XII-JEE M-2 Chemistry Final Booklets

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Chemistry
Volume 2 Class 12 JEE
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MASTER INDEX
VOLUME 1:
Solutions
General Organic Chemistry (Revision) & Isomerism
Alkyl and Aryl Halides
Alcohols, Phenols and Ethers
Aldehydes and Ketones
VOLUME 2:
Carboxylic Acid and Its Derivatives
Amines
Biomolecules
p -Block Elements (group 15-18)
d and f Block Elements
VOLUME 3:
Practical Organic Chemistry
Qualitative Analysis
Coordination Compounds
Chemical Kinetics
Electrochemistry
VOLUME 4:
Solid State
Polymers
Metallurgy
Chemistry in Everyday Life
Surface Chemistry
TABLE OF CONTENTS
CARBOXYLIC ACID AND ITS DERIVATIVES
Theory ............................................................................................................................................................................................... 7
Exercise - 1 : Basic Objective Questions.......................................................................................................................... 25
Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 30

Exercise - 3 : Advanced Objective Questions ............................................................................................................ 37
Exercise - 4 : Previous Year JEE Advanced Questions ........................................................................................... 44
Answer Key ..................................................................................................................................................................................... 234
AMINES
Theory ............................................................................................................................................................................................... 50

Answer Key ..................................................................................................................................................................................... 237
BIOMOLECULES
Theory ............................................................................................................................................................................................... 95

Answer Key ..................................................................................................................................................................................... 239
P -BLOCK ELEMENTS (GROUP 15-18)
Theory ............................................................................................................................................................................................... 141

Answer Key ..................................................................................................................................................................................... 241
D AND F BLOCK ELEMENTS
Theory ............................................................................................................................................................................................... 194

Answer Key ..................................................................................................................................................................................... 243
Chapter 06 7
1. INTRODUCTION Important Aromatic Adds

Carboxylic acids are the compounds containing the carboxy
functional group.
Structure of carboxylic acid group

The carboxylic acids may be aliphatic (R-COOH) or aromatic
(Ar-COOH) depending upon whether -COOH group is attached
to aliphatic alkyl chain or aryl group respectively.
These are further classified as mono, di, tri carboxylic acids
The general formula for carboxylic acids is C n H 2n O 2
depending upon number of carboxylic groups present in their
Carboxylic acids are used in the production of polymers molecules.
pharmaceuticals, solvents, and food additives. Industrial Mono Carboxylic Acids
important acids include acetic acid (component of vinegar
precursor to solvents and coatings), acrylic and methacrylic acid
(precursors to polymers, adhesives), adipic acid (polymers), citric
acid (beverages), ethylene diaminetetraacetic acid (chelatin
agent), fatty acids (coatings), maleic acid (polymers), propionic HCOOH CH3COOH
acid (food preservatives), terephthalic acid (polymers). Esters Formic acid Acetic acid Benzoic acid
fatty acids are the main components of lipids and polyamides Di Carboxylic Acids
aminocarboxylic acids are the main components of proteins.
The carboxylic acids ionize in water to give H  ions and hence
they arc acidic in nature.
Important Aliphatic Acids
HCOOH Formic Acid
CH 3 COOH Acetic Acid

2. PHYSICAL PROPERTIES AND ACIDIC CHARACTER
CH 2  CHCOOH Acrylic Acid
CH 3COCOOH Pyruvic Acid

(oxo-keto acid)
The high boiling points of carboxylic acids result from formation

of a stable, hydrogen-bonded dimer. This dimer contains an eight-
membered ring joined by two hydrogen bonds, effectively
doubling the molecular weight of the molecules leaving the liquid
phase.
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CARBOXYLIC ACID AND ITS DERIVATIVES 8
increases, acid strength increases and vice versa.
Hydrogen-bonded Acid Dimer

2.2 Melting Point and Physical State Strength of -I group decreases with increase in distance with -
COOH group.
Aliphatic acids upto nine carbon atoms are colourless liquids at
room temperature with unpleasant odours. The higher acids are
wax-like solids and are practically odourless due to low volatility.
They exist as dimer in aprotic and non-polar solvents.
Unbranched acids made up of an even number of carbon atoms
have melting points higher than the odd numbered homologous
having one more or one less carbon. This oscillating behaviour
in melting point is explained by the differences in the Negative inductive effect of is in order: F,Cl,Br,I
intermolecular attractive forces in the crystalline state. Hence, acid strength is
2.3 Solubility
F-CH2COOH > C1-CH2COOH > Br-CH2COOH > I-CH2COOH
Carboxylic acids form hydrogen bonds with water, and the lower
Relative acid strength is as follows :
molecular weight carboxylic acids (up through 4 carbon atoms)
are miscible with water. As the length of the hydrocarbon chain RCOOH > HOH > ROH > HC  CH > NH 3 > RH
increases, water solubility decreases until acids with more than
10 carbon atoms are essentially insoluble in water. 3. PREPARATION OF CARBOXYLIC ACIDS
Carboxylic acids are very soluble in alcohols because the acids 3.1 Alkanes
form hydrogen bonds with alcohols. Also, alcohols are not as
polar as water, so the longer-chain acids are more soluble in Long chain alkanes are oxidized by air at 120 C in presence of
alcohols than they are in water. Most carboxylic acids are quite catalyst manganese acetate or manganous stearate.
soluble in relatively nonpolar solvents such as chloroform because
the acid continues to exist in its dimeric form in the nonpolar
solvent. Thus, the hydrogen bonds of the cyclic dimer are not
disrupted when the acid dissolves in a nonpolar solvent.
2.4 Acidity of Carboxylic Acids
3.2 Alkenes
3.2.1 Ozonolysis
Monosubstitutcd alkenes give carboxylic acid on oxidative
ozonolysis.
Resonating structures of carboxylate ion 3.2.2 Oxidation

Carboxylate ion exists as two equivalent canonical structure A
Oxidising agents used are acidified or hot alkaline KMnO 4 and
and B. Due to more stability of carboxylate ion, carboxylic acid is
acidic in nature because the equilibrium in reaction favors the K 2 Cr2 O7 .
formation of stable ion.
Effect of Substituents on Acidity RCH  CHR' 4O 
k2Cr2O7 /H2SO4

RCOOH  R'COOH
Electron withdrawing groups ( -I effect) stabilise the anion and Cyclic alkenes can be oxidized to dicarboxylic acids.
hence increase acidic nature. As the no. of -I effect groups
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3.3 Alkynes
3.3.1 Ozonolysis
Alkynes on ozonolysis give carboxylic acids.
1. In oxidative cleavage, each C of multiple bond becomes the

carbon atom of the carbonyl group and a hydrogen substituent
on the double bond is replaced by a hydroxyl group.
2. The terminal -CH 2 group of 1 -alkene is completely oxidized to
CO 2 and H 2 O .
3.3.2 Oxidation
The use of strong oxidising agents such as KMnO4 , CrO3 etc.
directly gives the carboxylic acid.
3.2.3 Koch Reaction - Hydrocarbonylation

Alkene on treatment with CO,H 2 O at high temperature and
pressure causes carbonylation. Usually, H 3 PO 4 is used as the
acid catalyst. The similar effect is observed when Ni(CO) 4 is 3.4 Alkyl Halides
treated independently. 3.4.1 KCN + Hydrolysis
Number of carbons is one more than parent alkene.
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NOTE 3.4.3 Grignard Reagent + CO2
 In acidic medium, the products are RCOOH and
NH 4 while in alkaline hydrolysis, RCOO  and NH3 are
products.
 The acid formed contains one more C than parent alkyl
halide. The order of reactivity of alkyl halides is
1° > 2° > 3°.
 In case of 3° alkyl halide, elimination takes place.
 Vinylic, arylic halides are not appropriate as substitution
is difficult.
3.5 Alcohols
Oxidation of 1° alcohols yields carboxylic acids.
  O
RCH 2 OH   RCOOH
NOTE
 Strong Oxidizing Agents : K 2 Cr2 O 7 / H  or KMnO 4 / H  .
 Mild Oxidising Agents: MnO, CuO (Fehling’s Solution),

(CrO3 , H 2SO 4 ) in acetone solution, Ag 2 O (Tollen’ss
reagent), FeSO 4 + H 2 O 2 (Fenton’s reagent). These are
3.4.2 Hydrolysis of terminal trihalogen derivatives of Alkanes
used for preparing unsaturated acids.
3.6 Aldehydes and Ketones

3.6.1 Oxidation
Oxidation of aldehydes and ketones give carboxylic acids.
  O
RCHO   RCOOH
  O
RCOR'  RCOOH + R'COOH
Ketones arc oxidized under vigorous conditions such as hot
K 2 Cr2 O 7 / H  and give mixture of acids.
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3.8 Preparation of Aromatic Acids
3.8.1 Oxidation of Alkyl Benzenes
Alkyl side chain of benzene ring can be easily oxidized to
carboxylic group, irrespective of the length with acidic or alkaline
KMnO4 , Chromic acid or conc. HNO3.
* *
[O]
CH 3 C OCH 2 CH 2 CH 3 
  CH 3 C OOH
 CH 3 CH 2 COOH
Keto group (with C*) remains with smaller alkyl group.

3.6.2 Haloform Reaction
Methyl ketone on treatment with X 2 / OH  gives carboxylate

having one carbon atom less than the original ketone - Haloform
Reaction.
For conversion to carboxylic group, presence of  -hydrogen is

necessary. That is why tertiary alkyl side chains are not oxidized.
3.8.2 Kolbe - Schmidt Reaction

3.7 Carboxylic Acid Derivatives Sodium phenoxide is carboxylated by treatment of CO 2 in the
Acyl halide, carboxylic ester, anhydride and amide on acidic or ortho-position, mostly.
basic hydrolysis give carboxylic acids.
1° amide on treatment with nitrous acid.
H ,H O
2  RCOOH  R 'OH
RCOOR ' 
OH, H O
2  RCOO   NH
RCONH 2 
 3 4. REACTIONS OF CARBOXYLIC ACIDS
4.1 Reactions as an Acid
4.1.1 Reaction with Strongly Electropositive Metals
Monocarboxylic acids react with strong electropositive metals
(such as Na, K, Zn etc.) evolving hydrogen and forming
corresponding salts (acidic character).
2RCOOH  Na  2RCOONa  H 2
Acid Sodium salt
of Acid
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4.1.2 Reaction with Alkalies
Monocarboxylic acids neutralize hydroxides to form
corresponding salt and water.
CH 3 COOH + NaOH  CH 3 COONa+H 2 O
These salts, on being treated with dilute mineral acids regenerate
carboxylic acids.
CH 3 COONa + HC1  CH 3 COOH  NaC1
4.1.3 Reaction with Carbonates & Bicarbonates

This reaction is laboratory test of carboxylic group 5 membered ring is called  -lactone and 6 membered ring is
called  -lactone.
(-COOH) due to effervescence of CO 2 .
2CH 3 COOH + Na 2 CO3  2CH 3 COONa+CO 2 +H 2 O

4.2.2 Formation of Acid Chlorides
CH 3 COOH + NaHCO3  CH 3COONa+CO 2 +H 2O
NOTE
CO 2 evolves from carbonate or bicarbonate not from acid.
4.2 Nucleophilic Acyl Substitution

4.2.1 Formation of Esters
Out of these three, SOC12 method is preferred because here

R  COOH+HOR ' 
conc.

 RCOOR'+H 2 O other two products are gases that can easily escape.
H SO 2 4
This reaction is called esterification and is catalyzed by small 4.2.3 Formation of Acid Anhydrides
amount of inorganic acids.
In esterification C-OH bond of acid and O-H bond of alcohol
breaks.
Hydroxy acids undergo intramolecular esterification and makes

cyclic esters called as Lactones.
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4.4 Carboxyl Group Reactions
4.4.1 Decarboxylation
When anhydrous alkali salt of a carboxylic acid is heated with
soda lime (NaOH : CaO in ratio 3 : 1), an alkane is formed.
CaO  R  H  Na CO
RCOONa  NaOH  2 3
Sodium Salt Heat Alkane
The reaction proceeds through carbanion intermediate. Greater
Dicarboxylic acids on heating give cyclic anhydride (5 and 6 the stability of carbanion, greater the rate of decarboxylation.
membered rings).
Gem dicarboxylic acids decarboxylate simply on heating.
NOTE
Formic Acid (HCOOH) does not form anhydride.
4.2.4 Formation of Amides
4.3 Reduction
4.3.1 Reduction to Alcohols
Reducing Agents: LiA1H 4 in ether solution or with H2 in

presence of copper chromite ( CuCr2O4 ) catalyst or BH 3 /THF β -keto acids undergo decarboxylation through a cyclic transition
(or diborane, B2 H 6 ) or H 2 , Ru etc. state, giving ketone.
CH3 CH2 CH2COOH  

H2 ,Ru-C

CH3CH2CH2CH2OH
β -unsaturated acids decarboxylate on heating giving alkenes.
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4.4.4 Hunsdiecker Reaction
   Heat H C  CH  CH  CO 
H 2 C  C H  C H 2  COOH  2 3 2 An alkyl halide is formed when the silver salt of monocarboxyl
acid is heated with halogen. This is a step down reaction.
4.4.2 Dry Distillation of Calcium Salts of Carboxylic Acids
CCl
4 CH Br  AgBr  CO 
CH3COOAg  Br 
(RCOO) 2 Ca 

 RCOR + CaCO 3 3
Heat 2
Methyl Bromide
Calcium Salt Ketone
When calcium formate is heated, formaldehyde is evolved. 4.4.5 Simonini Reaction
(H C O O ) 2 C a  H
cat
 H C H O  C aC O 3
The reaction of silver salts of carboxylic acids with iodine is
called Simonini Reaction.
Formaldehyde
2RCOOAg I2

CO 2
 RCOOR
When a mixture of calcium salt of an acid (other than formic acid)
and calcium formate is heated an aldehyde is formed. NOTE
The ratio of reagents play an important role in determination
of products, namely.
4.4.3 Kolbe’s Synthesis  1 : 1 ratio of salt and I 2 - RI is formed
Electrolysis of sodium or potassium salts (concentrated aq.  2 : 1 ratio of salt and I 2 - RCOOR is formed
solution) of fatty acids yield alkanes.
 3 : 1 ratio of salt and I 2 - Both the products are obtained
 RCOO   Na 
RCOONa 
4.4.6 Schmidt Reaction
At Anode :2RCOO   R  R  2CO 2  2e
It involves treatment of hydrazoic acid with carboxylic acids.
 2H O
2  2NaOH  H
At Cathode :2Na   2e  2Na  2
Alkyl isocyanate is the intermediate. Primary amine formed
contains one carbon less than parent acid.
Reaction involves radical intermediates.
O
||
2CH 3 CH 2  C ONa  CH 3CH 2 CH 2 CH 3
Electrolysis of salt of succinic acid and its derivative give alkene.

Electrolysis of maleic acid/fumaric acid or their salts gives
corresponding alkynes.
4.4.7 Hell-Volhard Zelinsky Reaction

When carboxylic acid containing an  -hydrogen is treated with
CI 2 or Br2 in presence of a catalyst. The  -hydrogen is replaced
by chlorine or bromine atoms.
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5.1.1 Preparation
Industrial Preparation
Acid is regenerated by the action of H 2SO 4 .
5.1.2 Chemical Properties

(A) Acidic Nature
4.4.8 Oxidation
Prolonged heating with powerful oxidising agents oxidises acids (B) Action of Heat
into CO 2 and H 2 O .
With 3% H2O2 , they are oxidised to β -hydroxy acids.

(C) Dehydration
(D) Action of Heat on Formates
 COONa
(a) 2HCOONa   |  H2
360o C COONa

(b) HCOONa  NaOH  Na 2 CO 3  H 2
CaO

(HCOO) 2 Ca  HCHO  CaCO3
(c) Formaldehyde
4.4.9 Conversion to Nitriles

(d) HCOONH 4   HCONH 2  H 2 O
When mixture of acid and NH3 are passed over heated alumina,
alkane nitrile forms. (E) Reducing Properties
(a)
5. IMPORTANT COMPOUNDS
5.1 Formic Acid (HCOOH)
Naturally it occurs in sting of bees, wasps, redant stinging nettles
and fruits.
It was first prepared by the distillation of red ants and hence it is (b)
called as Formic Acid (Latin formica : ant)
SCAN CODE
(c) HCOOH  2HgCl 2  HgCl 2  2HCl  CO 2 5.2.1Preparation
HCOOH  Hg 2 Cl 2  2Hg  2HCl  CO 2
Black
(d) Tollen’s Reagent
  2Ag  CO  H O
HCOOH  Ag 2 O  2 2
Silver
Mirror
(e) Fehling’s Solution
HCOOH  2CuO  Cu 2 O   CO 2  H 2 O
Red
Pr ecipitate
5.1.3 Tests for HCOOH

1. Its aqueous solution turns blue litmus red.
2. It forms silver mirror with Tollens’ reagent.
3. It forms black ppt with Hg2Cl2 .
5.2.2 Chemical Properties
4. Heated with H 2SO 4 , it evolves CO which burns with blue
Acetic Acid is a typical member of fatty acids. It shows all the
flame on mouth of test tube. general characteristics of mono carboxylic acids listed earlier.
5. On reacting with neutral solution of FeCl3 , it gives red colour
5.2.3 Tests for CH 3 COOH
which converts in brown ppt on heating.
1. Its aqueous solution turn blue litmus red.
2 Its aqueous solution gives effervescences of CO2 with
5.1.4 Uses of Formic Acid NaHCO3
1. In lab preparation of CO. 3 Neutral CH3COOH 

Neutral
 red colour
FeCl 3
2. Textile dyeing and finishing.

