate on heating with iodine in the presence of sodium hydroxide. It neither
reduces Tollen’s or Fehling’s reagent nor does it decolourise bromine water or baeyer’s reagents . On drastic
oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C7H6O2.
Identify the compounds (A) and (B).
14. Write balanced chemical equations for the following reactions:
(i) Thionyl chloride reacts with benzoic acid
(ii) Acetic acid is reacted with red phosphorus and HI
(iii) Acetic acid is treated with Zn metal.
141
UNIT 9. AMINES
CURRICULUM / SYLLABUS OF UNIT AMINES 2023-24 :

Nomenclature, classification, structure, methods of preparation, physical and chemical properties, uses,
identification of primary, secondary and tertiary amines. Diazonium salts: Preparation, chemical reactions
and importance in synthetic organic chemistry.
GIST OF LESSON :
Like ammonia, amines also have trigonal pyramidal structure with three bond pairs and one lone pair of
electrons. The amino nitrogen atom is sp3- hybridized .
1. Classification : Amines are classified as primary ( 10) secondary ( 20) and tertiary ( 30) depending upon
the number of hydrogen atoms replaced by alkyl groups in ammonia molecule.
2. Amines are derivatives of ammonia. These are obtained by the replacement of one , two or three
hydrogen atoms by alkyl and /or aryl halides.
3. Structure of Amines :
Like ammonia, amines also have trigonal pyramidal structure with three bond pairs and one lone pair
of electrons. The amino nitrogen atom is sp3- hybridized.
4. Classification: Amines are classified as primary ( 10) secondary ( 20) and tertiary ( 30) depending
upon the number of hydrogen atoms replaced by alkyl groups in ammonia molecule.
Types of amines Formula Example

Primary amines RNH2 CH3-NH2 , C6H5NH2
Secondary Amines R2NH CH3NH-CH3
Tertiary Amines R3N CH3N(CH3)2
5. Nomenclature : Common names and IUPAC names are as follows

Compound Common Name IUPAC Name
CH3NH2 Methyl amines Methanamine
CH3CH2NH2 Ethylamine Ethanamine
CH3CH2CH2NH2 Propylamine Propan-1-amine
(CH3)2CHNH2 Isopropylamine Propane-2-amine
CH3NHCH2CH3 Ethylmethylamine N-Methylethanamine
(CH3)3N Trimethyl amine N, N-Dimethylmethanamine
C2H5N(C2H5)CH2CH2CH2CH3 N,N-Diethylbutanamine N,N-Diethylbutan-1-amine
NH2CH2CH=CH2 Allylamine Pro-2-en-1-amine
NH2(CH2)6-NH2 Hexamethylenediamine Hexan-1,6-diamine
C6H5NH2 Aniline Aniline or Benzenamine
C6H5NH2CH3 o-Toluidine 2-Aminotoulene
C6H5N(CH3)2 N,N-Dimethylaniline N,N-Dimethylbenzenamine
6. Preparation of Amines:
Method of Preparation Description
Reduction of Nitro compounds Reagents that can reduce nitro compounds to amines are :
142
Sn/HCl
C6H5NO2 → C6H5NH2 + 2H2O
Sn/HCl
C6H5NO2 → C6H5NH2 + 2H2O
*Reduction with Fe scrap /HCl is preferred because FeCl2 gets

hydrolysed to release HCl during the reaction. So , only a small
amount of HCl is required to initiate the reaction
Ammonolysis of alkyl halides Ammonia reacts with alkyl halide to form a mixture of three
types of amines along with quaternary ammonium salt.This
reaction is known as ammonolysis.
RX RX RX RX RX
NH3 → RNH2 → → RNH2 → R2NH → R3N → R4N+X- (
Quartenary ammonium salt.
The amines formed reacts with HX to form substituted
ammonium salts and the freee amine can be recovered from the
ammonium salt by treatment with a strong base like NaOH.
NH3 + R-X → R-NH3+X- (Sustituted ammonium salt.
RNH3+X- +NaOH → RNH2 + H2O + Na+X-
Reduction of nitriles Regents that can reduce nitrile to amines are :
-catalytic hydrogenation ( H2/Ni , Pt or Pd )
-lithium aluminium hydrides , LiAlH4
-Na-Hg /C2H5OH
4H
RCN → RCH2NH2
𝐇𝟐/𝐍𝐢 𝐨𝐫 𝐍𝐚(𝐇𝐠/ 𝐂𝟐𝐇𝟓𝐎𝐇
RCN → RCH2NH2
Reduction of amides Lithium aluminium hydride, LiAlH4 also reduces amides to yield
amines
LiAlH4
RCONH2 → RCH2NH2 + 2H2O
Substituted ammonium salt
Gabriel phthalimide Synthesis This method is used for the preparation of pure aliphatic
amines .Phthalimide is treated with alcohols KOH to form
potassium salt of phthalimide, which on heating with alkyl halide
(RX) followed by alkaline hydrolysis produces the primay
amine.This reaction involves SN2 attack of the anion formed by
phthalimide on R-X.
Hoffmann Bromamide degredation Amide on treating with bromine in aqueous ethanolic solution of
reaction NaOH or degradation reaction KOH yield primary amine with one
C less than that in the amide.
RCONH2 +Br2 +4NaOH → RNH2 +Na2CO3 +2NaBr +2H2O
143
PHYSICAL PROPERTIES Physical state ➢ The lower aliphatic amines are gases with fishy odour
➢ 10 amines with 3 or more carbon atoms are liquid and
higher ones are solid.Arylamine are usually colorless but get
coloured on storage due to atmospheric oxidation.
Solubility ➢ Lower aliphatic amines are soluble in water because they
can form H-bonds with water molecules.
➢ This solubility decreases with increase in size of the
hydrophobic alkyl part.
➢ Higher amines are almost insoluble in water.
➢ The solubility of amines is lesser than that of alcohols of
comparable molecular mass because alcohols are more polar
than amines and form stronger H-bonds.
Boiling Point ➢ The order of boiling points of isomers amines is as follows
:
➢ 10 Amines > 20 Amines > 3 0 amines
Higer B.P. of 1 0 Amines is because of the maximum extent of
H- bonding in them.
CHEMICAL REACTIONS Basic ➢ Amines are basic in nature an react with acid to form salt.
Character RNH2 +HX → RNH3+X- substituted ammonium salt.
➢ Order of basicity of amines in gaseous phase is as :
3 0 Amines > 2 0 Amines > 1 0 Amines > NH3
( According to + I effect )
However , in aqueous phase , there is subtle interplay of
inductive effect , steric effect an salvation effect. As a result
following observation is observed :
(CH3CH2)2 NH > (CH3CH2) 3 N > CH3 CH2 NH2 > NH3
(2 0) ( 3 0) ( 1 0 )
CH3)2 NH > CH3NH2 > (CH3)3N > NH3
(2 0 )amine (1 0 ) ( 3 0)
➢ Aryl amines are less basic than ammonia because the
lone pair of electrons on N- atom of aryl amines is involved in
resonance and is less available for protonation.
Alkylation ➢ Amines react with alkyl halide and undergo alkylation as
shown:
RX RX RX
RNH2 → R2NH → R3N → R4N+ X-
( 1 0 Amine ) ( 2 0 Amines ) ( 3 0 Amines )
Quaternary ammonium salt
Acylation ➢ Amines react with acyl chloride in the presence of base like
pyridine or acid anhydride and undergo acylation .
➢ For example ; C2H5NH + CH3COCl –Pyridine→ C2H5 NHCOCH3
+ HCl
Carbylamine raction ➢ All aliphatic and aromatic primary amines react with
chloroform (CHCl3) on heating in the presence of ethanolic
KOH to form foul smelling isocyanide or carbylamines
➢ RNH2 +CHCl3 + 3KOH –heat → RNC +3KCl +3H2O
( 1 0 amine) (Foul smelling isocyanide )
144
Reaction with nitrous acid , HNO2
(NaNO2/HCl)
➢ 1 0 aliphatic amines react with nitrous acid ( HNO2 ) to

form unstable diazonium salt as intermediate, which on
hydrolysis
Reaction with arylsulphonyl chloride ➢ Benzenesulphonyl chloride ( C6H5SO2Cl) is known as

Hinsberg reagent. This reagent is used to make distinction
between three types of amines .
In reaction
with
secondary
amine :
In reaction with secondary amine N,N-
diethyl benzenesulphonamide formed which
is insoluble in alkali.
In reaction with tertiary amine Tertiary amines do not react with benzene sulphonyl
chloride due to lack of hydrogen atom.
(1) Diazotization
(2) Sandmeyer’s reaction
(3) Gattermann reaction
(4) Gabriel Phthalimide

synthesis
145
(5) Ammonolysis
RX RX RX
RNH2 → R2NH → R3N → R4N+X-
146
1. What is the correct IUPAC name of H2N-(CH2)5-NH2?
a. Pentan-1,5-diamine
b. 1,5-Diaminopentane
c. Pentamethylenediamine
d. Pentane-1,5-diamine
2. Which of the following does not react with Hinsberg reagent?

a. C2H5NH2
b. (CH3)2NH
c. (CH3)3N
d. CH3 CH(NH2)CH3
3. Which of the following amines are insoluble in water?
a. Methanamine
b. Ethanamine
c. Propanamine
d. Benzenamine
4. Which of the following is formed when an alkyl primary amine reacts with nitrous acid?
a. Alkyl nitrite
b. Secondary amine
c. Nitroalkane
d. Alcohol
5. Arrange the following compounds in increasing order of bascity: CH3NH2, (CH3)2 NH, NH3,
C6H5NH2 in aqueous medium.
a. C6H5NH2 < NH3 < (CH3)2NH < CH3NH2
b. CH3NH2 < (CH3)2NH < NH3 < C6H5NH2
c. C6H5NH2 <NH3 < CH3NH2<(CH3)2NH
d. (CH3)2NH < NH3 < C6H5NH2 < CH3NH2
6. The correct IUPAC name for CH2 = CHCH2NHCH3 is
a. Allylmethylamine
b. 2-amino-4-pentene
c. 4-aminopent-1-ene
d. N-methylprop-2-en-1-amine
7. C3H8N cannot represent
a. 1° ammine
b. 2° ammine
c. 3° ammine
d. Quaternary ammonium salt
8. In this reaction acetamide is converted to methanamine
a. Gabriel phthalimide synthesis
b. Carbylamine reaction
c. Stephen’s reaction
d. Hoffmann bromamide reaction
147
9. Which of the following is not a final product of the reaction between propylamine and nitrous
acid?
a. CH3CH2CH2N2Cl
b. CH3CH2CH2OH
c. N2 gas
d. HCI
10. Hinsberg’s reagent is

a. Benzenesulphonic acid
b. Benzenesulphonyl chloride
c. p-toluenesulphonyl chloride
d. Chlorosulphuric acid
11. Starting from propanoic acid, the following reactions were carried out, what is the compound Z?
a. CH3-CH2−Br
b. CH3-CH2−NH2
c. CH3-CH2-COBr
d. CH3−CH2−CH2−NH2
148
12. Aniline in a set of reactions yielded a product D. The structure of D would be
a. C6H5CH2OH
b. C6H5CH2NH2
c. C6H5NHOH
d. C6H5NHCH2CH3.
13. The hybridization state of N of R2NH
a. sp3
b. sp2
c. sp
d. dsp2
14. Reduction of CH3CH2NC with hydrogen in presence of Ni or Pt as catalyst gives
a. CH3CH2NH2
b. CH3CH2NHCH3
c. CH3CH2NHCH2CH3
d. (CH3)3N
15. When hypo phosphorous acid is treated with diazonium salts, it is reduced to which
of thefollowing compound?
a. Arene
b. Methane
c. Ethyl alcohol
d. Amines
ANSWERS
1D 5C 9B 13A
2C 6D 10A 14B
3D 7D 11A 15A
4D 8A 12A
149
QUESTION BANK
CLASS XII (CHEMISTRY)
UNIT13: AMINES
Sl.No QUESTIONS :-
1 Which of the following is the strongest base?
2 Aniline first reacts with acetyl chloride producing compound A. A reacts

with HNO3 H2SO4 mixture and produces comp and B which hydrolyses to compound
C.What is the identity of C?
(a) Acetanilide
(b) p-Nitroacetanilide
(c) p-Nitroaniline
(d) Sulphanilic acid.
3 Considering the basic strength of amines in aqueous solution, which one has the
smallestpKb value?
(a) (CH3)3N
(b) C6H5NH2
(c) (CH3)2NH
(d) CH3NH2
4 The most basic compound among the following is:-
(a) Acetanilide
(b) Benzylamine
(c) p-Nitro aniline
(d) Aniline
5 In this reaction acetamide is converted to methanamine
(a) Gabriel phthalimide synthesis
(b) Carbylamine reaction
(c) Stephen’s reaction
(d) Hoffmann bromamide reaction
6 Which of the following is true for the basicity of amines?