4. It does not affect Tollen’s reagent, Fehling solution and
3. Leather tanning.
HgCl 2 .These reactions are used to differentiate it form
4. Coagulating agent for rubber latex. HCOOH.
5. As an antiseptic and treatment for gout.
5.2.4 Uses of Acetic Acid
6. As a strong irritant.
1. Good solvent and lab reagent.
NOTE 2. As vinegar and table purposes in houses.
 It is the strongest carboxylic acid.
3. In manufacturing pickles.
 Its unique nature is due to the presence of both carboxyl
and carbonyl group. 4. Making Al, Cr, Fe acetates which are used as mordants dyeing.
5.3 Benzoic Add (C6H5COOH)
Naturally it is obtained from Benzoin resin. It is a benzene
derivative and aromatic compound.
5.3.1 Preparation of Benzoic Acid
5.2 Acetic Acid ( CH3COOH ) 
(A) Ph  CH 3 
KMnO 4
KOH, 
Ph  COOK 
H O
 PhCOOH
3
In free state it is found in fermented fruit juices and in bound

Co  Mn Acetate
state it is found in biological fluids and plant extracts. (B) 2C6H5CH3  3O2  170º C
 2C6 H5COOH  2H 2O
It is a by-product of alcohol industry.
SCAN CODE
(C)
(D)
5.3.2 Reactions of Benzoic Acid

Benzoic acid, C6H5COOH shows all typical reactions of -COOH
group just like aliphatic acids. The properties of the derivatives Chemical reactions of benzoic acid
of benzoic acid are also similar to the properties of aliphatic acids.
5.3.3 Uses of Benzoic Acid

1. Used as food preservative.
2. Used as precursor for many compounds.
3. Used in making medicines for fungal diseases.
6. CARBOXYLIC ACIDS DERIVATIVES

Carboxylic acids form esters, acid halides, amides and acid
anhydrides as a functional derivatives. All these derivatives have
a carbonyl group and yield carboxylic acids on hydrolysis. Among
these derivatives, acyl chlorides are the most reactive towards
nucleophilic acyl substitution reactions and amides are least
reactive.
-COOH group attached to benzene nucleus in m-directing and a
deactivating group. It also gives electrophilic substitution
reactions.
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General Mechanism of Nucleophilic Acyl Substitution (B) Conversion to Amides
Step 1 : Addition of Nucleophile
Step 2 : Loss of Leaving Group
Leaving groups L: Cl , NH 2 , RO, RCOO (C) Conversion to Anhydrides
The weaker is the base, the better is the leaving group. The basic
nature of the above groups is in the order :
Cl   RCOO   OH   RO   NH 2  (D) Conversion to Alcohols

(i) Grignard Reagent
Hence, the leaving tendency of the groups is in order
NH 2   RO   OH   RCOO   Cl 
Therefore, the reactivity of the acids and their derivatives follows
the order:
RCOCl>  RCO 2 O>RCOOH>RCOOR>RCONH 2
6.1 Acyl Chlorides

6.1.1 Preparation
(A) RCOOH  PCl5  RCOCl  POCl3  HCl  (ii) Metal Hydrides

(B) RCOOH  SOCl2  RCOCl  SO2   HCl 
(C) RCOOH  PCl3  RCOCl  H 3 PO3
6.1.2 Reactions
(E) Conversion to Aldehydes
(A) Esterification
(i) Rosenmund’s Reduction
(ii) Metal Hydride LiAl(OCMe3)3H
SCAN CODE
(F) Conversion to Ketones (B)
(i) Dialkyl Cadmium
(ii) Gilman’s Reagent
(G) F riedel-Craft’s Acylation
(C)
(H) Curtius Reaction
(I) Hydrolysis
(J) Formation of  -Keto Adds
6.2 Acid Anhydrides

6.2.1 Preparation of Acid Anhydrides
6.2.2 Reactions of Acid Anhydrides

(A) Esterification
(A)
(B) Conversion to Amides
SCAN CODE
6.3 Esters
6.3.1 Preparation of Esters
(A) Esterification
The esters are formed by the reaction between an acid, RCOOH
and an alcohol by warming with mineral acid in a reaction called
as Esterification.
Mechanism
(C) Conversion to Acyl Chlorides
(D) Conversion to Alcohols
(E) Friedel-Craft’s Acylation
Since a tetrahedral intermediate occupies more space than a planar

carbonyl group, we would expect the rate of this reaction to be
retarded when bulky reactants are used. When the esterification
of acetic acid was compared with that of 2, 2 -dimethylpropanoic
acid, (CH3 )3 C  COOH the relatively small methyl group of acetic
(F) Perkin Reaction
acid is replaced by a larger tert-butyl group, and the bulkier acid
reacted fifty times slower than acetic acid. Similarly, increasing
the size of the alcohol reactant results in a similar rate reduction.
In its formation, steric factor is most important both in acids and
alcohols. If acid chlorides or acid anhydrides are esterified with
alcohols, it is considered as the better method.
(B)
(G) Hydrolysis
(C)
(D)
(E) Baeyer-Villiger Oxidation of Ketones
Oxygen is introduced on that side which has more electron
SCAN CODE
donating alkyl group. (iii) Grignard Reagent
(F) Carbonylation of Ethers

 
BF3 ,150  200 C
R  O  R  CO  Pr essure
 R  COOR
(G) Diazomethane CH2N2
R-COOH + CH 2 N 2  RCOOCH 3 +N 2
6.3.2 Reactions of Esters
(A) Hydrolysis
(E) Transesterification
Transesterification is the process of exchanging the alkoxy group
of an ester compound by another alcohol. These reactions are
often catalyzed by the addition of an acid or base.
Base catalysed hydrolysis is not reversible as carboxylate ion

formed is resonance stabilised.
(B) Conversion to Acyl Chloride
(C) Conversion to Amides
(F) Acyloin Formation

(D) Conversion to Alcohols
(i) Metal Hydrides
(G) Claisen Condensation
(ii) Bouveault-Blanc Reduction

Na
RCOOR '  RCH 2 OH  R 'OH
C2 H5OH
SCAN CODE
Intramolecular claisen condensation is called as Dieckmann (B) Conversion to Cyanides
Condensation.
RCONH 2 
P4 O10

 RC  N  H 2 O
Dehydrating Reagents such as P2 O5 ,SOCl 2 or POCl3 is used.

(C) Conversion to Amines
Amides are reduced to amines by reaction with reducing agents
such as LiAlH 4 or Na/C 2 H 5 OH .
6.4 Amides
Types of Amides
RCONH2 RCONHR RCONR2
1 amides
o
2 amides
o
3o amides
Alkanamides N-Alkyl N, N-Dialkyl
Alkanamides Alkanamides
6.4.1 Preparation of Amides

(A) RCOOH  NH 3  RCOONH 4   RCONH 2
(D) Reaction with HNO2
(B) RCOOH  PCl5  RCOCl 
NH3
 RCONH 2
RCONH 2  HNO 2  RCOOH  N 2   H 2 O
(E) Hofmann Bromamide Degradation

RCONH 2  4NaOH  Br2

(C)
RNH 2  2NaBr  Na 2 CO3  2H 2 O
(F) Conversion to Imidcs
Cyclic anhydrides are converted first into an amide on reaction
with NH3 and then heated to form imides.
(D)
6.4.2 Reactions of Amides

(A) Hydrolysis
RCONH 2  H 2 O 
H 2SO4
 RCOOH  NH 3
RCONH 2  NaOH 
H2O
 RCOONa  NH 3
This is typical of 1 amides to give off NH3
SCAN CODE
Derivatives of Carbonic Acid
6.5 Carbonic Acid Derivatives
Aqueous carbonic acid ( CO 2 gas dissolved in H 2 O ) is unstable

and behaves as dibasic acid.
SCAN CODE
SUMMARY
Properties of Carboxylic Acid Preparation of Carboxylic Acid
Properties of Benzoic Acid

Reactions of Carboxylic Acid
Properties of Carboxylic Acid
SCAN CODE
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Introduction to Carboxylic Acid and Its Derivatives 7. The IUPAC name of the molecule
1. The general formula for monocarboxylic acids is
(a) CnH2nO (b) CnH2n+1O2
(c) CnH2n+2O2 (d) CnH2nO2 is
O
|| (a) 4-oxo-2,3-dimethylpent-2-en-1-oic acid
2. H  C  Cl is called
(b) 3-carboxy-3-methylpent-2-en-3-one
(a) Acetyl chloride (b) Formyl chloride
(c) 4-carboxy-3-methylpent-3-en-2-one
(c) Chloretone (d) Oxochloromethane
(d) 2,3-dimethyl-4-oxopent-2-en-1-oic acid
3. The IUPAC name for
8. Monocarboxylic acids are functional isomers of
is :- (a) Alcohols (b) Ethers

(c) Esters (d) Aldehydes and ketones.
(a) 1-Hydroxy-4-methylpentanoic acid
9. The general formula CnH2nO2 could be for open chain
(b) 1-Methyl-3-hydroxypentanoic acid
(a) diketones (b) carboxylic acids
(c) 4-Hydroxy-2-methylpentanoic acid
(c) diols (d) dialdeydes
(d) 4-Carboxypentanol-2.
10. Which of the following does not contain a carboxyl group?
4. The IUPAC name of C6H5COCl is
(a) picric acid (b) aspirin
(a) Chlorobenzyl ketone
(c) benzoic acid (d) ethanoic acid
(b) Benzene chloroketone
Preparation of Carboxylic Acid
(c) Benzoyl chloride
11. Hydrolysis of hydrogen cyanide results in the formation
(d) Chlorophenyl ketone
of
(a) Formic acid (b) Oxalic acid
5. The IUPAC name of is
(c) Formaldehyde (d) Acetaldehyde
(a) 2-Bromo-3-methylbutanoic acid 12. Ethyl isocyanide on hydrolysis in acidic medium generates
(b) 2-Methyl-3-bromobutanoic acid (a) ethylamine salt and methanoic acid
(c) 3-Bromo-2-methylbutanoic acid (b) propanoic acid and ammonium salt
(d) 3-Bromo-2,3-dimethylpropanoic acid (c) ethanoic acid and ammonium salt
(d) methylamine salt and ethanoic acid
6. The IUPAC name of is
13. The compound formed as a result of oxidation of ethyl
(a) but-3-enoic acid (b) but-1-enoic acid benzene by KMnO4 is
(c) pen-4-enoic acid (d) prop-2-enoic acid (a) benzophenone (b) acetophenone
(c) benzoic acid (d) benzyl alcohol
14. In the following reaction sequence.
CuCN/Pyridine
2 4 Y Dil.H SO
C6 H5 Br 
523 K  X 
Boil
The product Y is
(a) Benzonitrile (b) Benzene
(c) Benzoic acid (d) Benzamide
15. Ethanoic acid is prepared commercially from
(a) Ethyne (b) Ethanol
(c) Methanal (d) Both ethyne and ethanol.
16. The major product obtained on interaction of phenol with
sodium hydroxide and carbon dioxide is
(a) benzoic acid (b) salicylaldehyde
(c) salicylic acid (d) phthalic acid
Physical and Chemical properties of Carboxylic
17. Acetic acid is obtained when
Acids
(a) Methyl alcohol is oxidised with potassium permanganate
21. Which of the following has the highest boiling point ?
(b) Formaldehyde is oxidised with potassium dichromate and
sulphuric acid (a) CH3OCH2CH3 (b) CH3CH2CH2OH
(c) Acetonitrile is hydrolysed with a dilute mineral acid (c) CH3COOH (d) CH3CH2CH2CH3
(d) Glycerol is heated with sulphuric acid. 22. The carboxylic acid which has maximum solubility in water
is
 CH 3 2 CO 
+
 HCl   A  B
NaCN H3 O
18. (a) Phthalic acid (b) Succinic acid
in the above sequence of reactions A and B are (c) Malonic acid (d) Salicylic acid
(a) (CH3)2C(OH)CN, (CH3)2CHCOOH 23. In the anion HCOO the two carbon-oxygen bonds are
(b) (CH3)2C(OH)CN, (CH3)2C(OH)2 found to be of equal length. What is the reason for it.
(c) (CH3)2C(OH)CN, (CH3)2C(OH)COOH (a) Electronic orbitals of carbon atom are hybridised
(d) (CH3)2C(OH)CN, (CH3)2 C = O (b) The C = O bond is weaker than C – O bond
19. The acid D obtained through the following sequence of (c) The anion HCOO– has two resonating structures.
reactions is
(d) The anion is obtained by removal of a proton form the
Alc.KOH Br2 KCN H3O acid molecule
C2 H5 Br  A 
CCl4  B 
(excess)  C  D
24. The weakest acid among the following is
(a) Succinic acid (b) Malonic acid
(a) CH3COOH (b) Cl2CHCOOH
(c) Maleic acid (d) Oxalic acid
(c) ClCH2COOH (d) Cl3CCOOH
20. p-cresol reacts with chloroform in alkaline medium to give
the compound A which adds hydrogen cyanide to form the 25. When CH 2  CH  COOH is reduced with LiAlH4, the
compound B. The latter, on acidic hydrolysis gives chiral compound obtained will be
carboxylic acid. The structure of the carboxylic acid is
(a) CH3— CH2— COOH
(b) CH 2  CH  CH 2 OH
(c) CH3— CH2— CHO
(d) CH3  CH 2  CH 2  OH
26. Sodium formate on heating yields 34. The increasing order of acidity of ,  and – chlorobutyric
(a) oxalic acid and H2 acids is
(b) sodium oxalate and H2 (a)  <  <  (b)  <  < 
(c) CO2 and NaOH (c)  <  <  (d)  <  < 
(d) sodium oxalate. 35. Which of the following is the weakest acid
27. Treatment of benzoic acid with Cl2/FeCl3 will give

(a) p-chlorobenzoic acid (a) (b) CH3COOH
(b) o-chlorobenzoic acid
(c) 2,4-dichlorobenzoic acid
(d) m-chlorobenzoic acid (c) HCOOH (d)
28. H
The reaction, CH3COOH + CH3OH   CH3COOCH3 + 36. Consider the acidity of the carboxylic acids :
H2O is called
(i) C6H5COOH (ii) o–NO2C6H4COOH
(a) Acidification reaction
(iii) p–NO2C6H4COOH (iv) m–NO2C6H4COOH
(b) Dehydration reaction
Which of the following order is correct ?
(c) Dehydrogenation reaction
(a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iv) > (iii) > (i)
(d) Esterification reaction
(c) (ii) > (iv) > (i) > (iii) (d) (ii) > (iii) > (iv) > (i)
29. Heating a mixture of ethyl alcohol and acetic acid in presence
37. The strongest acid amongst the following compounds is
of conc. H2SO4 produces a fruity smelling compound. This
(a) CH3COOH (b) HCOOH
reaction is called
(c) CH3CH2CH(Cl)CO2H (d) ClCH2CH2CH2COOH
(a) Neutralisation (b) Ester hydrolysis
38. Among the following, the acid which undergoes fastest
(c) Esterification (d) Williamson’s synthesis
decarboxylation is
30. Which reagent will bring about the conversion of
carboxylic acids into esters O O
|| ||
(a) Ph  C COOH (b)
(a) C2H5OH (b) Dry HCl + C2H5OH Ph  C CH 2  COOH
(c) LiAlH4 (d) Al(OC2H5)3
(c) PhCOOH (d) Ph  CHOH  COOH
31. In esterification, OH  ion for making H2O comes from
39. In the reaction,
(a) Acid (b) Alcohol

 
 
(c) Ketone (d) Carbohydrate
32. Which of the following would be expected to be the most the product C is :
highly ionized in water ? (a) Acetylene (b) Ethylene
(a) ClCH2CH2CH2COOH (b) CH3CCl2CH2COOH (c) Acetyl chloride (d) Acetaldehyde
(c) CH3CH2CCl2COOH (d) CH3CH2CHClCOOH Cl ,Red P
Alc. KOH
40. 2
CH 3 CH 2 COOH 
 X  Y
33. Rewrite the following in the increasing order of acidity ?
(i) Benzoic acid (ii) p-methoxybenzoic acid Compound Y is
(iii) o-methoxybenzoic acid (a) CH3CH2OH (b) CH3CH2CN
(a) (i) < (ii) < (iii) (b) (iii) < (i) < (ii) (c) CH 2  CHCOOH (d) CH3CHClCOOH
(c) (ii) < (i) < (iii) (d) (iii) < (ii) < (i).
41. Propanoic acid or its sodium salt can be converted into 48. Which will not give acetamide on reaction with ammonia
alkanes by reduction with Hl/red P or decarboxylation (a) Acetic acid (b) Acetyl chloride
reaction or kolbe’s reduction. Which of the following
(c) Acetic anhydride (d) Methyl formate
alkanes is not formed in any of these reactions ?
49. Among the following acids which have the lowest pKa
(a) Methane (b) Ethane
value:
(c) Propane (d) Butane
(a) CH3COOH (b) HCOOH
42. The reaction : RCOOAg + Br2 CCl4 , Reflux
(c) (CH3)2COOH (d) CH3CH2COOH
R – Br + AgBr + CO2 50. Hydrolysis of acetamide produces
is called (a) Acetic acid (b) Acetaldehyde
(a) Wurtz reaction (c) Methylamine (d) Formic acid
(b) Hunsdiecker reaction 51. In the following reaction, product P is
(c) Friedel-Crafts reaction O
(d) Kolbe’s reaction
|| H2
R  C Cl 
Pd BaSO
P
4
43. The reaction,
(a) RCH2OH (b) RCOOH
H  or OH 
RCOOR   R OH (excess)  RCOOR   R 
(c) RCHO (d) RCH3
OH is called
52. Sodium ethoxide has reacted with ethanoyl chloride. The
(a) Esterification (b) Trans-esterification
compound that is produced in the above reaction is
(c) Saponification (d) Hydrolysis
44. Which of the following will not undergo Hell - volhard
(a) diethyl ether (b) 2-butanone
Zelinsky (HVZ) reaction ?
(c) ethyl chloride (d) ethyl ethanoate
(a) HCOOH (b) CH3COOH
(c) CH3CH2COOH (d) CH3CHBrCOOH Chemical Properties of Carboxylic Acid Derivatives
45. When propionic acid is treated with aqueous sodium 53. Benzoyl chloride on treatment with ammonia gives
bicarbonate CO2 is liberated. The ‘C’ of CO2 comes from (a) Benzamide (b) Acetamide
(a) Methyl group (b) Carboxylic acid group (c) Benzylamine (d) Benzoic acid
(c) Methylene group (d) Bicarbonate 54. Ethyl acetate reacts with CH3MgBr to form
Preparation of Carboxylic Acid Derivatives (a) Secondary alcohol (b) Tertiary alcohol
46. Acetic anhydride is obtained from acetyl chloride by the (c) Primary alcohol and acid
reaction of (d) Acid
(a) P2O5 (b) H2SO4 55. The decreasing order of reactivity of
(c) CH3COONa (d) HOCl (i) CH3COCl (ii) CH3COOC2H5
47. Identify Z in the following reaction sequence. (iii) CH3CONH2 (iv) (CH3CO)2O
Towards nucleophilic acyl substitution is
(a) (i) > (iv) > (iii) > (ii)
(a) CH3COCH2COONa (b) (i) > (iv) > (ii) > (iii)
(b) (CH3CO)2O (c) (iv) > (iii) > (i) > (ii)
(c) CH3CO – O – COCH2Cl2 (d) (iii) > (i) > (iv) > (ii)
(d) CH3CO – OCOCHCl2
CH 3COCl 
H
 CH 3CHO  HCl; 60. Acetic anhydride reacts with excess of ammonia to form
56. 2
Pd / BaSO 4
(a) 2CH3COON4 (b) 2CH3CONH2
The above reaction is called
(c) CH3CONH2 + CH3COONH4
(a) Reimer-Tiemann reaction
(d) 2CH3COOH
(b) Cannizzaro reaction
Tests of Carboxylic Acids and Its Derivatives
(c) Rosenmund reaction
61. Which one of the following compounds forms a red
(d) Reformatsky reaction
coloured solution on treatment with neutral FeCl3 solution
57. Consider the following compounds:
(a) CH3COCH3 (b) CH3OCH3
(i) C6H5COCl
(c) CH3CH2OH (d) CH3COOH
(ii) 62. Phenol can be distinguished from acetic acid by

(a) Blue litmus test (b) Sodium bisulphite test
(c) With FeCl3 solution (d) Tollen’s reagent test.
(iii)
63. Tollen’s reagent in not reduced by
(a) Formic acid (b) Acetaldehyde
(iv)
(c) Benzaldehyde (d) Acetic acid
The correct decreasing order of their reactivity towards 64. Fehling’s solution can make distinction between following
hydrolysis is pairs
(a) (i) > (ii) > (iii) > (iv) I : CH3COOH, HCOOH II : CH3COOH,HCHO
(b) (iv) > (ii) > (i) > (iii) III : C6H5CHO, HCHO IV : CH3CHO, HCHO
(c) (ii) > (iv) > (i) > (iii) Select correct pairs :
(d) (ii) > (iv) > (iii) > (i) (a) I, II, III (b) II, III, IV
58. Self condensation of two moles of ethyl acetate in (c) II, III (d) II only
presence of sodium ethoxide yields
65. Formic acid can reduce
(a) ethyl propionate
(a) Tollen’s reagent (b) Mercuric chloride
(b) ethyl butyrate
(c) KMnO4 (d) All of these
(c) acetoacetic ester
(d) methyl acetoacetate.
59. Which of the following reaction is appropriate for
converting acetamide to methanamine?
(a) Hoffmann bromamide reaction
(b) Stephen’s reaction
(c) Gabriel phthalimide synthesis
(d) Carbylamine reaction
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

4. The major product formed in the following reaction is :
1.
(2021-08-26/Shift - 1)
Considering the above chemical reaction, identify the
product “X” : (2021-03-18/Shift - 1)
(a)
(a) (b)
(b)
(c)
(c) (d)
(d)
2. 5. The correct sequential addition of reagents in the

preparation of 3-nitrobenzoic acid from benzene is :
(2021-03-18/Shift - 1) (2021-08-26/Shift - 1)
(a) Br2/AlBr3, HNO3/H2SO4, Mg/ether, CO2, H3O+
(b) Br2/AlBr3, NaCN, H3O+, HNO3/H2SO4
(a) (b) (c) Br2/AlBr3, HNO3/H2SO4, NaCN, CO2, H3O+
(d) HNO3/H2SO4, Br2/AlBr3, Mg/ether, CO2, H3O+
6. Which one of the following reactions will not yield
(c) (d) propionic acid?
(2021-08-27/Shift - 2)
(a) CH3CH2COCH3 + OI /H3O
– +
(b) CH3CH2CH3 + KMnO4(Heat), OH–/H3O+

3. (c) CH3CH2CCl3 + OH–/H3O+
(d) CH3CH2CH2Br + Mg, CO2 dry ether/H3O+
(2021-07-25/Shift - 1)
(a) (b)
(c) (d)
7. The major products A and B in the following set of 10. In the following sequence of reactions a compound A,
reactions are (2021-08-31/Shift - 1) (molecular formula C6H12O2 ) with a straight chain
structure gives a C4 carboxylic acid. A is :
A 
LiAlH
H O
 B 
Oxidation
 C 4  carboxylic acid
3
(2021-09-01/Shift - 2)
(a) CH 3  CH 2  COO  CH 2  CH 2  CH 3
OH
|
(a) (b) CH 3  CH 2  CH  CH 2  O  CH  CH 2
(c) CH 3  CH 2  CH 2  COO  CH 2  CH 3
(d) CH 3  CH 2  CH 2  O  CH  CH 2  OH
(b) 11. In the following sequence of reactions

C3 H 6 
H2 / H2 O
 A 
KIO
dil.KOH
B C
The compounds B and C respectively are:
(2021-09-01/Shift - 2)
(c)
(a) Cl3COOK, HCOOH
(b) Cl3COOK, CH3I
(c) CH3I, HCOOK
(d) (d) CHI3, CH3COOK
8. The structure of product C, formed by the following

sequence of reactions is
(2021-08-31/Shift - 1)
12.
CH 3 COOH  SOCl 2  A 
Benzene
AlCl3
B 
KCN
 OH
C
In the above reaction, the reagent "A" is:

(2021-03-16/Shift - 2)
(a) (b) (a) NaBH4, H3O+ (b) Alkaline KMnO4, H+
(c) HCl, Zn–Hg (d) LiAlH4
13. The number of compound/s given below which
contain/s – COOH group is____. (Integer answer)
(c) (d) (A) Sulphanilic acid
(B) Picric acid
9. For the reaction given below : (C) Aspirin
(202108-31/Shift - 2)
(D) Ascorbic acid (2021-02-25/Shift - 2)
14. The number of nitrogen atoms in a semicarbazone
molecule of acetone is ______.
(2021-07-20/Shift - 1)
The compound which is not formed as a product in the

reaction is a:
(a) compound with both alcohol and acid functional
groups
(b) monocarboxylic acid
(c) dicarboxylic acid
(d) diol
15. Two statements are given below:

Statement I : The melting point of monocarboxylic
acid with even number of carbon atoms is higher than
that of with odd number of carbon atoms acid
immediately below and above it in the series.
Statement II : The solubility of monocarboxylic acids
in water decreases with increase in molar mass.
Choose the most appropriate option :
(d)
(JEE Main 2022)
(a) Both Statement I and Statement II are correct.
(b) Both Statement I and Statement II are incorrect.
(c) Statement I is correct but Statement II is incorrect.
(d) Statement I is incorrect but Statement II is correct.
16. Given below are two statements:
Statement I: The esterification of carboxylic acid with
an alcohol is a nucleophilic acyl substitution.
Statement II: Electron withdrawing groups in the
carboxylic acid will increase the rate of esterification 18.
reaction.
Choose the most appropriate option:(JEE Main 2022)
(a) Both Statement I and Statement II are correct
(b) Both Statement I and Statement II are incorrect
(c) Statement I is correct but Statement II is incorrect
Find out the major product for the above reaction.
(d) Statement I is incorrect but Statement II is correct
(JEE Main 2022)
17. Two isomers (A) and (B) with molar mass 184 g/mol
(a)
and elemental composition C, 52.5%; H, 4.9% and Br
42.9% gave benzoic acid and p-bromobenzoic acid,
respectively on oxidation with KMnO4. Isomer ‘A’ is
optically active and gives a pale yellow precipitate
when warmed with alcoholic AgNO3. Isomer ‘A’ and
(b)
‘B’ are, respectively. (JEE Main 2022)
(a)
(c)
(b)
(d)
(c)
19. 22. The major products A and B from the following

reactions are: (JEE Main 2023)
(a)
Consider the above reaction, the compound ‘A’ is:
(JEE Main 2022)
(a)
(b)
(b) (c)
(d)
(c)
23. The major product formed in the following reaction is
(d)
(JEE Main 2023)
(a)
20. In the given reaction
(b)
(Where Et is -C2H5)
The number of chiral carbon/s in product A is (c)
(JEE Main 2022)
21. In a reaction,
(d)
reagents ‘X’ and ‘Y’ respectively are :
(JEE Main 2023)
(a) (CH3CO)2O/H+ and CH3OH/H+, ∆
(b) (CH3CO)2O/H+ and (CH3CO)2O/H+
(c) CH3OH/H+, ∆ and CH3OH/H+, ∆
(d) CH3OH/H+ ∆ and (CH3CO)2O/H+
24. Match List I with List II (a)

List I (Name of List II (Reagent used)
reaction)
A. Hell – Volhard – I. NaOH  I
2
Zelinsky reaction
B. Iodoform reaction II.
 i  CrO2Cl2 , CS2  ii  H 2O (b)
C. Etard reaction III.  i  Br2 / red phosphorus
 ii  H 2O
D. Gatterman – Koch IV. CO , HCl , anhyd. (c)
reaction
AlCl3
Choose the correct answer from the options given
below: (JEE Main 2023)
(a) A - III, B - I, C - II, D - IV
(b) A - III, B - I, C - IV, D - II
(c) A - III, B - II, C - I, D - IV (d)
(d) A - I, B - II, C - III, D - IV
25. The major product formed in the following reaction is:
(JEE Main 2023) 27. In the reaction given below:

(a)
The product ‘X’ is: (JEE Main 2023)

(b) (a)
(c) (b)
(d) (c)
26. The major product ‘P’ formed in the given reaction is

(d)
(JEE Main 2023)

28. The reaction used for preparation of soap from fat is: 31. The major product ‘P’ formed in the following
(JEE Main 2023) sequence of reaction is
(a) An addition reaction
(b) An oxidation reaction
(c) Reduction reaction
(d) Alkaline hydrolysis reaction
29.
(JEE Main 2023)
(a)
‘A’ and ‘B’ in the above reactions are:

(JEE Main 2023)
(a)
(b)
(b)
(c)
(c)
(d)
30. Given below are two statements, one is labelled (d)

as Assertion A and the other is labelled as Reason R.
Assertion A: A solution of the product obtained by
heating a mole of glycine with a mole of chlorine in
presence of red phosphorous generates chiral carbon
atom. 32.
Reason R: A molecule with 2 chiral carbons is always
optically active.
In the light of the above statements, choose the correct
answer from the options given below:
(JEE Main 2023)
In the above conversion the correct sequence of
(a) A is false but R is true
reagents to be added is (JEE Main 2023)
(b) Both A and R are true but R is NOT the correct
(a) (i) KMnO4, (ii) Br2/Fe, (iii) Fe/H+, (iv) Cl2
explanation of A
(b) (i) Fe/H+, (ii) HONO, CuCl, (iv) KMnO4, (v) Br2
(c) A is true but R is false
(c) (i) Br2/Fe, Fe/H+, (iii) KMnO4, (iv) Cl2
(d) Both A and R are true and R is the correct
(d) (i) Br2/Fe, (ii) Fe/H+, (iii) HONO, (iv) CuCl, (v)
explanation of A
KMnO4
33. In the reaction given below 34. Number of compounds from the following which will
not dissolve in cold NaHCO3 and NaOH solutions but
will dissolve in hot NaOH solution is ____.
‘A’ is (JEE Main 2023)

(a)
(b)
(c)
(JEE Main 2023)

(d)
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only One Correct Option] 7. Select correct statements for the following base-catalysed
1. Which is hydrolysed to the maximum extent ? reaction
O O
(a) (b) || 18 ||
OH
R  C  O CH 3  R  C  O  CH3OH
(a) It is a straight forward nucleophilic acyl substitution

(c) (d) (addition and then ejection)
(b) O18 appears in methanol CH3OH
2. Hydrogenation of benzoyl chloride in the presence of Pd (c) The reaction is not reversible
on BaSO4 gives (d) All are correct statements
(a) benzyl alcohol (b) benzaldehyde 8. Hydrolysis of an ester gives acid A and alcohol B. A reduces
(c) benzoic acid (d) phenol Fehling solution and oxidation of B gives A. The ester is
(a) Methyl formate (b) Ethyl formate
3. A tribasic acid is
(c) Methyl acetate (d) Ethyl acetate
(a) Oxalic acid (b) Tartaric acid
(c) Lactic acid (d) Citric acid O H
|| |
4. Which of the following compounds will react with NaHCO3 9. CH 3 CO  C *  CH 2 CH 3 (ester) has chiral carbon (*).
solution to give sodium salt and carbon dioxide |
CH 3
(a) Phenol (b) n-hexanol
Alkaline hydrolysis gives an acid salt and an alcohol. Select
(c) Acetic acid (d) Both (a) and (b) correct statement about alcohol.
5. Peroxyacetic acid (CH3CO3H) is a weaker acid than acetic (a) Configuration about chiral carbon is retained
acid (CH3CO2H)since
(b) Configuration about chiral carbon is inverted
O (c) Product (alcohol) loses chirality
|| (d) None of the statements is correct
(a) Negative charge in CH 3 COO  can’t be
10. What is end product of the following reaction ?
delocalised into the carbonyl group
(b) CH3 group in CH3CO3H shows I-effect
(c) Both are correct
(d) None is correct
6. Select correct statement (s) :
(a) (b)
(a) Carboxylic acids have higher boiling points than isomeric
esters because of dimer formation by intermolecular H-
bonding.
O O
|| || (c) (d)
(b) R C NH 2 or R C NHR molecules are associated
by H-bonding
(c) The presence of carbonyl group in acid derivative
makes them polar compounds
(d) All of the above statements are correct
11. Acidic hydrolysis is least that of :
(a) (b)
(a)
(c) CH3CH2CHO (d)

(b) 14. End product of this conversion :
O
||
1.NaBH 4
CH 3 C CH 2 CH 2 CH 2 CO 2 H  
is :
2.H 2O,H
(c)
(a)
(d)
12. In a set of reactions, acetic acid yielded a product D.