(a) Alkylamines are generally less basic than arylamines because N is sp hybridised
(b) Arylamines are generally more basic than alkylamines due to aryl group
150
(c) Arylamines are generally less basic than alkylamines due to delocalisation of lone
pairof electrons in the benzene ring
(d) Alkylamines are generally less basic than arylamines because lone pair of electrons on
N in the arylamines are not delocalised in the benzene ring
7 Which of the following is formed in the reaction of an aldehyde and primary amine?
(a) Ketone
(b) Aromatic acid
(c) Schiff’s base
(d) Carboxylic acid
8. This on reduction with LiAlH4 produces secondary amine
(a) Methyl cyanide
(b) Nitroethane
(c) Methyl isocyanide
(d) Acetamide
9 Aniline is less basic than
(a) Benzylamine
(b) Triphenylamine
(c) p-Nitroaniline
(d) Diphenylamine
10 Which of the following does not react with Hinsberg reagent?
(a) Ethylamine
(b) (CH3)2NH
(c) (CH3)3N
(d) Propan-2-amine
11
above sequence, Z is
(a) Cyanoethane
(b) Ethanamide
(c) Methanamine
(d) Ethanamine
12 The strongest base among the following is?
151
13 Aniline in a set of reactions yielded a product D.
The structure of D would be

(a) C6H5CH2OH
(b) C6H5CH2NH2
(c) C6H5NHOH
(d) C6H5NHCH2CH3.
14 Reaction of aniline with benzaldehyde is
(a) Substitution
(b) addition
(c) Condensation
(d) polymerization
15 The correct order of increasing basic nature for the bases NH3, CH3NH2 and (CH3)2 NH is
(a) CH3 NH2 < (CH3)2 NH < NH3
(b) CH3NH2 < NH3 < (CH3)2NH
(c) (CH3)2 NH< NH3 < CH3NH2
(d) NH3 < CH3NH2 < (CH3)2NH
16 The amine that does not react with acetyl chloride is
(a) CH3NH2
(b) (CH3)2NH
(c) (CH3)3 N
(d) none of these
17 Oxidation of aniline with K2Cr2O7/H2SO4 gives
(a) phenylhydroxylamine
(b) p-benzoquinone
(c) nitrosobenzene
(d) nitrobenzene
18 C6H5CONHCH3 can be converted into C6H5CH2NHCH3 by
(a) NaBH4
(b) H2-Pd/C
(c) LiAlH4
(d) Zn-Hg/HCl
152
19 Which of the following cannot couple with benzene diazonium chloride?
(a) Aniline
(b) Phenol
(c) ß-Napthol
(d) Benzyl alcohol.
20 The hybrid state of N is R2NH is

(a) sp³
(b) sp²
(c) sp
(d) dsp²
21 Which of the following element is present in functional group of amine ?
(A) oxygen
(B) nitrogen
(C) Sulphur
(D) phosphorous
22 Which of the following reactions is appriopate for converting acetamide to
methanamine
(A) Hoffmann brmamide reaction
(B) Stephen reduction
(C) Gabriel pthalamide synthesis
(D) Carbylamines reaction
23 Method by which aniline cannot be prepared is
(A) Degradation of bezamide with bromine in alkaline solution.
(B) Reduction of nitrobenzene with H2 /Pd in ethanol .
(C) Potassium salt of pthamilimde treatedwith cholorobenzene followed by
hydrolysiswith aqueous NaOH
(D) Hydrolysis of phenylisocyanide with acidic solution .
24 The action of nitrous acid on an aliphatic primary amine gives
(A) Scecondary amine
(B) Alcohol
(C) Nitro alkane
(D) Aldehyde
25 The compound obtasined by heating a mixture of ethylamine and choloroform with
ethanolic potassium hydroxide is
(A) An amide
(B) An amide and nitro compound
(C) An ethyl isocyanide
(D) An alkyl halide
26 The electrolytic reduction of nitrobenzene in strongly acidic medium produces
(A) Azo benzene
(B) Aniline
(C) p- aminophenol
(D) azoxybenzene
27 For carbylamines reaction ,we need hot alcoholic KOH and
153
(A) Any primary amine and choloroform
(B) Choloroform and silver powder
(C) A primary amine and an alkyl halide
(D) A monoalkylamine and tricholoromethane
28 Which of the following is a 30 amine ?
(A) 1-methyl cyclohexylamine
(B) Triethylamine
(C) Tert-butylamine
(D) N-methylaniline
29 Which of the following compound is soluble in water
(A) Alkane
(B) Alkyl halide
(C) Alkyne
(D) Primary amine
30 The source on nitrogen in gabriel pthalimide syntesis of amine is
(A) Sodium azide
(B) Sodium amide
(C) potassium cyanide
(D) potassium pthalimide
31 The correct IUPAC name for CH2==CHCH2 NHCH3 is
(A) Allylmethylamine
(B) 2-amino-4-pentene
(C) 4-aminopent-1-ene
(D) N-methylprop-2-en-1-amine
32 Which of the following reagents would not be a good choice for reducing an aryl nitro
compound to an amine?
(A) H2 (excess)/Pt
(B ) LiAlH4 in ether
(C) Fe and HCl
(D) Sn and HCl
33 Hoffmann Bromamide Degradation reaction is shown by
(A) ArNH2
(B) ArCONH2
(C) ArNO2
(D)ArCH2NH2
34 The gas evolved when methylamine reacts with nitrous acid is

(A) NH3
(B) N2
(C) H2
(D) C2H6
35 Reduction of aromatic nitro compounds using Fe and HCl gives

(A) aromatic oxime
154
(B) aromatic hydrocarbon
(C) aromatic primary amine
(D) aromatic amide
36 Best method for preparing primary amines from alkyl halides without changing the
number of carbon atoms in the chain is
(A) Hoffmann Bromamide reaction
(B) Gabriel phthalimide synthesis
(C) Sandmeyer reaction
(D) Reaction with NH3
37 Primary secondary and tertiary amine can be differentiated by which method
(A) Lucas test
(B) Iodoform test
(C) Tollen test
(D) Hinsberg test
38 Which amine does not show Friedel craft reactions
(A) Ethanamine
(B) Aniline
(C) Diethylamine
(D) All of above
39 Boiling point of which amine is maximum
(A) Propanamine
(B) Ethyl methyl amine
(C) Trimethyl amine
(D) Dimethyl amine
40 Carbylamines test is used to distinguish between
(A) Primary and secondary amine
(B) Secondary and tertiary amine
(C) Aldehyde snd ketone
(D) Primary ,secondary and tertiary amine
41 The IUPAC name of the following compound is
(A) N,N-Dimethyl butan-1-amine

(B) N,N-Diethyl butan-1-amine
(C) N-ethyl-N-butyl ethanamine
(D) N-butyl-N-ethyl ethanamines
42 Which of the following name reaction is used to convert amides into amines?
(A) Carbylamine reaction
(B) Gabriel Phthalimide Reaction
(C) Sandmeyer reaction
(D) Hoffmann bromamide degradation reaction
155
43 Which of the following amines cannot be prepared by Gabriel Phthalimide
Synthesis/reaction?
(A) N-methyl aniline
(B) benzyl amine
(C) butyl amine
(D) isobutyl amine
44 Which of the following amines has the highest boiling point ?
(A) 2-Methylbutanamine.
(B) 3-Methylbutanamine
(C) Pentanamine
(D) 2,2-dimethylpropanamine
45 Which among the following amine has the highest basic strength in aqueous
solution?
(A) NH3
(B) C2H5-NH2
(C) (C2H5)2NH
(D) (C2H5)3N
ANSWER KEY FOR AMINES SECTION-A
(MULTIPLE CHOICE QUESTION)
1. (d) 2.(c) 3.(c) 4.(b) 5.(d) 6.(c) 7.(c)
8.(c) 9.(a) 10.(c) 11. (d) 12.(c) 13.(a) 14.(c)
15.(d) 16.(c) 17.(b) 18.(c) 19.(d) 20.(a) 21.(B)
22.c) 23.b. 24.d. 2 5(.b) 26.(c) 27.(C) 28.(A)
29.(C) 30.(B) 31.(B) 32.II. 33.I. 34.III. 35.(D)
36.(A) SP³ 37.D 38.ANILINE 39.A 40. 41.B
42.D 43.A 44.C 45.C
156
QUESTION BANK
CLASS XII (CHEMISTRY)
UNIT : AMINES
ASSERTION REASON QUESTIONS

These questions consist of two statements, each printed as Assertion and Reason. While answering these
questions, you are required to choose any one of the following four responses.
(A) If both Assertion and Reason are correct and the Reason is a correct explanation of the
Assertion.
(B) If both Assertion and Reason are correct but Reason is not a correct explanation of the
Assertion.
(C) If the Assertion is correct but Reason is incorrect.
(D) If both the Assertion and Reason are incorrect.
1.Assertion : Only small amount of HCl is required in the reduction of nitro compounds which iron scrap
and HCl in the presence of steam.
Reason : FeCl2 formed gets hydrolyzed to release HCl during the reaction.
2. Assertion : Acetanilide is less basic than aniline

Reason : Acetylation of aniline results in a decrease of electrons.
3. Assertion : Benzyl amine is more basic than ammonia.

Reason : NH2 is electron releasing group?
4.Assertion : Aromatic primary amines be prepared by Gabriel Phthalimide.

Reason : Aryl halides undergo nucleophilic substitution reaction with anion formed by Phthalimide.
5. Assertion : Nitration of aniline can be conveniently done by protecting the amino group by acetylation.
Reason : Acetylation increases the electron density in the benzene ring.
6. Assertion : Aniline does not undergo Friedel Craft reaction .

Reason : -NH2 group of aniline reacts with AlCl3 ( Lewis acid ) to give acid based reaction.
7. Assertion : Aniline and N-methyl aniline can be differentiated by Carbyl amine reaction.
Reason : Aniline is primary amine and N-Methyl aniline is secondary amine .
8. Assertion : (CH3)3N is less basic than (CF3)3 N .

Reason : F is highly electronegative element, so CF3 group is electron withdrawing group.
9. Assertion : Hoffman Bromamide reaction is a degradation reaction .

Reason : By Hoffman Bromamide reaction we can prepare primary amine.
10. Assertion : Tertiary amines are less basic than secondary amines in aqueous medium.
Reason : Stearic hindrance due to 3 alkyl groups hinders the attack of acid on tertiary amine.
157
ANSWER KEY FOR AMINES (ASSERTION REASON QUESTION)
1.D 2.D 3.B 4.A 5.C 6.A 7.A 8.D 9.B

10.A
CASE BASED QUESTIONS (CASE BASED Q 1.)