SOCl benzene
2 A  HCN 3 D H O (b)
CH3COOH  anhyd. AlCl  B  C 
3
The structure of D would be :
(c)
(d)
(a)
15. When propionic acid is treated with aqueous sodium bicarbonate,

CO2 is liberated. The C of CO2 comes from
(a) methyl group (b) carboxylic acid group
(c) methylene group (d) bicarbonate group
(b)
16. A, A is
(c)
(a) (b)
(d)
(c) (d) None
13. In the reaction sequence : 17. Sulphonation of benzoic acid produces mainly
SOCl2 LiAlH(O  Bu)3 (a) o–sulphobenzoic acid
CH 3 CH 2 COOH   A  B
(b) m–sulphobenzoic acid
2 2HOCH CH OH
C (c) p–sulphobenzoic acid
‘C’ is most likely to be : (d) o–and p–sulphobenzoic acid
18. CH3Br can be prepared by 23.


(a) CH 3 COOAg  Br2  
P/Br2 Sodalime , 
(b) CH 3 COOH  
Reagents I and II are
(c) Both 
(a) Pt / H2, H3O
(d) None 
19. Benzoic acid gives benzene on being heated with X and (b) Li / NH3, H3O

phenol gives benzene on being heated with Y. Therefore X (c) H2 / Lindlar catalyst, H3O
and Y are respectively (d) H2O/Na, H3O

(a) Sodalime and copper 24. Name the end product in the following series of reactions
(b) Zn dust and NaOH 
CH3COOH 
NH3
 A 
P O5
B
(c) Zn dust and sodalime 2
(d) Sodalime and zinc dust (a) CH4 (b) CH3OH

(c) Acetonitrile (d) Ammonium acetate
25. Silver benzoate reacts with bromine to form
20. A, A is
(a) (b)
(a) (b) (c) (d)
26. Reaction of ethyl formate with excess of CH3MgI followed

by hydrolysis gives
(c) (d) (a) n-propyl alcohol (b) Ethanal
(c) Propanal (d) Isopropyl alcohol
27. Which is hydrolysed to a maximum extent ?
21. Give the order of ease of the esterification of the following acids
O O
|| ||
(a) CH 3 C Cl (b) CH 3 C NH 2
O O
|| ||
(c) CH3 COC 2 H5 (d) CH 3 C CH 3
28. Which is not the source of carbonyl compounds ?
(a) I > II > III > IV (b) IV > III > II > I LiAlH4
(a) RCOCl  
(c) II > I > IV > III (d) I > II > IV > III
R 2 CuLi
(b) RCOCl 
22. Acid hydrolysis of an ester is reversible because : 
(a) alcohol and acid react together to form ester H2 /Pd BaSO4
(c) RCOCl  
(b) protonation of ester makes carbonyl carbon more
reactive for nucleophilic attack Li(t  BuO) AlH
3
(d) RCOCl 
200 K,H O

(c) proton being strong nucleophile, favours hydrolysis 3
(d) H3 O is a nucleophile as well as electrophile

Ag O Br
29. What are the organic products formed 34. 2
PhCH2CH2COOH  2
PhCH2CH2COOAg 
CH3  
1. LiAIH 4
C6H5 COO 2. H3O PhCH 2 CH 2 Br  CO 2  AgBr. The reaction is known as
(a) C6H5 COOH and CH4
Hunsdiecker reaction. Choose incorrect statement(s) re-
(b) C6H5 CH2 OH and CH4
garding the Hunsdiecker reaction.
(c) C6H5 CH3 and CH3 OH
(a) A more convenient way to perform the Hunsdiecker
(d) C6H5 CH2 OH and CH3 OH
reaction is the use of a mixture of acid and mercuric oxide.
(b) Reaction involves radical intermediates.
30. A, A is
(c) The trend in the yield of the resulting halide is primary
> secondary > tertiary.
(a) (d) The reaction starts with decarboxylation.
35. Identify (P) and (Q) in the following reaction
(b)
(c) Both are correct

(d) None is correct
31. In which cases RCO2H is not the product ?
H3O
I : RCN 
 OH
II : RCN 
 
DIBAL-H
III : RCN  SnCl2 /HCl
IV : RCN  (a) (P) is

LiAlH4
V : RCN  
(a) All except III (b) All except III, V
(c) All except I (d) All except I, II (b) (Q) is
Objective Questions II
[One or more than one correct option]
32. Which of the following intermediate are formed during
(c) (P) is
acidic hydrolysis of MeC  N to MeCOOH ?
(a) (b)
(d) (Q) is
(c) (d)
33. Which of the following reagents will reduce a carboxylic

acid to a 1°–alcohol under mild conditions ?
(a) BH3– ether (b) NaBH4, CH3CH2OH
(c) H2 and Pt catalyst (d) LiAlH4 in ether
36. Which of the following intermediates are involved in the  O 
 || 
acid catalysed esterification of carboxylic acid ?
R  C  OH 
42. Assertion (A) : Carboxylic acids   have a
 
carbonyl group but it does not give the test of carbonyl
(a) (b) group.
Reason (R) : Due to resonance, the double bond character
of group is greatly reduced.
(c) (d) (a) A (b) B

(c) C (d) D
43. Assertion (A) : Formic acid reduces mercuric chloride.
Reason (R) : Formic acid reducing aldehydic group.
Assertion Reason
(a) A (b) B
(A) If both Assertion and Reason are correct and (c) C (d) D
Reason is the correct explanation of Assertion.
Pragraph type questions
(B) If both Assertion and Reason are true but Use the following passage, solve Q.44 and Q.45
Reason is not the correct explanation of Assertion. Passage
(C) If Assertion is true but Reason is false. The characteristic and important reaction of carboxylic acid
derivatives is nucleophillic acyl substitution which is
(D) If Assertion is false but Reason is true.
possible only when the incoming nucleophile ( Nu  or
37. Assertion (A) : Formic acid is a weaker acid than acetic
acid. HN u ) must not be a much weaker base than the group or
Reason (R) : pKa of formic acid is less than acetic acid. substituent attached to the acyl group in the acid derivative.
It is a two step process involving nucleophillic attack
(a) A (b) B
followed by the loss of the leaving group.
(c) C (d) D
38. Assertion (A) : Acetic acid does not give haloform reaction.
Reason (R) : Acetic acid has no -hydrogen.
(a) A (b) B
(c) C (d) D
39. Assertion (A) : (CH3)3C–COOH does not give HVZ reaction.
Reason (R) : It does not have any -hydrogen
(a) A (b) B
(c) C (d) D
40. Assertion (A) : The pKa value of acetic acid is lower than 44. Arrange the following in the decreasing order of leaving
that of phenol. group ability ?
Reason (R) : Phenoxide ion is more resonance stabilized.
  
(a) A (b) B (I) X (II) NH 2 (III) OH (IV) OR (V) RCOO
(c) C (d) D
41. Assertion (A) : Resonance energy of carboxylate ion is (a) I > V > III > IV > II (b) I  V  III  IV  II
much greater than that of undissociated carboxylic acid. (c) V > I > II > IV > III (d)    
Reason (R) : Carboxylate ion is a resonance hybrid of
equivalent resonating structures.
(a) A (b) B
(c) C (d) D
45. Which of these order are correct for hydrolysis ?
O O (ii)
|| ||
(I) R  COCl  R  C  O  C  R  R  COOR  RCONH 2
53. A hydrocarbon A of the formula C8H10, on ozonolysis gives
compound B (C4H6O2) only. The compound B can also be
obtained from the alkyl bromide C (C3H5Br) upon treatment
(II) with magnesium in dry ether, followed by carbon dioxide
and acidification. Identify A, B and C and also give
equations for the reactions.
54. Write the chemical equation to show what happens when,
“Ethyl acetate is treated with sodium ethoxide in ethanol
(III) and the reaction mixture is acidified”.
55. In the following reactions identify the compounds A, B, C
and D.
(a) I, III (b) II, III
(i) PCl5 + SO2 A+ B
(c) I, II (d) I, II, III (ii) A + CH3COOH C + SO2 + HCl
Subjective Type Questions (iii) 2C + (CH3)2 Cd 2D + CdCl2
46. Give reason in one or two sentences for the following : 56. Give reasons for the following in one or two sentences.
“Formic acid is a stronger acid than acetic acid”. “Acetic acid can be halogenated in the presence of P and
47. Complete the following with appropriate structures : Cl2, but formic acid cannot be halogenated in the same
way”.
(CH3CO)2 O CH3COOH + ? 57. Complete the following sequence of reactions with
48. Arrange the following as stated : appropriate structures
“Increasing order of acidic strength”. P and
CH 3  CH 2  COOH 
bromine  A
(a) (b) (c)
ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, (i)Alc.KOH(excess)
A   B
(ii)H
(d) (e)
(CH3)2CHCOOH, CH3COOH 58. Which of the following carboxylic acids undergoes
decarboxylation easily ? Explain briefly.
49. Give reasons for :
(i) C6H5—CO—CH2—COOH
“Carbon–oxygen bond lengths in formic acid are 1.23 Å
and 1.36 Å and both the carbon–oxygen bonds in sodium (ii) C6H5—CO—COOH
formate have the same value, ie, 1.27 Å”. (iii) C6 H5  CH  COOH
50. State with balanced equation, what happens when, “Acetic |
OH
anhydride reacts with phenol in presence of a base.
51. Write down the reaction involved in the preparation of the (iv) C6 H5  CH  COOH
following using the reagents indicated against in |
NH2
parenthesis.
“Propionic anhydride from propionaldehyde” 59. Write the structural formula of main organic product formed
when ethyl acetate is treated with double the molar quantity
[AgNO3, NH4OH, P2O5]
of methyl magnesium bromide and the reaction mixture is
52. Complete the following sequence of the reactions with poured into water.
appropriate structures
60. Predict the major product in the following reaction :
(i)CH3MgBr  excess 
(i) C6 H 5  CH 2 CO 2 CH3  
ii  H

61. Arrange the following in order of their increasing ease of True / False
hydrolysis : 66. COOH
200 C o
CH3COOC2H5, CH3COCl, (CH3CO)2O, CH3CONH2 |   CO2   CO  H 2 O
COOH
62. Explain briefly the formation of the products giving the Oxalic acid
structures of the intermediates
(a) Right (b) Wrong
67.
(a) Right (b) Wrong

68.
(a) Right (b) Wrong
63. In the following identify the compounds/reaction conditions 69.

represented by the alphabets A, B, and C :
C6H5COOH A B C6H5CN C
(a) Right (b) Wrong
64. How will you bring about the following conversion ?
70.
“Benzamide from nitrobenzene”.
Fill in the Blanks
65. Formic acid when heated with conc H 2SO4 produces
................... (a) Right (b) Wrong
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Single Choice Questions [Only One Correct Option]
1. Benzoyl chloride is prepared from benzoic acid by
(c)
(a) Cl2, hv (b) SO2Cl2 (2000)
(c) SOCl2 (d) Cl2, H2O
2. Identify the correct order of boiling points of the following
compounds (2002)
(A) CH3CH2CH2CH2OH (B) CH3CH2CH2CHO
(C) CH3CH2CH2COOH
(a) A > B > C (b) C > A > B
(c) A > C > B (d) C > B > A (d)
3.
CH MgBr
3
4. Ethyl ester   P , the product ‘P’ will be (2003)
 excess 
(2003)
(a) (b)
(a)
(c) (d)
5. An enantiomerically pure acid is treated with racemic

mixture of an alcohol having one chiral carbon. The ester
formed will be (2003)
(b) (a) optically active mixture (b) pure enantiomer
(c) meso compound (d) racemic mixture
6. Benzamide on treatment with POCl3 gives (2004)
(a) aniline (b) benzonitrile
(c) chlorobenzene (d) benzyl amine
7. When benzene sulphonic acid and p–nitrophenol are
treated with NaHCO3, the gases released respectively, are
(a) SO2, NO2 (b) SO2, NO
(c) SO2, CO2 (d) CO2, CO2 (2006)
8. In the reaction, 10. List-I includes starting materials and reagents of
Alcoholic KCN
R  X  Dilute HCl
A  B selected chemical reactions. List-II gives structures of
compounds that may be formed as intermediate
The product B is (2008)
products and/or final products from the reactions of
(a) alkyl chloride (b) aldehyde
List-I. (2019)
(c) carboxylic acid (d) ketone
9. The correct order of acid strength of the
following carboxylic acids is: (2019)
(a) I > II > III > IV
(b) II > I > IV > III
(c) I > III > II > IV
(d) III > II > I > IV
Which of the following options has correctcombination

considering List-I and List-II
(a) (III), (S), (R)
(b) (IV), (Q), (U)
(c) (IV), (Q), (R)
(d) (III), (T), (U)

Numeric Value Type Question 13. The compound R is
11. In the following reaction compound Q is obtained

from compound P via an ionic intermediate
(a) (b)
(c) (d)
What is the degree of unsaturation of Q?
(2020)
Assertion Reason 14. The compound S is
(A) If both Assertion and Reason are true and Rea-

son is the correct explanation of the Assertion.
(B) If both Assertion and Reason are true but Rea-
son is not the correct explanation of the Asser- (a) (b)
tion.
(C) If Assertion is true but Reason is false.
12. Assertion (A) : p–hydroxybenzoic acid has a lower boiling
point than o–hyroxybenzoic acid.
Reason (R) : o–hydroxybenzoic acid has intramolecular
hydrogen bonding. (2007) (c) (d)
(a) A (b) B
Subjective Type Questions
(c) C (d) D
15. Write the structures of the products A and B. (2000)
Paragraph Type Questions
O
Use the following Passage, solve Q. 13 to Q. 14 || H3O
CH 3  C  O18 C2 H 5  A  B
Paragraph
16. Identify X and Y in the following synthetic scheme and write
An organic acid P (C11H12O2) can easily be oxidized to a their structures. Explain the formation of labelled formaldehyde
dibasic acid which reacts with ethyleneglycol to produce (H2CO) as one of the products when compound (Z) is treated
a polymer dacron. Upon ozonolysis, P gives an aliphatic with HBr and subsequently ozonolysed. Mark the C carbon
*
ketone as one of the products. P undergoes the following in the entire scheme. (2001)
reaction sequences to furnish R via Q. The compound P
also undergoes another set of reactions to produce S. *
Ba C O 3  H 2 SO 4  X
(2018) *
(C  C 14 gas)
(1) H 2 /Pd  C
(2) NH 3 /  (1) H 2 /Pd  C (1) HCl
(i)M g /ether LiAlH
(3) Br2 / NaOH (2) SOCl2 (2) Mg/Et 2 O CH 2  CH  Br       Y    4 Z
S   P   Q  R
(4) CHCl3 , KOH,  (3) MeMgBr, CdCl (3) CO (dry ice)
2 2 (ii)X
(5) H 2 /Pd  C (4) NaBH 4 (4) H3O 
(iii)H O 
3
17. Five isomeric para–disubstituted aromatic compounds A (c) Treating Q with a solution of NaNO2 in aq. HCl liberates
to E with molecular formula C8H8O2 were given for N2.
identification. (2002) (d) P is more acidic than CH3CH2COOH.
Based on the following observations, given structures of 22. Considering the following reaction sequence (2022)
the compounds :
(i) Both A and B form a silver mirror with Tollen’s reagent;

also, B gives a positive test with FeCl3 solution.
(ii) C gives positive iodoform test.
(iii) D is readily extracted in aqueous NaHCO3 solution.
(iv) E on acid hydrolysis gives, 1, 4–dihydroxy benzene.
18. A racemic mixture of (±) 2–phenyl propanoic acid on

esterification with (±) 2–butanol gives two esters.
Mention the stereochemistry of the two esters
produced. (2003) the correct option is
(a) P = H2/Pd, ethanol, R = NaNO2/HCl, U = 1. H3PO2 2.
19. Convert (in not more than three steps) (2003)
KMnO4 – KOH, heat
(b) P = Sn/HCl, R = HNO2,
20. Compound A of molecular formula C9H7O2Cl exists in keto

form and predominantly in enolic form B. On oxidation (c) , ,
with KMnO4, A gives m–chlorobenzoic acid. Identify A
and B. (2003)
U = 1. CH3CH2OH2. KMnO4 – KOH, heat
21. Considering the reaction sequence given below, the correct
statement(s) is(are) (2022)
(d) , R = H 2 /Pd, ethanol,
(a) P can be reduced to a primary alcohol using NaBH4.

(b) Treating P with conc. NH4OH solution followed by
acidification gives Q.
23. Consider the following reaction scheme and choose the
correct option(s) for the major products Q,R and S.
(2023)
(d)
24. In the following reactions, P, Q, R, and S are the major

products. (2023)
(a)
(b)
(c)
The correct statement (s) about P, Q, R, and S is (are)

(a) P and Q are monomers of polymers dacron and glyptal,
respectively.
(b) P, Q, and R are dicarboxylic acids.
(c) Compounds Q and R are the same.
(d) R does not undergo aldol condensation and S does
not undergo Cannizzaro reaction.
Find Answer Key and Detailed Solutions at the end of this book
CARBOXYLIC ACID AND ITS

DERIVATIVES
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AMINES
Chapter 07 50
AMINES
1. INTRODUCTION The following are examples of quaternary (4o), ammonium salts.

CH 3 CH 2 I 
Amines are organic derivatives of ammonia with one or more |
alkyl or aryl groups bonded to the nitrogen atom. Amines serve H 3 CH 2 C  N   CH 2 CH 3
|
many functions in living organisms, such as bioregulation, CH 2 CH 3
neurotransmission, and defense against predators. Because of
Tetraethylammonium Iodide
their high degree of biological activity, many amines are used as
drugs and medicines. 3. NOMENCLATURE OF AMINES
The alkaloids are an important group of biologically active amines, Nomenclature of alkyl amines
mostly synthesized by plants to protect them from being eaten
by insects and other animals. Although some alkaloids are used
medicinally (chiefly as painkillers), all alkaloids are toxic and cause
death if taken in large quantities.
2. CLASSIFICATION
Amines are classified as primary (1o), secondary (2o), or tertiary

(3o), corresponding to one, two or three alkyl or aryl groups
bonded to nitrogen.
4. STRUCTURE OF AMINES
Ammonia has a slightly distorted tetrahedral shape. A lone pair
of nonbonding electrons occupies one of the tetrahedral
positions. This geometry is represented by sp3 hybridization of
nitrogen, with the bulky lone pair compressing the H–N–H bond
angles to 1070 from the “ideal” sp3 bond angle of 109.50 .
Trimethylamine shows less angle compression because the bulky
methyl groups open the angle slightly.
Quaternary ammonium salts have four alkyl or aryl group to a

nitrogen atom. The nitrogen atom bears a positive charge Just as A tetrahedral amine with three different substituents (and a lone
it does in simple ammonium salts such as ammonium chloride. pair) is non-superimposable on its mirror image. In most cases,
we cannot resolve such an amine into two enantiomers, however,
because the enantiomers interconvert rapidly. This
interconversion takes place by nitrogen inversion, in which the
lone pair moves from one face of the molecule to the other.
SCAN CODE
Amines
AMINES 51
(c) Reaction follows bimolecular substitution (SN2).
In case of quaternary ammonium salts with asymmetric nitrogen

atoms, inversion of configuration is not possible because there
is no lone pair to undergo nitrogen inversion.
Amines that cannot attain the sp2-hybrid transition state for

nitrogen inversion also show chirality. If the nitrogen atom is
contained in a small ring, for example, it is prevented from attaining 5.1.2 Gabriel’s Phthalimide Synthesis
the 120o bond angles that facilitate inversion Phthalamide is treated with KOH first and then potassium
phthalamide is heated with alkyl halide to yield alkyl phthalamide.
The subsequent hydrolysis produces exclusively 1o amine.
Alkyl phthalamide is also treated with hydrazine to get a better
yield of 1o amine.
5. PREPERATION OF AMINES
5.1 Alkyl Halides

5.1.1 Hofmann’s Ammonolysis Method
5.1.3 Grignard Reagent
It is an ammonolysis. An alkyl halide and an ethanolic solution of
ammonia are heated in a sealed tube at 100oC. Grignard reagent or a trialkyl borane on treatment with chloramine
gives the primary’ amine.
(a) The process gives a mixture of products.
(b) Tertiary alkyl halide is not suitable as it gives an alkene. RMgX  Cl NH 2  R  NH 2  MgXCl
SCAN CODE
Amines
AMINES 52
5.2 Alcohols
5.2.1 Sabatier Reaction
Alcohols and ammonia are heated under pressure in the presence
of a catalyst e.g., copper chromite or alumina. A mixture of products
is obtained.
5.4.3 Hofmann Degradation of Amides

5.3 Carbonyl Compounds Amide is warmed with bromine and concentrated aqueous KOH
5.3.1 Reductive Amination or NaOH solution.
Several aldehydes and ketones are converted into amines by (a) Product is 1° amine having one carbon less than amide.
reduction in the presence of ammonia. (b) Alkyl isocyanate is the intermediate and rearrangement is
Reduction can be accomplished catalylically. (hydrogen intramolecular.
(20-150 atm) over Raney nickel at 40o-150oC or by use of sodium
cyanoborohydride, NaBH3CN).
Example
NH ;H ,Ni
3 2  CH (CH ) CH NH
CH 3 (CH 2 )5 CHO  3 2 5 2 2
Heptanal 1-Aminoheptane
Example
5.4.4 Hydrolysis of Amides & Isocyanides

N-substituted amide and isocyanide on hydrolysis give 1° amine.
5.4 Carboxylic Acids & Derivatives Example
5.4.1 Schmidt Reaction
A treatment of cold conc. H 2SO 4 to the mixture of carboxylic acid

and hydrazoic acid gives 1 amine.
RCOOH + N 3 H 
Cold conc.
H 2SO4
 RNH 2 + CO 2 + N 2
NOTE
Example
 The product molecule contains one carbon atom less KOH, H O
than that in acid. R-NC 

2
 R-NH 2 +HCOOK
 Isocyanate is formed as an intermediate in the reaction. Hydrolysis of Isocyanates also yields amines.
5.4.5 Decarboxylation of Amino Acids
Amino acids on heating with barium hydroxide gives 1° amine.
Quaternary ammonium hydroxide on heating gets decomposed
into alcohol if  -hydrogen is not present in the alkyl group but
5.4.2 Curtius Reaction
if there is  -hydrogen, Hofmann elimination proceeds.
The reaction involves the pyrolysis of acyl azide to produce
isocyanates. The subsequent hydrolysis gives amine.
SCAN CODE
Amines
AMINES 53
Example
5.5 Nitrogen Compounds

5.5.1 Reduction of Cyanides, Isocyanides, Nitrile (–CN), oxime
(= NOH), imine (=NH)
NOTE
 The reduction of nitrile by Na/C 2 H 5 OH is known as
Mendius reaction.
 In most of the cases LiAlH 4 is also effective for

reduction.
 Reduction of alkyl isocyanidcs with Na/C 2 H 5 OH or

H 2 /Pt gives 2o amine. 6. PHYSICAL PROPERTIES
Example 6.1 State
CH 3  C 
H 2 .Ni
NOH  The lower aliphatic amines are gases with fishy odour. Primary
orNa,C2 H5 OH  CH 3  CH  NH 2
amines with three or more carbon atoms are liquid and higher
| |
ones are solid.
CH 3 CH 3
Acetonoxime Aniline and other aryl amines are usually colourless but gets
Example coloured on storage due to atmospheric oxidation.
Ph  CH  NH 
2 H ,Ni
PhCH 2  NH 2 6.2 Dipole Moment

Imine
Amines are strongly polar because the large dipole moment of
Example the lone pair of electrons adds to the dipole moments of the
.. and bonds.
 
4[H]
CH 3CH 2  N  C   CH 3CH 2 NHCH 3
2 Amine
5.5.2 Reduction of Nitro Compounds

Nitroalkanes are usually reduced by tin and hydrochloric acid or
lithium aluminium hydride into corresponding amine, H 2 and
6.3 Solubility
catalyst is also used for such a reduction.
Primary and secondary amines have N—H bonds, allowing them
NOTE to form hydrogen bonds. Having no N—H bonds, pure tertiary
 1o aromatic amines are usually prepared by the reduction amines cannot engage in hydrogen bonding. They can, however,
of corresponding nitro compounds by tin, iron or zinc with accept hydrogen bonds from molecules having O—H or N—H
bonds.
HCl or CH 3 COOH .
 Aqueous ethanolic ammonium hydrogen sulphide,
aqueous sodium sulphide or mcthanoic sodium hydrogen
sulphide selectively reduce one nitro group into a polynitro
compound.
Example
Sn,HCl
CH 3CH 2 NO 2  6[H]   CH 3CH 2 NH 2
SCAN CODE
Amines
AMINES 54
Basic strength of amines in gaseous phase increases with number
of alkyl group (+ I effect) attached with nitrogen atom.
Basic strength in aqueous phase
Basic character of amine depends upon the ease of formation of
the cation by accepting a proton and stability of this cation.
Greater the extent of H-bonding in water and more the basic
strength.
Therefore, lower aliphatic amines are soluble in water because
they can form hydrogen bonds with water. However, solubility
decreases with increase in molar mass of amines due to increase
in size of the hydrophobic alkyl part. Higher amines are essentially
insoluble in water.
6.4 Boiling Point
Because nitrogen is less electronegative than oxygen, the N—H
bond is less polar than O—H bond. Therefore, amines form weaker
More the steric hindrance, lesser the basic strength of amine.
hydrogen bonds than do alcohols of similar molecular weights.
Primary and secondary amines have boiling points that are lower
than those of alcohols, yet higher than those of ethers of similar
molecular weights. With no hydrogen bonding, tertiary amines
have lower boiling points than primary and secondary amines of
similar molecular weights.
Overall order of basic strength in aqueous phase:

Methyl substituted amine
(CH3)2NH > CH3NH2 > (CH3)3 N > NH3
2° 1° 3° Ammonia
6.5 Basic character of Amines Ethyl substituted amine
Amines are basic in nature like ammonia. The basic nature of an (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
amine is due to the presence of an unshared pair (lone pair) of
2° 3° 1° Ammonia
electrons on N atom.
6.6 Basic strength of aromatic amines
Aniline is less basic than ammonia and aliphatic amines. Because
lone pair of e- is less available for protonation due to resonance.
Basic strength in gaseous phase

Alkylamines (1°, 2°, and 3°) are stronger bases than ammonia.
Basic strength explained in terms of electron releasing inductive
effect of alkyl group. The electron density on the nitrogen atom
increases by + I effect. Alkylamines can donate the lone pair of I II III
electrons more easily than ammonia.
IV V
SCAN CODE
Amines
AMINES 55
Effect of substituents on basic character
I. EDG group or +M or + I effect
Basic strength increases
II. EWG group or - M or - I effect
Basic strength decreases
Example - Order of basic strength:
7. CHEMICAL PROPERTIES OF AMINE
7.1 Alkylation
7.5 Hofmann’s Exhaustive Methylation and Elimination
Amines undergo alkylation on reaction with alkyl halides.
 R ' X
R  NH 2  CH 3 I  R  N H  CH 3
RNH 2  R ' X 
 HX  RR ' NH 
 HX  RR '2 N
(1 ) (2 )
Primary
amine
Secondary
amine
Tertiary
amine
 CH 3 I
..
 
 R ' X   HX
R  N(CH 3 ) 3 I 
CH3I
 R  N(CH 3 ) 2
 Quatermary (3 )
RR '3 N Ammonium Salt
Quatemary
ammonium salt Quarternary ammonium iodides are converted to hydroxides with
7.2 Acylation moist Ag 2O . The hydroxide on heating undergo elimination to
Aliphatic and aromatic primary and secondary amines react with give 3° amines and alkenes. The important aspect of this
acid chlorides, anhydrides and esters by nucleophilic substitution elimination is that the least substituted alkene is the major product
reaction to form amide. The reaction is carried out in the presence (Hofmann Rule). This is known as Hofmann’s Elimination.
of a base (generally pyridine). Base removes HCl so formed and
shifts the equilibrium to the right hand side.
H
|
..
C 2 H 5  N:  CH3  C  Cl 
Base
 C2 H 5  N  C  CH 3  H  Cl
| || | ||
C2 H5 O C 2H5 O
N-Ethylethanamine N,N-Diethylethanamide
7.3 Reaction with aldehyde

Aldehydes and ketones react with primary amines in the presence
of an acid as catalyst to form azomethines called Schiff’s base. 8. INTRODUCTION OF ANILINE

RNH 2  O  HCR ' 
H
 RN  HCR ' One of the starting materials used for preparing sulpha drugs is
Alkylamine Aldehyde Schiff's base (Aldimine)
aniline. Aniline is a primary aromatic amine which consists of an
H –NH2 group attached to the benzene ring.
|

C 2 H 5 NH 2  O  C  CH3 
H
C 2 H 5 N  CHCH 3
Acetaldehyde Ethylidene ethylamine
7.4 Cope elimination

Tertiary amine oxides having  -hydrogen atom on heating
form an alkene and N, N-disubstituted hydroxylamine. The
alkene formed is the Hofmann elimination product.
SCAN CODE
Amines
AMINES 56
8.1 Nomenclature of aryl amines 9.3 From phenol and ammonia
9.4 By reduction of azo compound
9. PREPARATION OF AROMATIC AMINES
Besides the methods in the preparation of aliphatic amines,

following methods can also be used:
9.1 Reduction of Nitro Conipounds
9.1.1 Vapour-Phase Reduction
Reducing Agents :
CuO on SiO 2 or V  Pt Catalyst 10. REACTIONS OF AROMATIC AMINES
10.1 Oxidation
Aromatic amines are readily oxidised to various products
depending on conditions. Under controlled oxidation using
Na 2 Cr2 O7 and H 2SO4 aniline is oxidised to p-benzoquinone.
9.1.2 Catalytic Hydrogenation
In fact, on standing in air, p-benzoquinone is formed.
Nitro compounds on catalytic hydrogenation gives aromatic
If oxidation is not controlled, a black dye, aniline black is formed.
amine ( H 2 , Pd  C / Et  OH ).
10.2 Halogenation
9.2 By ammonolysis of aryl halides
Amine group (NH 2 ) is a very strong activating group and an
ortho/ para director. It forms 2,4,6- tribromo aniline on normal
bromination in H 2 O .
NOTE
If deactivating groups ( -NO 2 etc.) are at ortho or para
position, rcaction becomes quite easy to carryout.
SCAN CODE
Amines
AMINES 57
Ortho and para derivatives can be made by decreasing the 10.4 Sulphonation
activating power of amino group by acetylation of aniline.
 NHCOCH 3 group is a mild ortho and para director..
10.3 Nitration
NOTE
The normal nitration of aniline is not done as nitrating mixture is
Usually -NH2 group attached to benzene is unable to
oxidising and NH 2 is a strong activating group. Moreover, at form zwitter ion but here -SO3H is very strongly acidic.
288 K. aniline is protonated to form the anilinium ion which is Hence, sulphanilic acid forms zwitter ion. For example when
meta directing. That is why besides the ortho and para derivatives, -NH2 group is attached to benzoic acid in any position,
a significant amount of meta derivative is also formed. zwitter ion is not formed.
11. DIAZONIUM SALT AND REACTION
However, by protecting the -NH 2 group by acetylation reaction

with acetic anhydride, the nitration reaction can be controlled
and the p-nitro derivative can be obtained as the major product.
12. TEST OF AMINES
1. Sulphonylation-Hinsberg Test
2. Nitrous Acid Test
3. Carbylaminc Reaction
4. Treatment with CS2/HgCl2
12.1 Sulphonylation-Hinsberg Test
Treatment with benzene sulphonyl chloride (Hinsberg reagent)
or p-toluene sulphonyl chloride.
SCAN CODE
Amines
AMINES 58
(a) The reaction is used to separate the amine mixture. 12.3 Carbylamine Reaction
(b) 1o and 2o amine, due to the presence of active hydrogen
1° amine on treatment with chloroform and alcoholic KOH gives
react and give corresponding sulphonamidc while 3° amine out unpleasant or pungent vapours of alkyl carbylamine
does not react. (isocyanide). The reaction is known as a test for 1° amine.
(c) 1o amine product N-alkyl benzene sulphonamide is soluble
in KOH forming a water-soluble salt. CHCl3 + OH   :CCl 2 + H 2 O
12.4 Treatment with CS2/HgCl2
(a) 1o amine on warming with CS2 produces dithiocarbamic

acid, which is decomposed by mercuric chloride to alkyl
isothiocyanate. It is called as Hofmann’s Mustard Oil
Reaction.
(b) Although 2° amine gives dithiocarbamic acid but is not
decomposed by mercuric chloride.
12.2 Nitrous Acid Test
(c) 3° amine don’t react with CS2 .
(a) 1° amine on reaction with HNO 2 gives usually an alcohol.
The reaction involves the formation of diazonium salt as an
intermediate.
(b) 2° amine gives nitrosoamine which is a yellow oily liquid.
(c) 3° amine dissolves in cold HNO 2 to form an unstable salt

which on heating decomposes to give nitrosoamine and an
alcohol.
HNO
2  CH CH OH  N  H O
CH 3 CH 2 NH 2  3 2 2 2
 CH3 2 NH 
HNO2
  CH3 2 N  N  O  H 2 O
 CH3CH2 3 N 
HNO2
  CH3CH2 3 N.HNO2