Amines have higher boiling points than hydrocarbons of comparable molecular weight because the C—N
bond is more polar than a C—C bond. Also, primary and amines can form intermolecular hydrogen bonds
because they can act as both hydrogen bonddonors and acceptors. Tertiary amines have no hydrogen atoms
bonded to the nitrogen atomand therefore are not hydrogen bond donors.
Thus, tertiary amines cannot form intermolecular hydrogen bonds. As a result, they have lower boiling
points than primary and secondary amines of comparable molecular weight. Amines have lower boiling
points than alcohols because nitrogen is less electronegative thanoxygen. As a result the N—H bond is less
polar than the O—H bond, and the hydrogen bond in amines is weaker than the hydrogen bond in
alcohols.[ Robert J. Ouellette, J. David Rawn,in Organic Chemistry (Second Edition), 2018]
a) The boiling point of Ethyl alcohol is more than that of ethyl amine. Give reason.
b) The order of boiling points for the following amines is
CH3CH2CH2NH2>(CH3CH2CH2) NH>(CH3CH2) N(CH3),Explain
c) Arrange the following in the increasing order of molecular mass .
CH3CH2NH2, HCOOH,CH3CH2OH,CH3CH2CH3
ANSWERS OF CASE BASED Q 1.
a) N is less electronegative than oxygen and the hydrogen bond in amines are weakerthan that in
alcohols.
b) The boiling points of amines follows the order primary>secondary>tertiary Primaryamines have
2, secondary amines have 1 while tertiary amines have no hydrogen linked to nitrogen.
Among these compounds of comparable molecular masses, order of extend ofhydrogen
bond is hydrocarbons <amines<alcohols<carboxylic acids
c) Hence the order of given compounds of comparable molecular masses is
CH3CH2CH3< CH3CH2NH2< CH3CH2OH< HCOOH
-----------------------------------------------------------------------------------------------------------------------------------------
CASE BASED QUESTION 2
: Basicity of aliphatic amines in aqueous solution depends on +I effect, extent of hydrogen bonding with
water molecules, stearic effects of the alkyl group. In aromatic amines it depends on effect of substituent
on the ring. Basicity of alkyl amines, as the electrons arenot conjugated with benzene ring and not de-
localized. Hence electron pair is available forprotonation. In aromatic amines ortho effect refers mainly
to the set of stearic effects and some bonding interactions along with polar effects caused by the various
substituent whichare in a given molecule altering its chemical properties and physical properties. In a
generalsense the ortho effect is associated with substituted benzene compounds.
Anything ortho to the amine, no matter whether it is electron donating or withdrawing, willdecrease the
Basicity of the aromatic amine. This is because of the ortho effect, which is basically stearic effect. The
protonated amine will have a greater stearic interaction with the ortho group, so it will be less stable.
a) Compare the Basicity of aniline, m-nitroaniline, p- nitroaniline and ortho nitroaniline
b) Compare the Basicity of benzyl amine, aniline, methyl amine and ammonia
c) Aniline has pKb =9.38,p-aminophenol has pKb =8.50 and o-aminophenol haspKb=9.28, but m-
aminophenol has pKb=9.80. Explain.
158
ANSWERS of CASE BASED QUESTION 2
a) o-nitroaniline<p-nitroaniline<m-nitroaniline<Aniline(e.g. decreases the Basicity due to ortho effect o-
nitro aniline is the weak one among substituted anilines)
b) aniline<ammonia<benzyl amine<methyl amine (methyl group is more electron donating than benzyl
group, hence methyl amine is stronger base, in benzyl amine electrons are not delocalized. Hence better
base than aniline but ammonia with pkb value4.75 is more basic than benzyl amine(pKb=4.70)
c) Here though -OH group is in ortho position o-aminophenol is stronger base than aniline (pkb=9.38) and
m-aminophenol(pKb=9.80) due to stabilization of anilinium ion by hydrogen bonding.
VERY SHORT ANSWER TYPE QUESTIONS ( 2Marks)

1. Write the chemical equations involved when C2H5NH2 is treated with
(1) CH3COCl/Pyridine (2) CHCl3+KOH.
Ans1. (1) C2H5NH2+ CH3COCl/Pyridine → CH3CONHC2H5
(2) C2H5NH2+ CHCl3+3KOH(Alcoholic) →C2H5NC+3KCl+3H2O
2. Why aniline does not undergo Friedel -Crafts reaction?

Ans . Aniline does not undergo Friedel-Crafts reaction due to salt formation with aluminum
chloride, the Lewis acid, which is used as a catalyst.
3. Nitration of aniline yields considerable amounts of meta products. Why?
Ans 4 Nitration gives mixture of ortho, meta and para products.
In acidic medium aniline is protonated to anilinium ion which is meta directing. That is whybesides
ortho par products considerable amount of meta product is also formed.
4. Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?

Ans 5. Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution with the anion formed by the phthalimide.
5. Write equations of the following name reactions?
(1) Carbylamine reaction
(2) Hofmann’s bromamide degradation reaction.
Ans 6. (1) Carbylamine reaction
Aliphatic and aromatic primary amines on heating with chloroform and ethanolic KOH form
isocynides or carbylamines which are foul smelling substances. It is used as test for primary amines.
(2) Hofmann’s bromamide degradation reaction

Hoffmann developed a method for preparation of primary amines by treating with bromine in an
aqueous or ethanolic solution of NaOH. In this degradation reaction, migration of an alkyl or arylgroup
takes place from carbonyl carbon of the amide to the nitrogen atom. The amine so formed contains one
carbon less than that present in the amide.
159
LONG ANSWER TYPE QUESTIONS( 3 Marks)
1. How will you distinguish between primary ,secondary and tertiary amines? Write the
chemicalequations involved?
Ans 1 : Primary, secondary and tertiary amines can be distinguished by Hinsberg test.
The reaction of benzene sulphonyl chloride with primary amine yields N-ethylbenzenesulphonylamide
which is soluble in alkali.
In reaction with secondary amine, N,N-diethyl benzenesulphonamide is formed which is

insoluble in alkali.
Tertiary amines do not react with benzene sulphonyl chloride due to lack of hydrogen atom.
2. Complete the following reactions:

a)C6H5N2Cl+H3PO2+H2O→
b)C6H5NH2+H2SO4→
c)C6H5N2Cl+C2H5OH→
d)C6H5NH2+(CH3CO)2O→
Ans2 :
A. C6H5N2Cl+H3PO2+H2O →C6H6+ H3PO3+N2+HCl
B. C6H5NH2+H2SO4→C6H5NH3 +HSO4-
C. C6H5N2Cl+C2H5OH → C6H6+CH3CHO+ N2+HCl
D. C6H5NH2+(CH3CO)2O →C6H5NHCOCH3
3. An aromatic compound A on treatment with aqueous ammonia and heating forms a

compound B which on heating with Br2 and KOH forms a compound C of molecular formula
C6H7N.Write thestructures and IUPAC names of A, B, C.
Ans 3: C: C6H7N ie C6H5NH2

C is obtained from B on treating with Br2 and KOH
Br2 and KOH
B → C6H5NH2 ( C)
Hence B is C6H5CONH2
160
C6H5CONH2 + Br2 + KOH → C6H5NH2
B is obtained from A on treatment with aqueous ammonia
A: C6H5COOH: Benzoic acid
B: C6H5CONH2: Benzamide
C: C6H5NH2: Aniline
4. Accomplish the following conversions:

(1) Nitrobenzene to benzoic acid
(2) Benzoic acid to aniline
(3) Benzamide to toluene
(4) Aniline to benzyl alcohol
(5) Ethanoic acid to methanamine
---------------------------------------------------------------------------------------------------------------------------------------------
Sn/HCl . HNO2/50C H3PO2+H2O CH3Cl/AlCl3
Ans 4 : (1)C6H5NO2. → C6H5NH2 → C6H5N2Cl → . C6H6 → C6H5CH3

[O]
C6H5CH3 → C6H5COOH
--------------------------------------------------------------------------------------------------------------
NH3/heat Br2 and KOH
(2) C6H5COOH → C6H5CONH2 → C6H5NH2
------------------------------------------------------------------------------------------
Br2 and KOH HNO2/50C H3PO2+H2O CH3Cl/AlCl3
(3) C6H5CONH2 → C6H5NH2 → C6H5N2Cl → C6H6 → C6H5CH3
------------------------------------------------------------------------------------------------
HNO2/50C H3PO2+H2O CH3Cl/AlCl3 KMnO4/H+
(4) C6H5NH2 → C6H5N2Cl → C6H6 → C6H5CH3 → C6H5COOH
LiAlH4
→ C6H5CH2OH
-------------------------------------------------------------------------------------------------
NH3/heat Br2 and KOH
(5) CH3COOH → CH3CONH2 → C6H5NH2
161
QUESTION BANK
NOTE: VSA: 1 Mark SA: 2 Marks LA: 3 Marks VLA: 5 Marks

VERY SHORT ANSWER TYPE QUESTIONS
1. Give reasons for the following:
Primary amines have higher boiling point than tertiary amines. (1/3, AI 2016, Delhi
2008C)
2. Arrange the following in the increasing order of their boiling point:

C2H5NH2, C2H5OH, (CH3)3N (1/5, Delhi 2015)
3. Give a simple chemical test to distinguish between the following pair of compounds:
(CH3)2NH and (CH3)3N (1/5, Delhi 2015)
4. Arrange the following in increasing order of basic strength:
Aniline, p-nitroaniline, and p-toluidine (AI 2015C)
5. Why do amines act as nucleophiles? (AI 2007)
6. Complete the following reaction equation: C6H5N2Cl + H3PO2 + H2O ------------>
(Delhi 2015C, AI 2013, 2012)
LONG ANSWER TYPE QUESTIONS
7. Write the structures of main products when aniline reacts with the following
reagents:
a. Br2 water
b. HCl
c. (CH3CO)2O/pyridine (3/5, Delhi 2015)
VERY LONG ANSWER TYPE QUESTIONS