 CH3CH2 2 NNOCH3CH2OH
NOTE
Liebermann’s Nitroso Test -Test for 2° amines (nitroso
amines) and phenols.
SCAN CODE
Amines
AMINES 59
SUMMARY
 Properties of Amines  Properties of Aniline

 Reaction of Diazonium Salt
SCAN CODE
Amines
AMINES 60

8. Leakage of which gas was responsible for the Bhopal
Introduction to amines tragedy in 1984
1. C7H9N has how many isomeric forms that contain a
(a) (b)
benzene ring?
(c) CHCl3 (d) C6H5COCl
(a) 4 (b) 5
9. Which of the following is a secondary amine ?
(c) 6 (d) 7
(a) 2-Butanamine
2. Which of the following is a 3º amine ?
(b) N-Methylpiperidine
(a) 1-methylcyclohexylamine
(c) N-Methyl-2-pentanamine
(b) Trimethylamine
(d) p-Anisidine
(c) tert-butylamine
(d) N-methylaniline Preparation of amines
3. The correct IUPAC name for 10. Best method for preparing primary amines from alkyl halides
without changing the number of carbon atoms in the chain
CH2 = CHCH2NHCH3 is
is
(a) Allylmethylamine
(a) Hofmann Bromamide reaction
(b) 2-amino-4-pentene
(b) Gabriel phthalimide synthesis
(c) 4-aminopen-1-ene
(c) Sandmeyer reaction
(d) N-methylprop-2-en-1-amine
(d) Reaction with NH3
4. C3H9N represents
11. By heating ammonium chloride with two equivalents of
(a) Primary amine (b) Secondary amine formaldehyde it forms :
(c) Tertiary amine (d) All of these (a) dimethylamine (b) ethylamine
5. A secondary amine is (c) methylamine (d) ammonium formate
(a) An organic compound with two – NH2 groups 12. Which of the following reagents can be used to prepare
(b) A compound with two carbon atoms and an –NH2 ethyl carbylamine from ethyl iodide ?
group (a) KCN (b) AgCN
(c) A compound with an –NH2 group on the carbon atom (c) CuCN (d) HCN
in number 2 position
13. Which one of the following methods is neither meant for
(d) A compound in which two of the hydrogens of NH3 the synthesis nor for separation of amines ?
have been replaced by organic groups (a) Curtius reaction (b) Wurtz reaction
6. Allyl isocyanide has (c) Hofmann method (d) Hinsberg method
(a) 9 sigma bonds and 4 pi bonds 14. The best reagent for converting 2-phenylpropanamide into
(b) 8 sigma bonds and 5 pi bonds 2-phenylpropanamine is ..................... .
(c) 8 sigma bonds, 3 pi bonds and 4 non-bonding electrons (a) excesss H2
(d) 9 sigma bonds, 3 pi bonds and 2 non-bonding electrons (b) Br2 in aqueous NaOH
7. is a (c) iodine in the presence of red phosphorus
(a) Secondary amine (b) Primary amine (d) LiAlH4 in ether
(c) Tertiary amine (d) None of these 15. Mendius reduction converts an alkyl cyanide to
(a) a primary amine (b) an aldehyde
(c) a ketone (d) an oxime
AMINES 61
16. The source of nitrogen in Gabriel synthesis of amines is
(d) Treatment of amide with bromine in aqueous solution
.................
of sodium hydroxide.
(a) Sodium azide, NaN3 (b) Sodium nitrite, NaNO2
22. An organic compound ‘A’ on treatment with NH3 gives
(c) Potassium cyanide, KCN ‘B’ which on heating gives ‘C’, ‘C’ when treated with Br2
– +
(d) Potassium phthalimide, C6H4(CO)2N K in the presence of KOH produces ethylamine. Compound
‘A’ is
17. The best reagent for converting, 2-phenyl-propanamide
into 1-phenylethanamine is .................. . (a) CH3COOH (b) CH3CH2CH2COOH
(a) excess H2/Pt (b) NaOH/Br2 (c) (d) CH3CH2COOH
(c) NaBH4/methanol (d) LiAlH4/ether

18. Amongst the given set of reactants, the most appropriate
Physical & Chemical Properties of amines
for preparing 2º amine is ....................... .
23. Among the following isomeric C4H11N amines, one
(a) 2º R—Br + NH3
having the lowest boiling point
(b) 2º R—Br + NaCN followed by H2/Pt
(c) 1º R—NH2 + RCHO followed by H2/Pt (a) (b)
(d) 1º R—Br (2 mol) + potassium phthalimide followed by
+
H3O /heat (c) (d)
19. In the following sequence of reactions, what is D ?
24. Which of the following should be most volatile ?
(I) CH 3CH 2CH 2 NH 2 (II) (CH 3 )3 N
(III)
(a) Primary amine
(b) An amide (IV) CH3CH2CH3
(c) Phenyl isocyanate (a) II (b) IV
(d) Chain lengthened hydrocarbon (c) I (d) III
20. In order to prepare a 1º amine from an alkyl halide with 25. Amongst the following, the strongest base in aqueous
simultaneous addition of one CH2 group in the carbon medium is .............
chain, the reagent used as source of nitrogen is ............ . (a) CH3NH2 (b) NCCH2NH2
(a) Sodium amide, NaNH2 (c) (CH3)2NH (d) C6H5NHCH3
(b) Sodium azide, NaN3 26. Which of the following is the weakest Bronsted base ?
(c) Potassium cyanide, KCN
– +
(d) Potassium phthalimide, C6H4(CO)2N K
(a) (b)
21. Which of the following methods of preparation of amines
will not give same number of carbon atoms in the chain of
amines as in the reactant ?
(a) Reaction of alkyl nitrile with LiAlH4.
(c) (d) CH3NH2
(b) Reaction of amide with LiAlH4 followed by treatment
with water.
(c) Heating alkyl halide with potassium salt of phthalimide
followed by hydrolysis.
AMINES 62
27. Which of the following compounds is the weakest 32. Which of the following compounds is most basic ?
Bronsted base ?
(a)
(a) (b)
(b)
(c)
(c) (d)
28. Among the following amines, the strongest Bronsted base (d)
is ..................... .
33. The strongest base in aqueous solution among the
following amines is
(a) (b) NH3 (a) N, N-diethylethanamine
(b) N-ethylethanamine
(c) N-methylmethanamine
(d) ethanamine
(c) (d) 34. Strongest base is
29. The correct decreasing order of basic strength of the

following species is ............ . (a) (b)
H2O, NH3, OH , NH

–
2
(a) NH 
2  OH  NH3  H 2 O
(c) (d)

(b) OH  NH2  H2O  NH3
35. The most reactive amine towards dilute hydrochloric acid
(c) NH3  H 2 O  NH
2  OH

is ................
(d) H 2O  NH3  OH  NH

2
(a) CH3—NH2 (b)
30. Arrange the following in increasing order of their basic
strength (Given that amines in aqueous state) :
CH3NH2 (I), (CH3)2NH (II), (CH3)3N (III), C6H5CH2NH2 (IV).
(a) IV < III < II < I (b) IV < III < I < II (c) (CH3)3—N (d)
(c) I < II < III < IV (d) IV < III < I = II
31. The weakest base among the following is
(a) dimethylamine (b) aniline
(c) methylamine (d) ethylamine
AMINES 63
36. Consider the following compounds,
(c)
(d)
40. Amongst the following the most basic compound is

(a) p-nitroaniline (b) acetanilide
What is the correct order of basicity of the above
(c) aniline (d) benzylamine
compounds ?
41. Which of the following is more basic than aniline?
(a) I > II > III (b) III > I > II
(a) Benzylamine (b) Diphenylamine
(c) III > II > I (d) I > III > II
(c) Triphenylamine (d) p-Nitroaniline
37. The correct increasing order of basic strength for the
following compounds is ............... . 42. Acid anhydrides on reaction with primary amines give
................... .
(a) amide (b) imide
(c) secondary amine (d) imine
43. In the chemical reaction,
CH3CH2NH2 + CHCl3 + 3 KOH (A) + (B) + 3H2O, the
compound (A) and (B) are respectively.
(a) C2H5NC and 3 KCl
(a) II < III < I (b) III < I < II (b) C2H5CN and 3 KCl
(c) III < II < I (d) II < I < III (c) CH3CH2CONH2 and 3 KCl
38. The correct order of increasing basic nature of the following (d) C2H5NC and K2CO3
bases is
44. CH3NH2 + CHCl3 + 3KOH X + Y + 3H2O
compounds X and Y are :
(a) CH3CN + 3KCl (b) CH3NC + 3KCl
(c) CH3CONH2 + 3KCl (d) CH3NC + K2CO3
45. On heating benzyl amine with chloroform and ethanolic
KOH, product obtained is
(a) benzyl alcohol (b) benzaldehyde
(c) benzonitrile (d) benzylisocyanide
46. On heating an aliphatic primary amine with chloroform
(a) 2 < 5 < 1 < 3 < 4 (b) 5 < 2 < 1 < 3 < 4 and ethanolic potassium hydroxide, the organic compound
(c) 2 < 5 < 1 < 4 < 3 (d) 5 < 2 < 1 < 4 < 3 formed is :
39. Which of the following is the strongest base ? (a) an alkanediol
(b) an alkyl cyanide
(a) (c) an alkyl isocyanide
(d) an alkanol
(b)
AMINES 64
47. The compound obtained by heating a mixture of 55. C4H11N on reaction with HNO2 forms a tertiary alcohol.
ethylamine and chloroform with ethanolic potassium Thus, C4H11N is
hydroxide (KOH) is (a) primary amine
(a) an amide (b) secondary amine
(b) an amide and nitro compound (c) tertiary amine
(c) an ethyl isocyanide (d) quaternary ammonium salt
(d) an alkyl halide. 56. Which of the following will be most stable diazonium
48. For carbylamine reaction, we need hot alcoholic salt ( R N 2 X  )?
KOH and
(a) C H 3 N 2 X  (b) C 6 H 5 N 2 X 
(a) any primary amine and chloroform
(c) C H 3 CH 2 N 2 X  (d) C 6 H 5 C H 2 N 2 X 
(b) chloroform and silver powder
(c) a primary amine and an alkyl halide 57. Benzylamine may be alkylated as shown in the following
equation :
(d) a monoalkylamine and trichloromethane.
C6H5CH2NH2 + R–X C6H5CH2NHR
49. The action of nitrous acid on an aliphatic primary
Which of the following alkyl halides is best suited for this
amine gives
reaction through SN1 mechanism ?
(a) secondary amine
(a) CH3Br (b) C2H5Br
(b) nitro alkane
(c) C6H5CH2Br (d) None of these
(c) alcohol
58. The optically active compound (X)
(d) alkyl nitrite.
50. Hofmann Bromamide Degradation reaction is shown by
....................... .
(a) ArNH2 (b) ArCONH2
on treatment with NaNO2/HCl gives
(c) ArNO2 (d) ArCH2NH2
(a) 1º alcohol with retention of configuration
51. Which among the following amines can be directly oxidised
(b) 2º alcohol with inversion of configuration
to the corresponding nitro compound by potassium
permanganate ? (c) racemic mixture of 2º alcohols
(a) CH3NH2 (b) (CH3)2CH–NH2 (d) racemic mixture of 1º alcohols
(c) (CH3)2NH (d) (CH3)3C–NH2 Preparation and properties of Aniline

52. Methylamine reacts with HNO2 to form .............. . 59. Reduction of aromatic nitro compounds using Fe and HCl
(a) CH3–O–N = O (b) CH3–O–CH3 gives ............. .
(c) CH3OH (d) CH3CHO (a) aromatic oxime (b) aromatic hydrocarbon
53. The gas evolved when methylamine reacts with nitrous (c) aromatic primary amine
acid is ............. . (d) aromatic amide
(a) NH3 (b) N2 60. Reaction of aniline with benzaldehyde is :
(c) H2 (d) C2H6 (a) substitution (b) addition
54. Which of the following will give N2 gas on treatment with (c) condensation (d) polymerisation
nitrous acid (NaNO2 + HCl) ?
(a) C2H5NH2 (b) CH3NH2
(c) (CH3)2CH–NH2 (d) All will give N2
AMINES 65
61. Phenyl isocyanides are prepared by which of the 67. Which of the following statements about primary
following reaction? amines is false?
(a) Reimer—Tiemann reaction
(a) Alkyl amines are stronger bases than aryl amines.
(b) Carbylamine reaction (b) Alkyl amines react with nitrous acid to produce
(c) Rosenmund’s reaction alcohols.
(d) Wurtz reaction (c) Aryl amines react with nitrous acid to produce
62. Aniline on treatment with aqueous bromine gives : phenols.
(a) 2,4,6-tribromo aniline (d) Alkyl amines are stronger bases than ammonia.
(b) o-bromo aniline 68. The final product C, obtained in this reaction,
(c) 2,4-dibromo aniline
(d) p-bromo aniline
63. In the chemical reactions
A 
CuCN
B
Compounds A and B respectively are

(a) (b)
(a) fluorobenzene and phenol
(b) benzene diazonium chloride and benzonitrile
(c) nitrobenzene and chlorobenzene
(d) phenol and bromobenzene
64. In the reaction
(c) (d)
reduction CHCl /KOH reduction

69. A  B 
3
C  N-
methylaniline, then A is
A is
(a) H3PO2 and H2O (b) H+/H2O
(c) HgSO4/H2SO4 (d) Cu2C12 (a) (b)
65. The reaction, 

Cu / HCl
 ArCl + N2 + CuCl is
named as .............. .
(a) Sandmeyer reaction (b) Gattermann reaction
(c) C H 3 NH 2 (d)
(c) Claisen reaction (d) Carbylamine reaction
66. X is
(a) Na2S (b) Sn/HCl

(c) LiAlH4 (d) all of these
AMINES 66
70. In a set of reactions, m-bromobenzoic acid gave a product
D. Identify the product D.
(c)
(d)
73. Aniline in a set of reactions yielded a product D.
(a) (b)
The structure of the product D would be
(c) (d) (a) C6H5NHOH (b) C6H5NHCH2CH3

(c) C6H5CH2NH2 (d) C6H5CH2OH
74. Aniline on heating with fuming sulphuric acid gives :
71. m-Bromoaniline can be prepared by
(a) aniline sulphate
HNO3 1. Sn/HCl Br2
(a) C6 H 6       (b) sulphanilic acid
H 2SO 4 2. NaOH,H 2 O H 2O
(c) aniline 2,4-disulphonic acid
(d) nitrobenzene
(b)
75. Aniline is reacted with bromine water and the resulting
product is treated with an aqueous solution of sodium
nitrite in presence of dilute hydrochloric acid. The
compound so formed is converted into a
(c)
tetrafluoroborate which is subsequently heated to dry.
The final product is
(a) p-bromoaniline
(d) (b) p-bromofluorobenzene
(c) 1, 3, 5-tribromobenzene
72. Predict the product : (d) 2, 4, 6-tribromofluorobenzene.
76. Fluorobenzene (C 6 H 5F) can be synthesized in the
laboratory
(a) by heating phenol with HF and KF
(b) from aniline by diazotisation followed by heating the
(a) diazonium salt with HBF4
(c) by direct fluorination of benzene with F2 gas
(d) by reacting bromobenzene with NaF solution
(b)
AMINES 67
77. In the chemical reactions,
(b)
(c)
the compounds ‘A’ and ‘B’ respectively are
(a) nitrobenzene and fluorobenzene
(b) phenol and benzene (d)
(c) benzene diazonium chloride and fluorobenzene 80. Toluene is nitrated and the resulting product is reduced
(d) nitrobenzene and chlorobenzene with tin and hydrochloric acid. The product so obtained is
78. Aniline in a set of the following reactions yielded a diazotised and then heated with cuprous bromide. The
coloured product Y. reaction mixture so formed contains
(a) mixture of o- and p-bromotoluenes
(b) mixture of o- and p-dibromobenzenes
(c) mixture of o- and p-bromoanilines
(d) mixture of o- and m-bromotoluenes
The structure of ‘Y would be 81. Aniline when diazotised in cold and then treated with
dimethyl aniline gives a coloured product. Its structure
would be :
(a)
(a)
(b)
(b)
(c)
(c)
(d)
79. In the following reaction, the product (A) is

(d)
(a)
AMINES 68
Test of Amines 85. Which of the following is soluble in sodium hydroxide

82. In Hinsberg’s test the product of which amine does not
dissolve in NaOH ? (a)
(a) CH3CH2NH2 (b) (CH3)2CHNH2
(c) CH3NHCH3 (d) CH3N(CH3)2
83. Which of the following method is generally not employed for
(b)
the separation of primary, secondary and tertiary amines ?
(a) Fractional distillation
(b) Hinsberg’s method
(c)
(c) Hoffmann’s method
(d) Filtration
84. Which of the following compounds will dissolve in an
alkali solution after it undergoes reaction with Hinsberg’s (d)
reagent ?
(a) CH3NH2 (b) (CH3)3N
(c) (C2H5)2NH (d) C6H5NHC6H5
AMINES 69
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

1. ‘A’ and ‘B’ in the following reactions are (a) Low temperature
(b)  NH 2 group is highly meta-directive

(c) Formation of anilinium ion
(d) –NO2 substitution always takes place at meta-position
(2021-24-02-Shift-I) 3. The diazonium salt of which of the following compounds

will form a coloured dye on reaction with ß-Naphthol in
NaOH ? (2021-24-02-Shift-II)
(a)
(a) (b)
(b)
(c) (d)
4. Which of the following reaction/s will not given p-

aminoazobenzene? (2021-25-02-Shift-I)
(c)
(A)
(d)
2. In the following reaction the reason why meta-nitro

product also formed is (2021-24-02-Shift-I) (B)
(C)
(a) C only (b) A and B

(c) B only (d) A only
AMINES 70
5. carbylamines test is used to detect the presence of primary 8. A. Phenyl methanamine B. N,N-Dimethylaniline
amino group in an organic compound. Which of the C. N-Methyl aniline D. Benzenamine
following compound is formed when this test is performed
Choose the correct order of basic nature of the above
with aniline? (2021-25-02-Shift-II)
amines. (2021-26-02-Shift-II)
(a) D > B > C > A (b) A > C > B > D
(a) (b) (c) A > B > C > D (d) D > C > B > A
9. In the below chemical reaction, intermediate “X” and
reagent/condition “A” are: (2021-16-03-Shift-I)
(c) (d)
6. Correct statement about the given chemical reaction is:

(2021-25-02-Shift-II)
(a)
(a) Reaction is possible and compound (B) will be the

(b)
major product
(b) Reaction is possible and compound (A) will be major
product
(c) Group is ortho and para directive, so product (B) is not
possible
(d) The reaction will form sulphonated product instead of
nitration (c)
7. An amine on reaction with benzene sulphonyl chloride
produces a compound insoluble in alkaline solution. This
amine can be prepared by ammonolysis of ethyl chloride.
The correct structure of amine is : (2021-26-02-Shift-I)
(a) CH3CH2CH2NHCH3
H (d)
(b) CH 3 C H 2 C H 2 N  CH 2 CH 3
(c) CH3CH2NH2
(d)
AMINES 71
10. Which of the following reaction DOES NOT involve
Hoffmann bromamide degradation?
(2021-16-03-Shift-I)
13.
In the above reaction, the structural formula of (A), “X”

(a) and “Y” respectively are : (2021-03-17-Shift-II)
(b) (a)
(c)
(b)
(d)
11. Ammonolysis of Alkyl halides followed by the treatment

with NaOH solution can be used to prepare primary,
secondary and tertiary amines. The purpose of NaOH in
the reaction is : (2021-03-16-Shift-II)
(c)
(a) to increase he reactivity of alkyl halide
(b) to remove basic impurities
(c) to activate NH3 used in the reaction

(d) to remove acidic impurities
12. Which of the following reaction is an example of
ammonolysis? (2021-03-17-Shift-I)
(a) C 6 H 5 CH 2 CN 
[H]
 C 6 H 5 CH 2 CH 2 NH 2
(d)
(b) C6 H 5 COCl  C6 H 5 NH 2  C 6 H 5 CONHC 6 H 5
(c) C6 H 5 CH 2 Cl  NH 3  C6 H 5 CH 2 NH 2

(d) C6 H5 NH 2 
HCl
C6 H5 N H3 Cl 
AMINES 72
17.
14.
Considering the above reaction, X and Y respectively

are: (2021-03-18-Shift-I)
Consider the given reaction, percentage yield of:

(a) (2021-03-18-Shift-II)
(a) C > A > B (b) A > C > B
(c) C > B > A (d) B > C > A
18. An organic compound “A” on treatment with benzene
sulphonyl chloride gives compound B. B is soluble in dil.
(b) NaOH solution. Compound A is : (2021-03-18-Shift-II)
(a) C 6 H 5  NHCH 2 CH 3
(b) C6 H 5  N  (CH 3 ) 2
(c) C6 H 5  CH  NH 2
(c) |
CH 3
(d) C 6 H 5  CH 2 NHCH 3
19. Compound A is converted to B on reaction with CHCl3
and KOH. The compound B is toxic and can be
(d)
decomposed by C. A, B and C respectively are:
(2021-07-20-Shift-I)
(a) primary amine, nitrile compound, conc. HCl
15. Reagent, 1-naphthylamine and sulphanilic acid in acetic (b) secondary amine, isonitrile compound, conc. NaOH
acid is used for the detection of (2021-03-18-Shift-I) (c) primary amine, isonitrile compound, conc. HCl

(a) NO 2
(b) N 2 O (d) secondary amine, nitrile compound, conc. NaOH
(c) NO3 (d) NO

16. In the reaction of hypobromite with amide, the carbonyl
carbon is lost as : (2021-03-18-Shift-II)
(a) CO (b) HCO3
(c) CO 32 (d) CO 2

AMINES 73
20.
21.
Consider the above reaction, compound B is:

In the above reactions, product A and product B (2021-07-20-Shift-II)
respectively are: (2021-07-20-Shift-II)
(a)
(a)
(b)
(b)
(c)
(c)
(d)
22.
(d)
In the chemical reactions given above A and B respectively

are: (2021-22-07-Shift-II)
(a) H3PO2 and CH3CH2Cl (b) CH3CH2OH and H3PO2
(c) H3PO2 and CH3CH2OH (d) CH3CH2Cl and H3PO2
AMINES 74
23. Which one of the following reactions does not occur? 25. Which one of the products of the following reactions does
(2021-07-22-Shift-II) not react with Hinsberg reagent to form sulphonamide?
(2021-07-25-Shift-I)
(a)
(a)
(b)
(b)
(c)
(d) (c)
24. Given below are two statements, one is labelled as

Assertion (A) and other is labelled as Reason (R).
Assertion (A) : Gabriel phthalimide synthesis cannot be
used to prepare aromatic primary amines.
Reason (R) : Aryl halides do not undergo nucleophilic (d)
substitution reaction.
answer from the options given below: 26. Which one of the following compounds will liberate CO2,
(2021-07-25-Shift-I) when treated with NaHCO3? (2021-07-25-Shift-I)
(a) Both (A) and (R) true but (R) is not the correct
explanation of (A). (a) (b)
(b) (A) is false but (R) is true.
(c) Both (A) and (R) true and (R) is correct explanation of
(A). (c) (d)
(d) (A) is true but (R) is false.
AMINES 75
27.
(c) (d)
Consider the above reaction, the Product "P" is: 29. What is A in the following reaction?
(2021-07-25-Shift-II)
(a)
(2021-07-27-Shift-II)
(b)
(a)
(c)
(b) (c)
(d) (d)
30. The correct sequence of correct reagents for the following

28. What is the major product "P" of the following reaction? transformation is : (2021-07-27-Shift-II)
(2021-07-25-Shift-II)
(a) (i) Fe, HCl; (ii) Cl2, HCl; (iii) NaNO2, HCl, 0°C; (iv) H2O/
H+
(b) (i) Fe, HCl; (ii) NaNO2, HCl, 0°C; (iii) H2O/H+; (iv) Cl2,
FeCl3
(a) (b)
(c) (i) Cl2, FeCl3; (ii) Fe, HCl; (iii) NaNO2, HCl, 0°C; (iv)
H2O/H+
(d) (i) Cl2, FeCl3; (ii) NaNO2, HCl, 0°C; (iii) Fe, HCl; (iv)
H2O/H+
AMINES 76
31. Given below are two statements
Statement I: Aniline is less basic than acetamide.
Statement II: In aniline, the lone pair of electrons on
nitrogen atom is delocalized over benzene ring due to (d)
resonance and hence less available to a proton.
(2021-07-27-Shift-I)
Choose the most appropriate option :
(a) Statement I is true, but statement II is false. 33. The major product of the following reaction is
(b) Statement I is false, but statement II is true.

(c) Both statement I and statement II are true.
(d) Both statement I and statement II are false.
32.
(2021-08-27-Shift-I)
(a)
The major product in the above reaction is:
(2021-08-26-Shift-II)
(b)
(c)
(a)
(d)
34. Which of the following is not a correct statement for

primary aliphatic amines? (2021-08-27-Shift-I)
(b)
(a) The intermolecular association in primary amines is
less than the intermolecular association in secondary
amines.
(b) Primary amines on treating with nitrous acid solution
form corresponding alcohols except methyl amine.
(c) Primary amines are less basic than the secondary
amines.
(c) (d) Primary amines can be prepared by the Gabriel

phthalimide synthesis.
AMINES 77
35. The compound/s which will show significant
intermolecular H–bonding is/are :
(d)
37. Identify A in the following reaction
(2021-09-01-Shift-II)
(2021-08-27-Shift-II)
(a) (b) only (b) (c) only
(c) (a) and (b) only (d) (a), (b) and (c)
36. The major products A and B formed in the following
reaction sequence are : (2021-08-31-Shift-II) (a) (b)
(c) (d)
38. Which one of the following gives the most stable

Diazonium salt? (2021-09-01-Shift-II)
(a)
(a) CH 3  CH 2  CH 2  NH 2 (b)
(c) (d)
(b) 39. Which of the following is least basic?

(2021-03-16-Shift-II)
 
(a) (CH 3 CO) 2 NH (b) (CH 3 CO) NHC2 H 5
 
(c) (C2 H 5 )3 N (d) (C2 H 5 ) 2 N H
(c)
AMINES 78
40. Hoffmann bromomide degradation of benzamide gives 41. Primary, secondary and tertiary amines can be separated
product A, which upon heating with CHCl 3 and NaOH using : (2021-03-17-Shift-II)
gives product B. (2021-03-17-Shift-I)
(a) Benzene sulphonic acid
The structures of A and B are:
(b) Acetyl amide
(c) Chloroform and KOH
(d) para-Toluene sulphonyl chloride
(a) 42. The total number of amines among the following which
can be synthesized by Gabriel synthesis is:
(2021-02-24-Shift-II)
(a) (b) CH3CH2NH2
(b)
(c) (d)
43. 1.86 g of aniline completely reacts to form acetanilide.

10% of the product is lost during purification. Amount
of acetanilide obtained after purification (in g) is
________ × 10–2. (2021-02-24-Shift-II)
(c)
44. In gaseous triethylamine the “-C-N-C-“ bond angle is
________ degree. (2021-07-27-Shift-I)
45. The total number of reagents from those given below, that
can convert nitrobenzene into aniline is ______. (Integer
answer) (2021-08-31-Shift-I)
I. Sn – HCl II. Sn – NH4OH
III. Fe – HCl IV. Zn – HCl
(d)
V. H2 – Pd VI. H2 – Raney Nickel
AMINES 79
46. The conversion of propan-1-ol to n-butylamine 50. Decarboxylation of all six possible forms of
involves the sequential addition of reagents. The diaminobenzoic acids C6H3(NH2)2COOH yields three
correct sequential order of reagents is products A, B and C. Three acids give a product 'A’,
(JEE Main 2022) two acids gives a product ‘B’ and one acid give a
(a) (i) SOCl2 (ii) KCN (iii) H2/Ni, Na(Hg)/C2H5OH product ‘C’. The melting point of product ‘C’ is
(b) (i) HCI (ii) H2/Ni, Na(Hg)/C2H5OH (JEE Main 2022)
(c) (i) SOCl2 (ii) KCN (iii) CH3NH2 (a) 63oC (b) 90oC
(d) (i) HCI (ii) CH3NH2 (c) 104oC (d) 142oC
47. The reaction of R–CONH2 with bromine and KOH 51. Given below are two statements:
gives RNH2 as the end product. Which one of the Statement – I: In Hoffmann degradation reaction, the
following is the intermediate product formed in this migration of only an alkyl group takes place from
reaction? (JEE Main 2022) carbonyl carbon of the amide to the nitrogen atom.
(a) R–CONHBr (b) R–NH–Br Statement – II: The group is migrated in Hoffmann
(c) R–N=C=O (d) R–CONBr2 degradation reaction to electron deficient atom.
48. Which statement is NOT correct for p- In the light of the above statements, choose the most
toluenesulphonyl chloride? (JEE Main 2022) appropriate answer from the options given below:
(a) It is known as Hinsberg's reagent. (JEE Main 2022)
(b) It is used to distinguish primary and secondary (a) Both Statement I and Statement II are correct
amines. (b) Both Statement I and Statement II are incorrect
(c) On treatment with secondary amine, it leads to a (c) Statement I is correct but Statement II is incorrect
product, that is soluble in alkali. (d) Statement I is incorrect but Statement II is correct
(d) It doesn't react with tertiary amines. 52. Identify the major product formed in the following
49. The final product ‘C' in the following series of sequence of reactions: (JEE Main 2022)
reactions (JEE Main 2022)
(a)
(a) (b)
(b)
(c) (d)
53. A primary aliphatic amine on reaction with nitrous
(c) acid in cold (273 K) and there after raising temperature
of reaction mixture to room temperature (298 K), gives
a/an (JEE Main 2022)
(a) nitrile (b) alcohol
(d) (c) diazonium salt (d) secondary amine

AMINES 80
54. With respect to the following reaction, consider the 56. In Friedel-Crafts alkylation of aniline, one gets
given statements: (JEE Main 2022) (JEE Main 2022)
(a) alkylated product with ortho and para substitution.
(b) secondary amine after acidic treatment.
(c) an amide product.
(d) positively charged nitrogen at the benzene ring.
(A) o-Nitroaniline and p-nitroaniline are the 57. An organic compound 'A' on reaction with
predominant products NH3 followed by heating gives compound B. Which
(B) p-Nitroaniline and m-nitroaniline are the on further strong heating gives compound C
predominant products (C8H5NO2). Compound C on sequential reaction with
(C) HNO3 acts as an acid. ethanolic KOH, alkyl chloride and hydrolysis with
(D) H2SO4 acts as an acid. alkali gives a primary amine. The compound A is:
Choose the correct option. (JEE Main 2022)
(a) (A) and (C) are correct statements (a)
(b) (A) and (D) are correct statements
(c) (B) and (D) are correct statements
(d) (B) and (C) are correct statements
55.
(b)
Consider the above reactions, the product A and

product B respectively are (JEE Main 2022)
(c)
(d)
(a)
58. Given below are two statements: one is labelled as