8. An aromatic compound ‘A’ of molecular formula C7H7ON undergoes a series of
reactionsas shown below. Write the structures of A, B, C, D and E in the following
reactions:
162
9. (i) Write the structures of main products when benzenediazonium
chloride(C6H5 N2+Cl–) reacts with the following reagents:
(a) HBF4 (b) Cu/HBr
(ii) Write the structures of A, B and C in the following reactions:(a)
163
UNIT 10 - BIOMOLECULES
SYLLABUS
Carbohydrates - Classification (aldoses and ketoses), monosaccahrides (glucose and
fructose), D-L configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides
(starch, cellulose,glycogen); Importance of carbohydrates.
Proteins -Elementary idea of - amino acids, peptide bond, polypeptides, proteins, structure
of proteins- primary, secondary, tertiary structure and quaternary structures (qualitative
idea only), denaturation of proteins; enzymes. Hormones -Elementary idea excluding
structure.
Vitamins - Classification and functions.
Nucleic Acids: DNA and RNA.
GIST OF THE LESSON
Carbohydrates: Polyhydroxy aldehydes or polyhydroxy ketones or compounds on hydrolysis
give carbohydrates. Classification of carbohydrates:
Monosaccharides: (a) Simplest carbohydrates
(b) It cannot be hydrolyzed into simpler compounds
(c) Examples – Glucose, mannose
Oligosaccharides: (a) Carbohydrates which gives 2 to 10 monosaccharide units on hydrolysis
(b) Examples – Sucrose, Lactose, Maltose
Polysaccharides: (a)Carbohydrates which on hydrolysis give large number of
monosaccharide units.
(b) Examples – Cellulose, starch
Anomers: Pair of optical isomers which differ in configuration only around C1 atom are
called anomers.
Examples – α-form and β-form
Epimers: Pair of optical isomers which differ in configuration around any C atom other than
C1 atom are called epimers. E.g. D-glucose and D- mannose are C2 epimers.
164
POINTS TO BE REMEMBER
Aldose – The monosaccharaides containing an aldehyde group are called aldose. Example:
glucose.
Ketose - The monosaccharaides containing a ketone group are called ketose. Example:
fructose.
Sugars - In general, monosaccharides and oligosaccharides are crystalline solids, soluble in
water and sweet in taste. These are collectively called sugars. E.g. glucose, sucrose.
Non-sugars – The polysaccharides are amorphous, insoluble in water and tasteless are known
as non-sugars. e.g starch and cellulose
Reducing sugars – Those carbohydrates which contains free aldehydic or ketonic group and
reduces Fehling’s solution and Tollen’s reagent are called reducing sugars. E.g. all
monosaccharides, maltose and lactose.
Non-reducing sugars – Those sugars which do not have free aldehydic or ketonic group and
do not reduce Fehling’s solution and Tollen’s reagent are called non-reducing sugars. E.g.
sucrose.
Structure of glucose:
165
Structure elucidation of glucose:
166
Other Reactions of Glucose (Presence of ring structure)
Glucose does not give Schiff’s test and does not react with sodium bisulphite and NH3.
Pentaacetyl glucose does not react with hydroxyl amine.
This shows the absence of –CHO group and hence the presence of ring structure.
Cyclic structure of glucose:
Glycosidic linkage: The oxide linkage formed by the loss of a water molecule when two
monosaccharides are joined together through oxygen atom is called glycosidic linkage.
Fructose: It is a ketohexose obtained by hydrolysis of disaccharide.
Structure of Fructose:
Open chain structure

Sucrose (invert sugar):
a) Sucrose is a non-reducing sugar because the two monosaccharide units are held together
by a glycosidic linkage between C1 of -glucose and C2 of – fructose. Since the reducing groups
of glucose and fructose are involved in glycosidic bond formation, sucrose is a non-reducing
sugar.
167
b)Sucrose is dextrorotatory but on hydrolysis it gives dextrorotatory & laevorotatory and the
mixture is laevorotatory.
Haworth Projection of Sucrose:

Maltose:
1. Maltose is composed of two α-D-glucose units in which C1 of one glucose (I) is linked to C4
of another glucose unit (II).
2. The free aldehyde group can be produced at C1 of second glucose in solution and it shows
reducing properties so it is a reducing sugar.
Lactose (Milk sugar): It is composed of β-D-galactose and β-Dglucose. The linkage is between
C1 of galactose and C4 of glucose. Hence it is also a reducing sugar.
Starch: It is a polymer of α -glucose and consists of two components — Amylose and
Amylopectin.
Amylose:
1. It is a water soluble component
2. It is a long unbranched chain polymer
3. It contains 200 – 1000 -D-(+)- glucose units held by –glycosidic linkages involving C1 –
C4glycosidic linkage
4. It constitutes about 15-20% of starch
Amylopectin:
1. It is a water insoluble component
2. It is branched chain polymer
168
3. It forms chain by C1 – C4glycosidic linkage whereas branching occurs by C1 – C6 glycosidic
linkage
4. It constitutes about 80-85% of starch
Cellulose:
1. It occurs exclusively in plants.
2. It is a straight chain polysaccharide composed only of β –D-glucose units which are joined
by glycosidic linkage between C1 of one glucose unit and C4 of the next glucose unit.
Glycogen:
1. The carbohydrates are stored in animal body as glycogen.
2. It is also known as animal starch because its structure is similar to Amylopectin.
3. It is present in liver, muscles and brain.
4. When the body needs glucose, enzymes break the glycogen down to glucose.
Amino acids: Amino acids contain amino (–NH2) and carboxyl (–COOH) functional groups.
Most naturally occurring amino acids have L – Configuration.
Types of amino acids:

a). Essential amino acids: The amino acids which cannot be synthesized in the body and must
be obtained through diet, are known as essential amino acids. Examples: Valine, Leucine
b). Non-essential amino acids: The amino acids, which can be synthesized in the body, are
known as non-essential amino acids. Examples: Glycine, Alanine
Zwitter ion form of amino acids:
169
1. Amino acids behave like salts rather than simple amines or carboxylic acids. This behaviour
is due to the presence of both acidic (carboxyl group) and basic (amino group) groups in the
same molecule. In aqueous solution, the carboxyl group can lose a proton and amino group
can accept a proton, giving rise to a dipolar ion known as zwitter ion. This is neutral but
contains both positive and negative charges.
2. In zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids
and bases.
Isoelectronic point: The pH at which the dipolar ion exists as neutral ion and does not migrate
to either electrode cathode or anode is called isoelectronic point.
Proteins: Proteins are the polymers of α-amino acids and they are connected to each other
by peptide bond or peptide linkage. A polypeptide with more than hundred amino acid
residues, having molecular mass higher than 10,000u is called a protein.
Peptide linkage: Peptide linkage is an amide linkage formed by condensation reaction
between –COOH group of one amino acid and –NH2 group of another amino acid.
Two shapes of proteins:
Fibrous Protein Globular Protein
(i) Polypeptide chains run parallel oranti-parallel (i) Chains of Polypeptide coil around to give a
and held together by spherical shape.
Hydrogen and disulphide bonds.
(ii) Generally insoluble in water. E.g. Keratin, Usually soluble in water. e.g., insulin,
collagen,myosin,fibroin. thyroglobin,albumin, haemoglobin and
fibrinogen gets converted into fibrous protein
fibroin on clotting of blood.
Structure of proteins:
QuaternaryStructure
Primary SecondaryStructure Tertiary Structure
Structure
170
The specific It is the shape inwhich the Represents overall folding Protein can be composed
sequence of long polypeptide chain of the polypeptide chain. of two or more
amino acids inthe can exist.It is of two types Itgives rise to the fibrous Polypeptide chainscalled
polypeptide : α-helix and β-pleated or globular molecular sub units.The spatial
chain. These structures arisedue shapes. Forces stabilizing arrangement of these sub
Change in amino to regularfolding of the the 2oand 3o structures unitswith respect
acidssequence backbone of the are hydrogen bonds, toeach other
changes the polypeptide chain due to disulphide linkages, van is
protein H-bonding between the der Waal’s and electrostatic quaternary structure of
completely. C=o and –NH- forces of attraction. theprotein.
They have Groups of the peptide
Covalentbonds. bond.
Denaturation of proteins:
The loss of biological activity of proteins when a protein in its native form, is subjected to
physical change like change in temperature or chemical change like change in pH. This is called
denaturation of protein.During denaturation secondary and tertiary structures get
destroyed,only primary structure remains intact.
Example: coagulation of egg white on boiling, curdling of milk.
Nucleic acids:
Nucleoside: Base + sugar
Nucleotide: Base + sugar + phosphate group
Nucleic acids (or polynucleotides):

1. Long chain polymers of nucleotides.
171
2. Nucleotides are joined by phosphodiester linkage between 5’ and 3’ C atoms of a pentose
sugar.
Two types of nucleic acids: DNA
1. It has a double stranded -helix structure in which two strands are coiled spirally in opposite
directions.
2. Sugar present is –D–2-deoxyribose
3. Bases:
i) Purine bases: Adenine (A) and Guanine (G)
ii) Pyrimidine bases: Thymine (T) and cytosine (C)
4. It occurs mainly in the nucleus of the cell.
5. It is responsible for transmission for heredity character.
RNA
1. It has a single stranded -helix structure.
2. Sugar present is –D–ribose
3. Bases: i) Purine bases: Adenine (A) and Guanine (G)
ii) Pyrimidine bases: Uracil (U) and cytosine (C)
4. It occurs mainly in the cytoplasm of the cell.
5. It helps in protein synthesis.
172
Double helix structure of DNA:
1. It is composed of two right handed helical polynucleotide chains coiled
spirally in opposite directions around the same central axis.
2. Two strands are anti-parallel i.e., their phosphodiester linkage runs in
opposite directions.
3. Bases are stacked inside the helix in planes to the helical axis.
4. Two strands are held together by H – bonds (A = T, G Ξ C).
5. The two strands are complementary to each other because the hydrogen
bonds are formed between specific pairs of bases.
6. Adenine forms hydrogen bonds with thymine whereas cytosine forms
hydrogen bonds with guanine.
7. Diameter of double helix is 2 nm.
8. Double helix repeats at intervals of 3.4 nm. (One complete turn)
9. Total amount of purine (A + G) = Total amount of pyrimidine (C + T)
Vitamins and their deficiency diseases:
173
S.No. Vitamin Sources Deficiency diseases
1 A Fish liver oil,carrot,butter,milk Night

blindness, xeropthalmia
2 C Citrus fruits,amla,green leafy curvy
vegetables
3 D Fish, egg yolk, exposure to sun Rickets,osteomalacia,
light
4 E Sunflower oil, wheat, germ oil Muscular
weakness, increased fragility of
RBCs
5 K Green leafy vegetables Increased blood clotting time
6 B1 Yeast,milk,cereals,green vegetables Beri beri,
7 B2 Milk, egg white, liver ,kidney Cheilosis, digestive

disorders
8 B6 Yeast,milk,egg yolk,cereals convulsions
,grams
9 B12 fish ,meat, ,egg, curd Pernicious anaemia
MCQ’S
Q.1. Name the simplest amino acid
(a). Alanine (b). Tyrosine (c). Asparagine (d). Glycine
Q.2. The helical structure of protein is stabilized by:
(a) Peptide band (b) Dipeptide band (c) Hydrogen bands (d) vander Waal’s forces
Q.3. The functional group which is found in amino acids is
(a) COOH (b) -NH2 (c) -CH3 (d) both (a) and (b).
Q.4. The vitamins absorbed from intestine along with fats are
(a) A and D (b) A, B (c) A, C (d) D, B
Q.5.Which of the following in the sweetest sugar:
(a) Sucrose (b) Glucose (c) Fructose (d) Maltose
174
Q.6. Which of the following bases is not present in DNA?
(a) Adenine (b) Thymine (c) Cytosine (d) Uracil
Q.7. Sucrose (cane sugar) is a disaccharide. One molecule of sucrose on hydrolysis gives
_________.
(a) 2 molecules of glucose
(b) 2 molecules of glucose + 1 molecule of fructose
(c) 1 molecule of glucose + 1 molecule of fructose
(d) 2 molecules of fructose
Q.8. Which one is correct?
(a) Starch is a polymer of α-glucose
(b) Amylose is a component of cellulose.
(c) Proteins are composed of only one type of amino acids
(d) In cyclic structure of furanose, these are 4 carbons and one oxygen atom.
Q.9. Which of the following reactions of glucose can be explained only by its cyclic
structure?
(a) Glucose forms pentaacetate.
(b) Glucose reacts with hydroxylamine to form an oxime.
(c) Pentaacetate of glucose does not react with hydroxylamine.
(d) Glucose is oxidized by nitric acid to gluconic acid.
Q.10. Each polypeptide in a protein has amino acids linked with each other in a specific
sequence. This sequence of amino acids is said to be ____________.
(a) Primary structure of proteins. (b) Secondary structure of proteins.
(c) Tertiary structure of proteins. (d) Quaternary structure of proteins.
Q.11. α-D (+) Glucose and β-D (+) glucose are
(a) Epimers (b) Anomers (c) Enantiomers (d) Conformational isomer
Q.12. Complete the following analogy:
Curdling of milk : A :: α-helix : B
(a) A: Primary structure B: Secondary structure
(b) A: Denatured protein B: Primary structure
(c) A: Secondary structure B: Denatured protein
(d) A: Denatured protein B: Secondary structure
Q.13. In disaccharides, if the reducing groups of monosaccharides i.e. aldehydic or ketonic
groups are bonded, these are non-reducing sugars. Which of the following disaccharide is a
non-reducing sugar?
175
176
Q.14.Which of the following pairs represents anomers?
Directions: These questions consist of two statements, each printed as Assertion and
Reason. While answering these questions, you are required to choose any one of the
following four responses.
(a) If both Assertion and Reason are correct and the Reason is a correct explanation of the
Assertion.
(b) If both Assertion and Reason are correct but Reason is not a correct explanation of the
Assertion.
(d) If both the Assertion and Reason are incorrect.
Q.15. Assertion: D(+)– Glucose is dextrorotatory in nature.

Reason: ‘D’ represents its dextrorotatory nature.
177
Q16. Assertion: Sucrose is called an invert sugar.
Reason: On hydrolysis, sucrose bring the change in the sign of rotation from dextro (+) to
laevo(–).
Q.17. Assertion: β-glycosidic linkage is present in maltose
Reason: Maltose is composed of two glucose units in which C–1 of one glucose unit is linked
to C–4 of another glucose unit.
Q.18. Assertion: Polysaccharides are called non-sugars.
Reason: Carbohydrates which yield a large number of monosaccharide units on hydrolysis
are called polysaccharides.
Q.19. Assertion: Vitamin D cannot be stored in our body
Reason: Vitamin D is fat soluble vitamin and is excreted from the body in urine
Q.20. Assertion: All naturally occurring α-amino acids except glycine are optically active.
Reason: Most naturally occurring amino acids have L-configuration.
1 d 2 c 3 d 4 a 5 C
6 d 7 c 8 a 9 c 10 A
11 b 12 d 13 b 14 c 15 C
16 a 17 d 18 b 19 d 20 b
Q.21.Match the items of Column I and Column II in the following questions. More than one
option in Column II may match with the items given in Column I.
Match the vitamins given in Column I with the deficiency disease they cause given in Column
II.
178
Ans. (i) → (c), (f) (ii) → (g) (iii) → (a) (iv) → (h) (v) →(d) ,(i)
(vi) → (e) (vii) → (b)
Directions: After reading the passage, answer the following questions:

Q.22. After watching a programme on TV about the presence of carcinogens (cancer causing
agents) Potassium bromate and Potassium iodate in bread and other bakery products, Ritu a
class XII student decided to aware others about the adverse effects of these carcinogens in
foods. She consultanted the school principal and requested him to instruct canteen
contractor to stop selling sandwiches, pizza, burgers and other bakery products to the
students. Principal took an immediate action and instructed the canteen contractor to replace
the bakery products with some proteins and vitamins rich food like fruits, salads, sprouts etc.
The decision was welcomed by the parents and students.
i. Which polysaccharide component of carbohydrates is commonly present in bread?
ii. Write the two types of secondary structure of proteins.
iii. Give two examples of water soluble vitamins.
iv. Write the name of the vitamin whose deficiency causes bleeding of gums.
Ans. i. The main component of polysaccharide present in bread is starch.
ii. α – helix and β – pleated sheet structures.
iii. Vitamin B and vitamin C
iv. Vitamin C
179
Q.23. Shanti, a domestic helper of Mrs. Anuradha, fainted while mopping the floor. Mrs.
Anuradha immediately took her to the nearby hospital where she was diagnosed to be
severely ‘anemic’. The doctor prescribed an iron rich diet and multivitamins supplement to
her. Mrs. Anuradha supported her financially to get the medicines. After a month, Shanti was
diagnosed to be normal.
i. Name the vitamin whose deficiency causes ‘pernicious anaemia’.
ii. Give an example of a water-soluble vitamin.
iii. Write the name of vitamin whose deficiency causes bone deformities in children.
iv. Deficiency of which vitamin causes night-blindness?
Ans. i. Deficiency of vitamin B12 (cyanocobalamin ) causes the disease pernicious anaemia.
ii. Vitamin B and vitamin C
iii. Vitamin D
iv. Vitamin A
VERY SHORT ANSWER TYPE QUESTIONS

Q.1.Which one of the following is a monosaccharide: starch, maltose, fructose, cellulose?
Ans. fructose
Q.2.Why cannot vitamin C be stored in our body?
Ans. Vitamin C cannot be stored in our body because it is water soluble. As a result, it is readily
excreted in the urine.
Q.3. What are reducing sugars?

Ans. Reducing sugars are carbohydrates that reduce Fehling’s solution and Tollen’s reagent.
All monosaccharides and disaccharides are reducing sugars.
Q.4. What do you understand by the term glycosidic linkage?

Ans. Glycosidic linkage refers to the linkage formed between two monosaccharide units
through an oxygen atom by the loss of a water molecule.
For example, in a sucrose molecule, two monosaccharide units, ∝-glucose and β-fructose, are
joined together by a glycosidic linkage.
Q.5. What is meant by denaturation of Protein?
Ans. The protein in native state, when subjected to a physical change like temperature, pH
etc. undergoes uncoiling and loses its biological activity. The 2oand 3ostructures are
destroyed, only 1o structure is retained.Eg.boiling of egg white.
180
Q.6. What are the different types of RNA found in the cell?
Ans. (i) Messenger RNA (m-RNA), (ii) Ribosomal RNA (r-RNA). (iii) Transfer RNA (t-RNA)
Q.7. How many atoms are present in the ring of pyranose structure of glucose?
Ans. 5 Carbon atoms and one Oxygen atom.
Q.8. Write the formula of Zwitter ion for Glycine.
Ans.
R-CH-COO- CH2-COO-
NH3+ NH3+
General Formula Zwitter ion of glycine
Q.9. Which proteins possess α-Helix structure?
Ans. Keratin and myosin possess α-Helix structure.
Q.10. What is the native state of protein?
Ans. The energetically most stable shape of the protein at normal pH and temperature is
called native state.
Q.11. Fresh tomatoes are a better source of Vitamin C that which have been stored for
some time. Explain.
Ans. Vitamin C is destroyed on prolonged exposure to air due to its oxidation.
Q.12. Why are carbohydrates generally active?
Ans. It is due to the presence of Chiral Carbon atoms in their molecules.
Q.13. What type of linkages hold together monomers in DNA?
Ans. Monomers in DNA are linked by phosphate linkages.
Q.14. Why is cellulose not digested in human body?
Ans. It is due to the fact that human beings do not have enzyme to digest cellulose.
181
SHORT ANSWER TYPE QUESTIONS
Q.1.Differentiate between globular and fibrous proteins.
Fibrous protein Globular protein
It is a fiber-like structure formed by the The polypeptide chain in this

polypeptide chain. These proteins are protein is folded around
1. 1.
held together by strong hydrogen and itself, giving rise to a
disulphide bonds. spherical structure.
2. It is usually insoluble in water. 2. It is usually soluble in water.
Fibrous proteins are usually used for

All enzymes are globular
structural purposes. For example,
proteins. Some hormones
3. keratin is present in nails and hair; 3.
such as insulin are also
collagen in tendons; and myosin in
globular proteins.
muscles.
Q.2. How do you explain the amphoteric behaviour of amino acids?
Ans. In aqueous solution, the carboxyl group of an amino acid can lose a proton and the amino
group can accept a proton to give a dipolar ion known as zwitter ion.
Therefore, in zwitter ionic form, the amino acid can act both as an acid and as a base.
Thus, amino acids show amphoteric behaviour.
Q.3. What is the difference between a nucleoside and a nucleotide?
Ans. A nucleoside is formed by the attachment of a base to position of sugar.
182
Nucleoside = Sugar + Base.
On the other hand, all the three basic components of nucleic acids (i.e., pentose sugar,
phosphoric acid, and base) are present in a nucleotide.
Nucleotide = Sugar + Base + Phosphoric acid
Q.4. Write the important structural and functional differences between DNA and RNA.
Ans. The structural differences between DNA and RNA are as follows:
DNA RNA
The sugar moiety in DNA molecules is The sugar moiety in RNA molecules
1. 1.
β-D-2 deoxyribose. is β-D-ribose.
DNA contains uracil (U). It does not RNA contains thymine (T). It does
2. 2.
contain thymine (T). not contain uracil (U).
The helical structure of DNA is The helical structure of RNA is

3. 3.
double-stranded. single-stranded.
183
The functional differences between DNA and RNA are as follows:
DNA RNA
DNA is the chemical basis

1. 1. RNA is not responsible for heredity.
of heredity.
Proteins are synthesized DNA molecules do not synthesize proteins, but

2. by RNA molecules in the 2. transfer coded message for the synthesis of
cells. proteins in the cells.
Q.5. Write the products of hydrolysis of following carbohydrates.
Carbohydrate Products on hydrolysis(monomers)

Sucrose α-D- Glucose & β-D fructose
Maltose α-D- Glucose & α-D Glucose
Lactose β-D Glucose & β-D Galactose
Starch α-D-Glucose
Cellulose β-D-Glucose
Q.6. (I) What type of linkage is present in nucleic acid?

(II) Give one example each for fibrous protein and globular protein.
Ans. (i) Phosphodiester linkage.
(ii) Fibrous protein: Myosin, Keratin, Collagen, etc.
Globular protein: insulin, haemoglobin, etc.
Q.7.Write the differences between essential and non-essential amino acids.
Essential amino acids Non-essential amino acids

those which cannot biosynthesized in amino acids, which can be synthesized
the body and must be obtained in the body, are known as nonessential
through diet, are known Amino acids. Eg.Giycine
as essential amino acid,Eg.Valine
LONG ANSWER TYPE QUESTIONS

Q.1. What happens when D-glucose is treated with the following reagents?
(i) HI (ii) Bromine water (iii) HNO3
184
Ans. (i) When D-glucose is heated with HI for a long time, n-hexane is formed.
(ii) When D-glucose is treated with Br2 water, D- gluconic acid is produced.
(iii) On being treated with HNO3, D-glucose get oxidized to give saccharic acid.
Q.2.i) Name the protein and its shape present in oxygen carrier in human body.
ii) What type of linkage is present in proteins?
iii) If one strand of a DNA has the sequence –ATGCTCAC-, what is the sequence of the bases
in the complementary strand?
Ans. i) Globular protein and its shape is spherical
ii) Peptide linkage (−CONH−)
iii) In DNA molecule ,Adenine (A)always pairs with thymine(T)and Cytosine (C)always pairs
with Guanine (G),Thus ,
Sequence of bases in one strand –ATGCTCAC Sequence of bases in the complementary strand
−TACGAGTG−
185
Q.3.Give reasons for the following
i) Amino acids have relatively higher melting point as compared to corresponding halo alkane.
ii) Amino acids are amphoteric in nature
iii) On electrolysis in acidic solution amino acid migrate towards cathode while in alkaline
solution these migrate towards anode
Ans. I)due to ionic form amino acids become crystalline solids and due to this salt like
structural show higher melting points .
ii) Due to presence zwitter ion amino react with acid and acid react with amine thus they
show amphoteric nature
iii) Amino acids exist in the form of zwitter ion .In acidic solution –ve charge on COO group
gets neutralized thus they move towards cathode, due to the presence positive charge on
NH3+ on electrolysis in basic solution +ve charge on –NH3 gets neutralized thus they move
towards anode, due to the presence of –ve charge on COO- group on electrolysis
Q.4.Write the chemical reaction to show the presence of the following facts in the structure
of the glucose?
i) All the six carbons of glucose are linked in a straight chain.
Ii) Presence of carbonyl group
iii) Presence of an aldehyde group
iv) 5-OH groups are attracted to different carbon atoms
v) Presence of a primary alcoholic group
Ans. i) on prolonged heating of glucose with HI, it gives n Hexane, which conforms that all the
six carbon atoms are linked in a straight chain.
ii) Glucose adds one molecule of Hydrogen cyanide and form hydrin as well as on reaction
with hydroxyl amine it gives an oxime.
iii) Glucose gets oxidized to six carbon carboxylic acid, gluconic acid when it is treated with a
mild oxidizing agent like bromine water.
iv) On acetylation with acetic anhydride glucose gives penta acetate which confirms the
presence of five OH groups.
186
v) On oxidation with nitric acid, glucose as well as gluconic acid both forms saccharic acid, a
dicarboxylic acid.
Q.5. (i) (A) What is the difference between native protein and denatured protein?
(b) Which one of the following is a disaccharide?
Glucose, Lactose, Amylose ,Fructose
(c) Name the location where protein synthesis occurs in our body
(ii) Define the following terms:
(a) Native protein (b) Nucleotide.
Ans. (i) (a) Protein found in a biological system with unique 3D structure( unique sequence of
amino acids) and biological activity is called native protein .When a protein in its native form
is subjected to change such as change in
Temperature, change in pH, its structures are destroyed and it loses its biological activity .the
protein thus formed is called denatured protein.
(b) Lactose
(c) RNA (Nucleic acid)
(ii) (a) Protein found in a biological system with unique 3D structure (unique sequence of
amino acids) and biological activity is called native protein.
b) A unit formed by the combination of nitrogenous base, pentose sugar and phosphate.
UNSOLVED QUESTIONS:
1. Nucleosides are composed of

(a) a pentose sugar and phosphoric acid (b) a nitrogenous base and phosphoric acid
(c) a nitrogenous base and a pentose sugar. (d) a nitrogenous base, a pentose sugar
and phosphoric acid
2.Amino acids which cannot be synthesized in the body and must be obtained through
diet are known as
(a) Acidic amino acids (b) Essential amino acids.
(c) Basic amino acids. (d) Non-essential amino acids
187
3.Which of the following sugar is known as dextrose?
(a) Glucose. (b) Fructose. (c) Ribose. (d) Sucrose
4. The base which is present in DNA but not in RNA, is
(a) Cytosine. (b) Guanine. (c) Adenine. (d) Thymine
5. Nucleic acids are polymer of
(a) Amino acids. (b) Nucleosides. (c) Nucleotides. (d) Glucose.
6. Glucose on reaction with Br2 water gives:
(a) Saccharic acid. (b) Hexanoic acid. (c) Gluconic acid. (d) Salicylic acid
7. Assertion (A): Two strands in DNA are complementary to each other.
Reason (R): Two strands in DNA held by intermolecular H-bond between bases.
(a) Both A and R are true and R is the correct explanation of A.
(b) Both A and R are true but R is not the correct explanation of A
(c) A is true but R is false.
(d) A is false but R is correct.
8. Anyone who has fried an egg has observed denaturation. The clear egg white turns
opaque as the albumin denatures and coagulates. No one has yet reversed that process.
However, given the proper circumstances and enough time, a protein that has unfolded
under sufficiently gentle conditions can refold and may again exhibit biological activity.
After reading the above passage, answer the following questions:
(I)Define the term ‘denaturation of protein.
(ii) Which of the following structures remains intact during denaturation?
(a) Primary structure (b) Secondary structure (c) Tertiary structure (d) Quaternary
structure
(III)Write two examples of denaturation of proteins.
(iv) Differentiate fibrous proteins and globular proteins
9. Classify the following into monosaccharides and disaccharides.
Ribose, fructose, lactose and maltose
10. Why vitamins A&C are essential for us.
188
11. Name the type of vitamins responsible for clotting blood and fertility in human beings.
12. What type of linkage is present in polysaccharides?
13. Write the name of two monosaccharides obtained on hydrolysis of lactose sugar.
14. Deficiency of which vitamin causes rickets?
15. Why Vitamin C cannot be stored in our body?
16. Write any two reactions of glucose which cannot be explained by the open chain
structure of glucose molecule.
17. Define the following terms with a suitable example in each:
(i) Polysaccharides (ii) Denatured protein (iii) Fibrous protein
18. Differentiate between following:
(i) Amylose and Amylopectin (ii) Globular protein and Fibrous protein
(iii) Nucleotide and Nucleoside
19. Write chemical reactions to show that open structure of D-glucose contains the
following: (i) Straight chain (ii) Five alcohol groups
(iii) Aldehyde as carbonyl group (iv) primary alcoholic group
20. Define the following with an example of each:
(i) Anomers (ii) Inversion of sugars (iii) Essential amino acids
CBSE BOARD QUESTIONS
21. Give the plausible explanation for the following :
(a) Glucose doesn’t give 2,4-DNP test.
(b) The two strands in DNA are not identical but are complementary.
(c) Starch and cellulose both contain glucose unit as monomer, yet they are structurally
different[CBSE 2020]
22.(a) How can you explain the absence of an aldehyde group in the pentaacetate of D-
glucose ?
(b) Name the bases present in RNA. Which one of these is not present in DNA ? [CBSE 2020]
23.(a) What is the difference between a nucleoside and nucleotide?
(b)What products would be formed when a nucleotide from DNA containing thymine is
hydrolyzed? [CBSE 2022]
189
24. Proteins are polymers of
(a) Nucleic acids (b )Amino acids (c) Monosaccharides (d) Amines [CBSE 2022]
25. Give the reaction of glucose with acetic anhydride. Presence of which group is
confirmed by this reaction? [CBSE 2023]
26. Give reasons for any three of the following observations:
a) Penta acetate of glucose does not react with hydroxylamine.
b) amino acids behave like salts.
c) water soluble vitamins must be taken regularly in diet. d) the two strands in DNA are
complementary to each other. [CBSE 2023]
----------------- END ----------------
190
SAMPLE PAPER (2023-24)
CHEMISTRY THEORY (043)
Max. Marks:70 Time: 3 hours
General Instructions:
Read the following instructions carefully.
(a) There are 33 questions in this question paper with internal choice.
(b) SECTION A consists of 16 multiple-choice questions carrying 1 mark each.
(c) SECTION B consists of 5 short answer questions carrying 2 marks each.
(d) SECTION C consists of 7 short answer questions carrying 3 marks each.
(e) SECTION D consists of 2 case- based questions carrying 4 marks each.
(f) SECTION E consists of 3 long answer questions carrying 5 marks each.
(g) All questions are compulsory.
(h) Use of log tables and calculators is not allowed
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries 1 mark.
There is no internal choice in this section.
1. Which of the following solutions will have the highest conductivity at 298 K?
(a) 0.01 M HCl solution (b) 0.1 M HCl solution
(c) 0.01 M CH3COOH solution (d) 0.1 M CH3COOH solution
2.
Identify A and B:
(a) A = 1-phenylethanal , B = acetophenone (b) A = Benzophenone B = formaldehyde
(c) A= Benzaldehyde , B = Acetophenone (d) A = Benzophenone , B = Acetophenone
3. The vitamins which can be stored in our body are:
(a) Vitamin A, B, D and E (d) Vitamin A, C, D and K
(c) Vitamin A, B, C and D (d) Vitamin A, D, E and K
4. What is IUPAC name of the ketone A, which undergoes iodoform reaction to give
CH3 CH= C(CH3)COONa and yellow precipitate of CHI3 ?
(a) 3-Methylpent-3-en-2one (b) 3-Methylbut-2-en- one
(c) 2, 3-Dimethylethanone (d) 3-Methylpent-4-one
5. Which of the following is not correct?
(a) In haloarenes, the electron pairs on halogen atom are in conjugation with π-electrons of the ring.
(b) The carbon-magnesium bond is covalent and non-polar in nature .
(c) During SN1 reaction, the carbocation formed in the slow step being sp2 hybridised is planar.
(d) Out of CH2= CH-Cl and C6H5CH2Cl, C6H5CH2Cl is more reactive towards SN1 reaction
6. Match the properties with the elements of 3d series:
(i) lowest enthalpy of atomisation (p) Sc
(ii) shows maximum number of oxidation states (q) Mn
(iii) transition metal that does not form coloured compounds (r) Zn
(s) Ti
(a) (i) (r), (ii) (q), (iii) (p) (b) (i) (r), (ii) (s), (iii) (p)
(c) (i) (p), (ii) (q), (iii) (r) (d) (i) (s), (ii) (r), (iii) (p)
7. Which of the following statement is true?
(a) molecularity of reaction can be zero or a fraction.
(b) molecularity has no meaning for complex reactions.
(c) molecularity of a reaction is an experimental quantity
(d) reactions with the molecularity three are very rare but are fast.
8. In which of the following solvents, the C4H8NH3 + X– is soluble;
(a) ether (b) acetone (c) water (d) bromine water
9. Which of the following observation is shown by 2-phenyl ethanol with Lucas Reagent?
(a) Turbidity will be observed within five minutes
(b) No turbidity will be observed
(c) Turbidity will be observed immediately
(d) Turbidity will be observed at room temperature but will disappear after five minutes.
10. If the initial concentration of substance A is 1.5 M and after 120 seconds the concentration of
substance A is 0.75 M, the rate constant for the reaction if it follows zero - order kinetics is:
(a) 0.00625 molL-1s-1 (b) 0.00625 s-1 (c) 0.00578 molL-1s-1 (d) 0.00578 s-1
11. Anisole undergoes bromination with bromine in ethanoic acid even in the absence of iron (III)
bromide catalyst
(a) Due to the activation of benzene ring by the methoxy group.
(b) Due to the de-activation of benzene ring by the methoxy group.
(c) Due to the increase in electron density at ortho and para positions
(d) Due to the formation of stable carbocation .
12 . The trend of which property is represented by the following graph?
(a) ionization enthalpy (b) atomic radii

(c) enthalpy of atomization (d) melting point
For Visually Challenged Learners
12. Which of the following is not considered a transition element?
(a) Scandium (b) Silver (c) Vanadium (d) Zinc
13. Given below are two statements labelled as Assertion (A) and Reason (R)
Assertion (A): Alcohols react both as nucleophiles and electrophiles.
Reason (R): The bond between C–O is broken when alcohols react as nucleophiles.
Select the most appropriate answer from the options given below:
(a) Both A and R are true and R is the correct explanation of A
(b) Both A and R are true but R is not the correct explanation of A.
(d) A is false but R is true.
Assertion (A): Strong oxidising agents oxidises toluene and its derivatives to benzoic acids.
Reason (R): It is possible to stop the oxidation of toluene at the aldehyde stage with suitable
reagents.
Assertion : Enzymes are very specific for a particular reaction and for a particular substrate.
Reason : Enzymes are biocatalysts.
Assertion (A): During electrolysis of aqueous copper sulphate solution using copper electrodes
hydrogen gas is released at the cathode.
Reason (R): The electrode potential of Cu2+ /Cu is greater than that of H+/H2
3
SECTION B
This section contains 5 questions with internal choice in one question. The following questions are
very short answer type and carry 2 marks each.
17. The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
1
concentration of the reactant to its th value? [log2 = 0.30, log4 = 0.60]
16
18. A 5% solution of Na2SO4.10H2O (MW = 322) is isotonic with 2% solution of non- electrolytic, non
volatile substance X. Find out the molecular weight of X.
19. (a) Arrange the isomeric dichlorobenzene in the increasing order of their boiling point and melting
points.
(b) Explain why the electrophilic substitution reactions in haloarenes occur slowly and require
more drastic conditions as compared to those in benzene.
20. (a) Out of p-tolualdehyde and p-nitrobenzaldehyde ,which one is more reactive towards
nucleophilic addition reactions, why?
(b) Write the structure of the product formed when acetone reacts with 2,4 DNP reagent .
OR
Convert the following:
(a) Benzene to m-nitrobenzaldehyde
(b) Bromobenzene to benzoic acid
21. (a) DNA fingerprinting is used to determine paternity of an individual. Which property of DNA
helps in the procedure?
(b) What structural change will occur when a native protein is subjected to change in pH?
SECTION C
This section contains 7 questions with internal choice in one question. The following questions are
short answer type and carry 3 marks each.
22. (a) Write the formula for the following coordination compound
Bis(ethane-1,2-diamine) dihydroxidochromium(III) chloride
(b) Does ionization isomer for the following compound exist? Justify your answer.
Hg[Co(SCN)4]
(c) Is the central metal atom in coordination complexes a Lewis acid or a Lewis base? Explain.
23. (a) Can we construct an electrochemical cell with two half-cells composed of ZnSO4 solution and
zinc electrodes? Explain your answer.
(b) Calculate the λ0m for Cl- ion from the data given below:
Λ0m MgCl2 = 258.6 Scm2mol–1 and λ0m Mg2+ = 106 Scm2mol–1

(c) The cell constant of a conductivity cell is 0.146 cm-1. What is the conductivity of 0.01 M solution
of an electrolyte at 298 K, if the resistance of the cell is 1000 ohm?
4
24. Write the name of the reaction, structure and IUPAC name of the product formed when:
(a) phenol reacts with CHCl 3 in the presence of NaOH followed by hydrolysis.
(b) CH3CH2 CH(CH3)CH(CH3)ONa reacts with C2H5Br
25. You are given four organic compounds “A”, “B”, “C” and “D”. The compounds “A”, “B” and “C”
form an orange- red precipitate with 2,4 DNP reagent. Compounds “A” and “B” reduce Tollen’s
reagent while compounds “C” and “D” do not. Both “B” and “C” give a yellow precipitate when
heated with iodine in the presence of NaOH. Compound “D” gives brisk effervescence with sodium
bicarbonate solution. Identify “A”, “B”, “C” and “D” given the number of carbon atoms in three of
these carbon compounds is three while one has two carbon atoms. Give an explanation for your
answer.
26. When sucrose is hydrolysed the optical rotation values are measured using a polarimeter and are
given in the following table:
S.No. Time (hours) Specific Rotation

1 0 + 66.5o
2 ∞ -39.9o
(a) Account for the two specific rotation values.
(b) What is the specific name given to sucrose based on the above observation.
(c) One of the products formed during the hydrolysis of sucrose is a glucose, that reacts with
hydroxylamine to give compound A. Identify compound A.
27. An organic compound A with the molecular formula (+)C4H9Br undergoes hydrolysis to form (+ )
C4H9OH. Give the structure of A and write the mechanism of the reaction.
28. The rate constants of a reaction at 200K and 500K are 0.02s–1 and 0.20s–1 respectively. Calculate the
value of Ea (Given 2.303R = 19.15 JK-1mol-1)
SECTION D
The following questions are case-based questions. Each question has an internal choice and carries
4 (1+1+2) marks each. Read the passage carefully and answer the questions that follow.
29. Crystal field splitting by various ligands
Metal complexes show different colours due to d-d transitions. The complex absorbs light of specific
wavelength to promote the electron from t2g to eg level. The colour of the complex is due to the
transmitted light, which is complementary of the colour absorbed.
The wave number of light absorbed by different complexes of Cr ion are given below:
Complex Wavenumber of light Energy of light absorbed

absorbed (cm-1) (kJ/mol)
[CrA6]3- 13640 163
[CrB6]3+ 17830 213
[CrC6]3+ 21680 259
[CrD6]3- 26280 314
5
(a) Out of the ligands “A”, “B”, “C” and “D”, which ligand causes maximum crystal field splitting?
Why?
OR
Which of the two, “A” or “D” will be a weak field ligand? Why?
(b) Which of the complexes will be violet in colour? [CrA6]3- or [CrB6]3+ and why? (Given: If 560 -
570 nm of light is absorbed, the colour of the complex observed is violet.)
(c) If the ligands attached to Cr3+ ion in the complexes given in the table above are water, cyanide
ion, chloride ion, and ammonia (not in this order)
Identify the ligand, write the formula and IUPAC name of the following:
(i) [CrA6]3- (ii) [CrC6]3+
30. We commonly use voltaic cell as convenient, portable sources of energy. Flash-lights and radios are
examples of devices that are often powered by the zinc-carbon dry cells or Lclanche cell. This voltaic
cell has a zinc can as the anode, a graphite rod in the centre, surrounded by a paste of manganese
dioxide, ammonium and zinc chloride and carbon black is the cathode. The voltage of this dry cell is
initially about 1.5 V, but it decreases as current is drawn off. The voltage also deteriorates rapidly in
cold weather.
An alkaline dry cell is similar to the Lclanche cell but it has potassium hydroxide in place of
ammonium chloride. This cell perform better under current drain and in cold weather. The half
reaction are:
 ZnO(s)  H 2 O( )  2e 
Anode: Zn(s)  2OH  (aq) 
Cathode: HgO(s)  H 2 O()  2e   Hg(s)  2OH 
A dry cell is not truly ‘dry’, because the electrolyte is an aqueous paste. Once a dry cell is completely
discharged, the cell is not easily reversed or recharged and is normally discarded. Lead storage cell
is rechargeable cell. The spongy lead act as anode and lead dioxide as cathode. Aqueous sulphuric
acid used as an electrolyte. The half reactions during discharging of lead storage cells are:
Anode: Pb(s)  SO 24  (aq)  PbSO 4 (s)  2e 
Cathode: PbO 2 (s)  4H  (aq)  SO 42 (aq)  PbSO 4 (s)  2H 2O
The lead storage cell can be recharged by using an external electric current. [Chemical
demonstration vol 4 University of Wisconsin]
(a) Write the cathodic reaction during the discharging of Lclanche dry cell.
(b) What is the net reaction when the alkaline dry cell is in use and how does the cell potential
depends on the concentration of KOH?
(c) How many coulombs have been transferred from anode to cathode in order to consume one
mole of sulphuric acid during the discharging of lead storage cell?
OR
How much work can be extracted by using lead storage cell if each cell delivers about 2.0 V of
voltage? [F = 96500 C mol–1)
6
SECTION E
The following questions are long answer type and carry 5 marks each. All questions have an
internal choice.
31. Attempt any five of the following:
(a) Which of the following ions will have a magnetic moment value of 1.73 BM.
Sc3+, Ti3+, Ti2+, Cu2+, Zn2+
(b) In order to protect iron from corrosion, which one will you prefer as a sacrificial electrode, Ni or
Zn? Why? (Given standard electrode potentials of Ni, Fe and Zn are -0.25 V, -0.44 V and -0.76 V
respectively.)
(c) The second ionization enthalpies of chromium and manganese are 1592 and 1509 kJ/mol
respectively. Explain the lower value of Mn.
(d) Give two similarities in the properties of Sc and Zn.
(e) What is actinoid contraction? What causes actinoid contraction?
(f) What is the oxidation state of chromium in chromate ion and dichromate ion?
(g) Write the ionic equation for reaction of KI with acidified KMnO4 .
32. (a) What is the effect of temperature on the solubility of glucose in water?
(b) Ibrahim collected a 10mL each of fresh water and ocean water. He observed that one sample
labeled “P” froze at 0oC while the other “Q” at -1.3oC. Ibrahim forgot which of the two, “P” or
“Q” was ocean water. Help him identify which container contains ocean water, giving
rationalization for your answer.
(c) Calculate Van't Hoff factor for an aqueous solution of K3 [Fe(CN)6] if the degree of dissociation
(α) is 0.852. What will be boiling point of this solution if its concentration is 1 molal? (Kb=0.52 K
kg/mol)
OR
(a) What type of deviation from Roult’s Law is expected when phenol and aniline are mixed with
each other? What change in the net volume of the mixture is expected? Graphically represent
the deviation.
(b) The vapour pressure of pure water at a certain temperature is 23.80 mm Hg. If 1 mole of a non-
volatile non- electrolytic solute is dissolved in 100g water, Calculate the resultant vapour
pressure of the solution.
33. (a) Write the structure of the main products when aniline reacts with the following reagents.
(i) Br2 water (ii) (CH3CO)2 O/pyridine
(b) Arrange the following in the increasing order of basicity in the vapour phase
C2H5NH2, (C2H5)2N, (CH3 CH2)NH
(c) Complete the following:
(i) CH3CH2CH2NH2 + CHCl 3 + KOH (alc) 
(ii) CH3CONH2 + Br2 + KOH 
7
OR
(a) Write the structure of A to D
(i) NaNO2/HCl H3O+

NO2 Sn/HCl A B C
(ii) Cu2(CN)2
H2SO4, 475 K
(b) Arrange in order of increasing boiling point CH3CH2CH2NH2, CH3CH2NHCH3, (CH3 )3N,
(c) (i) Prepare propylamine by Gabriel phthalimide synthesis
(ii) What happens when benzene diazonium chloride is being heated with C2H5OH?
SAMPLE PAPER (2023-24)
CHEMISTRY THEORY (043)
MARKING SCHEME
SECTION A
1. (b) 0.1 M HCl solution, conductivity is higher for strong electrolyte, conductivity decreases with
dilution
2. (c) A= Benzaldehyde , B= Acetophenone. This is an example of crossed Aldol condensation.
3. (d) Vitamin A,D, E and K These are fat soluble vitamins
4. (a) 3-Methylpent-3-en-2-one
5. (b) The carbon-magnesium bond is covalent and non-polar in nature .
6. (a) (i) (r) , (ii) (q), (iii) (p)
Zinc has no unpaired electrons in 3d or 4s orbitals, so enthalpy of atomization is low
Mn = 3d54s2 shows +2,+3,+4,+5,+6 and+7 oxidation state , maximum number in 3d series
7. (b) molecularity has no meaning for complex reactions.
8. (c) water
9. (b) no turbidity will be observed, given compound is a primary alcohol
10. (a) 0.00625 molL-1s-1 for zero order k = [Ro] –[R] / t = 1.5 -0.75 /120
11. (a) Due to the activation of benzene ring by the methoxy group.
12. (b) atomic radii
for visually challenged learners
12. (d) Zinc
13. (c) A is true but R is false
14. (b) Both A and R are true but R is not the correct explanation of A
15. (b) Both A and R are true and R is not the correct explanation of A.
16. (d) A is false but R is true.
Cu will deposit at cathode
SECTION B
17. (a) (½+½+1)
k = 60 s–1
2.303 [R] 2.303
t log  log16
k 1 60
[R]o
16
2.303 2.303
t log 24   4 log 2
60 60
2.303
t  4  0.30  0.04606s
60
18. π1 = π2 (1/2)
iC1RT = C2RT (1/2)
1
35 2
 (1/2)
322 M
2  322
M (1/2)
3 5
M = 42.9 g
19. (a) m-dicholrobenzene < o-dicholrobenzene < p-dicholrobenze (1/2)
symmetrical structure and close packing in para isomer
ortho has a stronger dipole dipole interaction as compared to meta (1/2)
(b) the halogen atom because of its –I effect has some tendency to withdraw electrons from the
benzene ring. As a result, the ring gets somewhat deactivated as compared to benzene and hence
the electrophilic substitution reactions in haloarenes occur slowly and require more drastic
conditions as compared to those in benzene. (1)
20. (a) p-nitrobenzaldehyde is more reactive towards the nucleophilic addition reaction than p-
tolualdehyde as Nitro group is electron withdrawing in nature . Presence of nitro group decrease
electron density, hence facilitates the attack of nucleophile . Presence of -CH3 leads to +I effect as -
CH3 is electron releasing group. (1)
(b)
( (1)
OR
(a)
(1)
(b)
(1)
21. (a) Replication
A sequence of bases on DNA is unique for a person and is the genetic material transferred to the
individual from the parent which helps in the determination of paternity. (1)
(b) During denaturation secondary and tertiary structures are destroyed but the primary structure
remains intact. (1)
SECTION C
22. (a) [Cr(en)2(OH)2]Cl or [Cr(H2NCH2CH2NH2)2(OH)2]Cl (1)
(b) No, ionization isomers are possible by exchange of ligand with counter ion only and not by
exchange of central metal ion. (1)
(c) The central atom is electron pair acceptor so it is a Lewis acid. (1)
23. (a) Yes, if the concentration of ZnSO4 in the two half cell is different , the electrode potential will be
different making the cell possible. (1)
(b) Λ0m (MgCl2 ) = λ0m ( Mg2+) + 2 λ0m ( Cl-)
258.6 = 106 + 2 λ0m ( Cl-)
λ0 m ( Cl-) = 76.3 Scm2mol–1 (1)
(c) cell constant G* = k x R
k= G*/R = 0.146/ 1000 = 1.46 x 10-4 Scm-1. (1)
24. (a) Reimer Tiemann , (1/2)
OH
CHO
2-Hydroxybenzaldehyde (1/2+1/2)
(b) Williamson synthesis, CH3CH2CH(CH3)CH(CH3)O C2H5

2- Ethoxy-2-methylpentane (1/2+1/2+1/2)
25. A, B and C contain carbonyl group as they give positive 2,4 DNP test
A and B are aldehydes as aldehydes reduce Tollen’s reagent
C is a ketone, as it contains carbonyl group but does not give positive Tollen’s test (1/2)
C is a methyl ketone as it gives positive iodoform test
B is an aldehyde that gives positive iodoform test (1/2)
D is a carboxylic acid
Since the number of carbons in the compounds A,B,C and D is three or two
B is CH3CHO as this is only aldehyde which gives a positive iodoform test (1/2)
The remaining compounds A, C and D have three carbons
A is CH3CH2CHO, C is CH3COCH3 and D is CH3CH2COOH (1/2 each)
26. (a) The reactant Sucrose is dextrorotatory. On hydrolysis it give glucose dextrorotatory and
fructose which is leavoroatatory. The specific rotation of fructose is higher than glucose
Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and laevorotatory
fructose. Since the laevorotation of fructose (–92.4°) is more than dextrorotation of glucose (+ 52.5°),
the mixture is laevorotatory. (1)
(b) Invert sugar, The hydrolysis of sucrose brings about a change in the sign of rotation, from
dextro (+) to laevo (–) and the product is named as invert sugar. (1)
(c) Glucose (1)
3
27. C2H5 CH CH3 (1)
Br
(1+1)
k  Ea  1 1 
28. log  2     
k
 1 2.303R  T1 T2 
0.20 Ea  1 1 
log  
0.05 2.303R  200 500 
Ea  300 
log10 
19.15  200  600 
19.15  200  500
Ea 
300
Ea  6383 J / mol
SECTION D
29. (a) D. Energy is directly proportional to the wave number. Maximum energy of light is required
for an electron to jump from t2g to eg in case of [CrD6]3- (1/2+1/2)
OR
(a) A, The splitting caused in least in this case as the energy required for electron to jump from t2g
to eg., is minimum. (1/2 +1/2)
(b) [CrB6]3+, wavelength of light absorbed is 1/17830 = 560nm for the complex while 1/13640 = 733
nm for [CrA6]3- complex. (1/2+1/2)
(c) (i) [CrCl6]3- , Hexachloridochromate(III) ion (1 each)
(ii) [Cr(NH3)6]3+, Hexaamminechromium(III) ion
A = Cl –, B= H2O, C= NH3, D= CN–
30. (a) Cathode reaction when Lclanche dry cell is under discharging mode is (1)
MnO2 (s)  NH 4 (aq)  e  

 MnO(OH)(s)  NH3
(b) Net reaction is (1)
Zn(s) + HgO(s)  ZnO(s) + Hg(s)
Since there is no KOH appearing in the net reaction, cell potential is independent of the
concentration of KOH.
(c) Pb(s)  SO 24 (aq) 
 PbSO4 (s)  2e (2)
 PbSO 4 (s)  2H 2 O()

PbO2 (s)  4H  (aq)  SO 42 (aq)  2e 
_____________________________________________________________
 2PbSO 4 (s)  2H 2O()

Pb(s)  PbO 2 (s)  2H 2SO 4 (aq) 
2 mol e– (or 2F) have been transferred from anode to cathode to consume 2 mol of H2SO4 therefore,
one mole H2SO4 requires one faraday of electricity or 96500 coulombs.
OR
wmax = – nFE° = – 2× 96500 × 2.0
wmax = – 386000 J
So, 386000 J of work can be extracted using lead storage cell when the cell is in use.
SECTION E
31. (a) Both Ti3+ and Cu2+ have 1 unpaired electron, so the magnetic moment for both will be 1.73 BM
(b) Zn, it has a more negative electrode potential so will corrode itself in place of iron.
(c) Mn+ has 3d54s1 configuration and configuration of Cr+ is 3d5 , therefore, ionisation enthalpy of
Mn+ is lower than Cr+ .
(d) Sc and Zn both form colourless compound and are diamagnetic.
(e) The decrease in the atomic and ionic radii with increase in atomic number of actinoids due to
poor shielding effect of 5f electron.
(f) In both chromate and dichromate ion the oxidation state of Cr is +6
(g) 10I– + 2MnO4 – + 16H+ → 2Mn2+ + 8H2 O + 5I2 (1 each, any 5)
32. (a) Addition of glucose to water is an endothermic reaction. According to Le Chatelier’s principle,
on increase in temperature, solubility will increase.
(b) Q is ocean water, due to the presence of salts it freezes at lower temperature (depression in
freezing point)
(c) K3 [Fe(CN)6 ] gives 4 ions in aqueous solution (1/2)
i=1+(n−1)α (1/2)
i=1+(4−1)×0.0.852
i = 3.556 1/2)
ΔTb = iKb m = 3.556 x 0.52 x 1 = 1.85 (1)
Tb = 101.85oC (1/2)
5
OR
(a) Negative Deviation is expected when phenol and aniline are mixed with each other. The net
volume of the mixture will decrease, ΔV< 0 due to stronger intermolecular interactions.
(1)
(1)
(b) Relative lowering of vapour pressure = (P° – P) / P° = x2 (1/2)
x2 = n2/ n1
n2 = 0.1
n1 = 100/18
x2 = 0.1/ 5.55 +0.1 = 0.1/ 5.65 = 0.018 (1/2)
P° = 23.8 mm Hg
Relative lowering of vapour pressure = (23.80 – P) / 23.80 = 0.018 (1/2)
23.80 - P = 0.428 (1/2)
P = 23.80 -0.428 = 23.37 mm Hg (1)
O
NH2 NH C CH3
Br Br
33. (a) (i) (ii)
Br
(b) CH3CH2NH2 < (CH3CH2)3NH < (CH3CH2 )3N
warm
(c) (i) CH3CH2CH2NH2 + CHCl3 + KOH (alc)  CH3CH2CH2NC + KCl + H2O
(ii) CH3CONH2 + Br2 + KOH  CH3NH2 + KBr + K2CO3 + H2O
OR
NH2 CN
(a) A  B
COOH NH2
C D
SO3H
(b) (CH3)3N < CH3CH2NHCH3 < CH3 CH2CH2NH2

(c)
CO CO
1. KOH H 2O
(i) NH N CH2CH2CH3 CH3CH2CH2NH2
2. CH3CH2CH2Br KOH
CO CO
(ii) Benzene is formed
+ -
N2 Cl + C2H5OH + N2 + HCl + CH3CHO

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KENDRIYA VIDYALAYA SANGATHAN

CONTENT ENRICHMENT STUDY MATERIAL

CONTENT ENRICHMENT STUDY MATERIAL

CO PATRON MRS PREETI SAXENA

SHRI JUGAL KISHORE

CHIEF COORDINATOR Mr. RAKESH KUMAR

Ms. Kavita Kaur

Ms. Simran Kaur

Mr. Ajay Singh

Mr. Ajay Kumar

Mr. Sudhir Maingi

Mr. Vijesh Kumar

CHEMISTRY 043 (THEORY)

S.No. Unit Page No. No. of Periods Marks

Brass (mixture of copper and zinc)

1. Solid Solid Solid in solid = Solid Alloys - brass, bronze,

2. Liquid Solid Liquid in solid = Solid Sodium Amalgam (Na- Hg)

5. Liquid Liquid Liquid in liquid = liquid Benzene in toluene, alcohol in water.

9. Gas Gas Gas in gas=gaseous Air

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑊1)

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉1)

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

For a solution sum of all the mole fractions is unity =1

SOLUBILITY OF GASES IN LIQUIDS

Example- A mixture of phenol + aniline. A mixture of chloroform + acetone .

COLLIGATIVE PROPERTIES AND DETERNMINATION OF MOLAR MASS

1) Relative lowering of vapour pressure

𝑃10 −𝑃1 𝑛2 𝑃10 −𝑃1 𝑤2 𝑋 𝑀1

2) Elevation in boiling point

Kf = Cryoscopic constant /Freezing point depression constant / Molal depression Constant

Abnormal molar masses

Van’t Hoff factor for CH3COOH= 0.5, KCl = 2 ; K2SO4 = 3

ASSERTION -REASON-ASSERTION TYPE QUESTIONS

22. Assertion: Molarity of a solution in liquid state changes with temperature.

23. Assertion: Depression of freezing point is a colligative property.

1. Is Raoult’s law applicable to non-volatile liquids ?

SA TYPE -I QUESTIONS ( 1 MARKS)

1. Calculate the molarity of NaOH solution obtain by dissolving 2g NaOH in 50 ml of its

SA TYPE -II (2 MARKS)

1. What is Henry’s law? Give one application of it? (CBSE 2023)

X water = 1 - 0.11= 0.89

1.22 𝑋 0.083 𝑋300

SA TYPE – III QUESTIONS (3 Marks)

1. a) Differentiate between ideal and non-ideal solution (CBSE 2017 ,2023)

2. Give reasons: (CBSE 2018 , 2023)

Ans: mass of solute = 222.6 g

So, molarity = 3.59/394.2 x 1000= 9.1 mol/L

Long Answer Type Question (5 MARKS)

𝟑.𝟖𝟑 𝐗 𝟏𝟎𝟎𝟎 𝑋 2.56

E (cel) = E0 (cell) – O.O591 log [Zn+2]

E (cel) = E0 (cell) – O.O591 log [Zn+2]

Ni(s)/ Ni2+ (aq) II Ag+ (aq)/Ag

The cell reaction is Ni(s) + 2Ag+ (aq) →Ni2+(aq) + 2Ag(s)

E(cell) = E0cell ) – RT ln [Ni ]+2

EQUILIBRIUM CONSTANT FROM NERNST EQUATION

E(cell) = E0(cell ) – O.O591 log KC

ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION

CONDUCTANCE OF ELECTROLYTIC SOLUTIONS

SPECIFIC CONDUCTANCE OR CONDUCTIVITY:

2. for calculation of degree of dissociation

3. for calculation of dissociation constant

ELECTROLYTIC CELLS AND ELECTROLYSIS

Cathode: Na+ (l) + e– → Na(s)

Anode: Cl–→ 1⁄2Cl2+e–