Assertion (A) and the other is labelled as Reason (R).
(b) Assertion (A): Experimental reaction of CH3Cl with
aniline and anhydrous AlCl3 does not give o and p-
methylaniline.
Reason (R): The –NH2 group of aniline becomes
deactivating because of salt formation with anhydrous
AlCl3 and hence yields m-methyl aniline as the
product.
In the light of the above statements, choose the most
(c) appropriate answer from the options given below :
(JEE Main 2022)
(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)
(c) (A) is true, but (R) is false.
(d) (A) is false, but (R) is true.
AMINES 81
59. The correct sequential order of the reagents for the (JEE Main 2022)
given reaction is : (JEE Main 2022) (a) Both A and R are true and R is the correct
explanation of A
(b) Both A and R are true but R is NOT the correct
explanation of A
(c) A is true but R is false
(d) A is false but R is true
63. Which among the following represent reagent ‘A’?
(a) HNO2, Fe/H+, HNO2, KI, H2O/H+ (JEE Main 2022)
(b) HNO2, KI, Fe/H+, HNO2, H2O/warm
(c) HNO2, KI, HNO2, Fe/H+, H2O/H+
(d) HNO2, Fe/H+, KI, HNO2, H2O/warm
60. Match List I with List II
List I List II
A.Benzenesulphonyl
I. Test for primary amines
chloride
B. Hoffmann bromamide (a)
II. Anti Saytzeff
reaction
C. Carbylamine reaction III. Hinsberg reagent
IV. Known reaction of
D. Hoffmann orientation
Isocyanates.
Choose the correct answer from the options given (b)
(a) A-IV, B –III, C-II, D-I
(b) A-IV, B –II, C-I, D-III
(c) A-III, B –IV, C-I, D-II
(d) A-IV, B –III, C-I, D-II
(c)
61. An organic compound ‘A’ contains nitrogen and
chlorine. It dissolves readily in water to give a solution
that turns litmus red. Titration of compound ‘A’ with
standard base indicates that the molecular weight of
‘A’ is 131  2. When a sample of ‘A’ is treated with
aq. NaOH, a liquid separates which contains N but not (d)
Cl. Treatment of the obtained liquid with nitrous acid 64. The Hinsberg reagent is : (JEE Main 2022)
followed by phenol gives orange precipitate. The
compound ‘A’ is : (JEE Main 2022)
(a)
(a) (b)
(b)
(c) (d)
62. Given below are two statements : one is labelled as
Assertion A and the other is labelled as Reason R (c)
Assertion A: Aniline on nitration yields ortho, meta &
para nitro derivatives of aniline.
Reason R: Nitrating mixture is a strong acidic
mixture.
In the light of the above statements, choose
the correct answer from the options given below (d)
AMINES 82
65. Given below are two statements: 68. Match List I with List II
Statement I: Pure Aniline and other arylamines are List I List II
usually colourless. Reaction Reagents
Statement II: Arylamines get coloured on storage due (A) Hoffmann
I. Conc. KOH , 
to atmospheric reduction. Degradation
In the light of the above statements, choose the most (B) Clemenson
II. CHCl3 , NaOH / H 3 O 
appropriate answer from the options given below : Reduction
(JEE Main 2023) (C) Cannizaro reaction III. Br2 NaOH
(a) Both Statement I and Statement II are incorrect
(D) Reimer-Tiemann IV. Zn-Hg/HCl
(b) Both Statement I and Statement II are correct
(JEE Main 2023)
(c) Statement I is correct but Statement II is incorrect
(a) A  III , B  IV , C  II , D  I
(d) Statement I is incorrect but Statement II is correct
66. Choose the correct colour of the product for the (b) A  II , B  IV , C  I , D  III
following reaction. (c) A  III , B  IV , C  I , D  II
(d) A  II , B  I , C  III , D  IV
69. Reaction of propenamide with Br2 / KOH  aq 
produces: (JEE Main 2023)
(a) Ethylntrile (b) Propylamine
(c) Propanenitrile (d) Ethylamine
(JEE Main 2023) 70. Benzyl isocyanide can be obtained by:
(a) Yellow (b) White
(c) Red (d) Blue
67. Identify the product formed (A and E)
(JEE Main 2023)

(a) below : (JEE Main 2023)
(a) A and D (b) Only B
(c) A and B (d) B and C
71.
(b)
In the above conversion of compound (X) to product

(Y), the sequence of reagents to be used will be:
(c)
(JEE Main 2023)
(a) (i) Br2, Fe (ii) Fe, H+ (iii) LiAlH4
(b) (i) Br2(aq) (ii) LiAlH4 (iii) H3O+
(c) (i) Fe, H+ (ii) Br2(aq) (iii) HNO2 (iv) CuBr
(d) (i) Fe, H+ (ii) Br2(aq) (iii) HNO2 (iv) H3PO2
(d)
AMINES 83
72. 74. In the following reaction, ‘A’ is
(JEE Main 2023)
‘A’ Major product. (JEE Main 2023)
(a)
(a)
(b)
(b)
(c)
(d) (c)
73. An organic compound [ A] ( C4H11N) , shows optical
activity and gives N2 gas on treatment with HNO2. The
compound [ A] reacts with PhSO2Cl producing a
compound which is soluble in KOH. The structure of
A is: (JEE Main 2023)
(a) (d)
75.
(b)
Compound P is neutral, Q gives effervescence with

NaHCO3 while R reacts with Heinsberg’s reagent to
give solid soluble in NaOH. Compound P is
(JEE Main 2023)
(c)
(d)
AMINES 84
77. The product (P) formed from the following multistep

reaction is:
(a)
(JEE Main 2023)
(b)
(a)
(c) (b)
(d) (c)
76. Match List I with List II:
is reacted with reagents in List I to (d)

form products in List II 78. Isomeric amines with molecular formula C8H11N give
List I the following tests
List II (Product)
(Reagent) Isomer (P) ⇒ Can be prepared by Gabriel phthalimide
A. synthesis
Isomer (Q) ⇒ Reacts with Hinsberg's reagent to give
solid insoluble in NaOH
I. Isomer (R) ⇒ Reacts with HONO followed by β –
naphthol in NaOH to give red dye.
B. HBF4, ∆ Isomers (P), (Q) and (R) respectively are
II. (JEE Main 2023)
III. (a)
C. Cu, HCl
(b)
D. CuCN/KCN
IV.
Choose the correct answer from the options given (c)
(a) A-III, B-I, C-II, D-IV
(b) A-III, B-I, C-IV, D-II
(c) A-IV, B-III, C-II, D-I
(d) A-I, B-III, C-IV, D-II (d)
AMINES 85
79. o - Phenylenediamine 

HNO 2
 'X' 81. Consider the following sequence of reactions:
Major product
‘X’ is (JEE Main 2023)
The product ‘B’ is (JEE Main 2023)
(a)
(a)
(b)
(b)
(c)
(c)
(d)
(d)
80. The incorrect statement regarding the reaction given 82. Compound A from the following reaction sequence is:
below is
(JEE Main 2023)

(a) Benzoic Acid (b) Aniline
(c) Phenol (d) Salicylic acid
(JEE Main 2023)
83. At 27C , a solution containing 2.5 g of solute in 250.0
(a) The electrophile involved in the reaction is NO 
mL of solution exerts an osmotic pressure of 400 Pa.
(b) The product ‘B’ formed in the above reaction is p-
The molar mass of the solute is ____ g mol–1 (Nearest
nitroso compound at low temperature
integer)
(c) The reaction occurs at low temperature
(Given: R = 0.083 L bar K–1 mol–1)
(d) ‘B’ is N-nitroso ammonium compound
(JEE Main 2023)
84. Number of isomeric aromatic amines with molecular
formula C8H11N, which can be synthesized by Gabriel
Phthalimide synthesis is ________ (JEE Main 2023)
AMINES 86

Objective Questions I [Only one correct option] 7. C3H9N represents
1. Examine the following two structures for the anilinium ion (a) Primary amine (b) Secondary amine
and choose the correct statement from the ones given (c) Tertiary amine (d) All
below :
8. Which of the following reactions does not yield an amine
(a)
(b)
(c)
(d)
(a) II is not an acceptable canonical structure because
Na  C2 H 2 OH
carbonium ions are less stable than ammonium ions 9. CH3 CN  X
(b) II is not an acceptable canonical structure because it The compound X is
is non-aromatic
(a) CH3CONH2 (b) CH3CH2NH2
(c) II is not an acceptable canonical structure because
(c) C2H6 (d) CH3NHCH3
the nitrogen has 10 valence electrons
10. Which of the following on reduction with hydrogen and
(d) II is an acceptable canonical structure
Raney nickel gives benzylamine ?
2. The boiling points of amines and their corresponding
(a) Benzonitrile (b) Acetonitrile
alcohols and acids vary in the order :
(c) Propionitrile (d) Butyronitrile
(a) RCH2NH2 > RCOOH > RCH2OH
(b) RCH2NH2 > RCH2OH > RCOOH
(c) RCH2NH2 < RCOOH < RCH2OH
(d) RCH2NH2 < RCH2OH < RCOOH 11.
3. A solution of ethylamine :
(a) Phenyl isocyanide (b) Benzyl amine
(a) turns blue litmus red
(c) Benzyl chloride (d) None of these
(b) turns red litmus blue
12. Carbylamine test is performed in alc. KOH by heating a
(c) does not affect the litmus mixture of
(d) bleaches the litmus (a) chloroform and silver powder
4. Which has the highest pKb value ? (b) trihalogenated methane and a primary amine
(a) R3C – NH2 (b) R2NH (c) an alkyl halide and a primary amine
(c) RNH2 (d) NH3 (d) an alkyl cyanide and a primary amine
5. The hybridization of nitrogen atom in amines is : 13. Ethyl amine on heating with CS2 in presence of HgCl2 forms
(a) sp (b) sp2 (a) C2H5NCS (b) (C2H5)2S
(c) sp3 (d) dsp2 (c) (C2H5)2CS (d) C2H5(CS)2
6. Trimethylamine has : 14. Ethyl amine undergoes oxidation in the presence of
(a) planar geometry KMnO4 to form
(b) trigonal bipyramidal geometry (a) An acid (b) An alcohol
(c) pyramidal shape (c) An aldehyde (d) A nitrogen oxide
(d) octahedral geometry
AMINES 87
15. Azo dye test is given by 24. Match the List I with List II and pick the correct matching
(a) All amines from the codes given below :
(b) Only secondary amines List - I List - II
(c) Only primary aliphatic amines (Reactants) (Products)
(d) Only primary aromatic amines
ethanol
16. A mixture of 1°, 2° and 3° amines can be separated by A. RX+KCN   1.
Hinsberg’s reagent which is
(a) Benzoyl chloride B. RX+CH 3COOAg 
 2. RCN
(b) Acetyl chloride LiAlH
C. CH 3C  N 
4
 3. CH3COOR
(c) Benzensulphonyl chloride
(d) Benzyl chloride
D. 4. CH3CH2NH2
17. Which of the following reacts with hinsberg’s reagent
(Benzene sulphonyl chloride) to form the product soluble Hofmann 's
 
in KOH ? degradation
(a) Primary amine (b) Secondary amine Carbylamine

E. R  NH 2 
reaction
 5. RNC
(c) Tertiary amine (d) Quaternary amine CHCl3 / KOH
18. Which of the following amides will not undergo Hofmann Codes :
bromamide reaction ? (a) A–3, B–1, C–2, D–5, E–4
(a) CH3CONH2 (b) CH3CH2CONH2 (b) A–2, B–3, C–4, D–1, E–5
(c) C6H5CONH2 (d) CH3CONHCH3 (c) A–3, B–2, C–1, D–5, E–4
19. Acetamide is treated separately with the following (d) A–5, B–3, C–2, D–4, E–1
reagents. Which one of these would give methylamine ? 25. In the following reaction X is
(a) PCl5 (b) Sodalime
(c) NaOH + Br2 (d) Hot conc. H2SO4
20. Ethylamine reacts with nitrous acid to form :
(a) methyl alcohol (b) ethyl alcohol
(c) ethane (d) ethyl nitrite (a) benzoic acid (b) salicylic acid
21. The compound which on reaction with aqueous nitrous (c) aniline (d) phenol
acid at low temperature produces an oily nitrosoamine, is 26. Aniline in a set of reactions yielded a product D
(a) methylamine (b) ethylamine
(c) diethylamine (d) triethylamine
22. In the explosive amatol, TNT is mixed with
(a) Ammonium citrate (b) Ammonium nitrate
(c) Ammonium oxalate (d) Ammonium sulphate
23. H 2 / Pt
(A)  1° Amine The structure of the product (D) would be
(a) C 6 H 5 CH 2 OH (b) C 6 H 5 NHOH

(B) 
H 2 / Pt 2° Amine
(A) and (B) respectively are : (c) C 6 H 5 NHCH 2 CH 3 (d) C 6 H 5 CH 2 NH 2
(a) RNC, RNC (b) RCN, RCN

(c) RCN, RNC (d) RNC, RCN
AMINES 88
27. What is the end product in the sequence of following
(c) the hydrolysis of dialkyl cyanamide
reactions ?
(d) thermal decomposition of quaternary ammonium
HNO3 H 2SO 4 Sn / HCl hydroxide
C6 H 6 
333 K
 A 
B
34. When methyl iodide is treated with ammonia, the product
(a) Nitrobenzene (b) Aniline obtained is/are :
(c) Benzonitrile (d) Phenyl carbylamine (a) methylamine
Objective Questions II [One or more than one (b) dimethylamine
correct option] (c) trimethylamine
28. All the three amines (pri., sec. and tert.) react with : (d) quaternary ammonium salt
(a) HOH (b) RX 35. A positive carbylamine test is given by
(c) HCl (d) CH3COCl (a) N, N-dimethyl aniline
29. Which of the following amines will show positive (b) 2, 4-dimethyl aniline
Liebermann’s nitroso test : (c) N-methyl-o-methyl aniline
(d) p-methyl benzylamine
36. C4 H11 N HNO2  C4 H10 O (3° alcohol)

X
(a) (b)
hence, (X) will give :
(a) Carbylamine reaction
(b) Hoffmann’s mustard oil reaction
(c) (d) None of these (c) Diazonium salt (as the intermediate)
Reduction (d) Hoffmann’s bromamide reaction
30. (A) 
H Primary amine
37. p-chloroaniline and anilinium hydrochloride can be
The compound (A) may be : distinguished by
(a) alkyl isocyanide (b) alkyl cyanide (a) Sandmeyer reaction (b) NaHCO3
(c) acidamide (d) 1° nitroalkane (c) AgNO3 (d) Carbylamine test
31. A mixture of three amines (pri., sec. and tert.) can be 38. Reaction of RCONH2 with a mixture of Br2 and KOH gives
prepared by : RNH2 as the main product. The intermediates involved in
the reaction are :
(a) Hofmann’s bromamide reaction
(b) the reduction of nitroalkanes, cyanides and oximes (a) RCONHBr (b)
(c) (d) RCONBr2
(c) ammonolysis of alkylhalides.
39. Primary, secondary and tertiary amines can be
(d) ammonolysis of alcohols
distinguished by the action of :
32. Primary amines may be obtained by :
(a) CS2/HgCl2 (b) NaNO2/HCl
(a) the reduction of nitroalkanes
(c) CHCl3/KOH (d) X2/NaOH
(b) the reduction of alkyl isocyanide
40. A mixture of three amines can be separated into individual
(c) the decarboxylation of amino acids one by :
(d) the hydrolysis of alkyl isocyanate (a) Carbylamine reaction
33. Tertiary amines may be obtained by : (b) Hinsberg’s method
(a) Gabriel phthalimide synthesis (c) Fractional distillation method
(b) heating an alcoholic solution of ammonia with excess (d) Hofmann’s method
of RX
AMINES 89
Assertion Reason 46. Assertion (A) : In strongly acidic solutions, aniline
becomes more reactive towards electrophilic reagents.
(A) If both Assertion and Reason are correct
and Reason is the correct explanation of Reason (R) : The amino group being completely protonated
in strongly acidic solution, the lone pair of electrons on
Assertion. the nitrogen is no longer available for resonance.
(B) If both Assertion and Reason are true but (a) A (b) B
Reason is not the correct explanation of (c) C (d) D
Assertion. 47. Assertion (A) : In Hoffmann Bromamide reaction, the amine
(C) If Assertion is true but Reason is false. formed has one carbon atom less than the parent 1° amide.
(D) If Assertion is false but Reason is true. Reason (R) : N-methyl acetamide undergoes Hoffmann
Bromamide reaction.
41. Assertion (A) : n-Propylamine has a higher boiling point
than trimethylamine. (a) A (b) B
Reason (R) : Among n-propylamine molecules there is (c) C (d) D

hydrogen bonding, but there is no hydrogen bonding 48. Assertion (A) : Aniline hydrogen sulphate, on heating,
among trimethylamine molecules. forms a mixture of o-and p-amino benzene sulphonic acid.
(a) A (b) B Reason (R) : The sulphonic acid group is electron
(c) C (d) D withdrawing.
42. Assertion (A) : Me3N reacts with BF3 whereas Ph3N does (a) A (b) B
not. (c) C (d) D
Reason (R) : The electron pair on nitrogen atom in Ph3N is Match the Following
delocalised in the benzene ring and is not available to
Each question has two columns. Four options are
boron in BF3.
given representing matching of elements from Col-
(a) A (b) B
umn-I and ColumnII. Only one of these four options
(c) C (d) D
corresponds to a correct matching.For each ques-
43. Assertion (A) : In order to convert R–Cl to pure R–NH2,
tion, choose the option corresponding to the cor-
Gabriel pthalimide synthesis can be used.
rect matching.
Reason (R) : With proper choice of alkyl halides, pthalimide
synthesis can be used to prepare 1°, 2° or 3° amines. 49. Column - I Column - II
(a) A (b) B (A) Gabriel phthalimide reaction (p) C6H5CH2NH2
(c) C (d) D (B) Reduction product of nitriles (q) C6H5NH2
44. Assertion (A) : Benzene diazonium chloride does not give (C) Reaction product of amines with (r) C6H5NC
tests for nitrogen. alcoholic KOH and CHCl3
Reason (R) : N2 gas is lost during heating. (D) Reaction product of 1º amides (s) CH3CH2NH2
(a) A (b) B with Br2 + KOH
(c) C (d) D
45. Assertion (A) : p-Anisidine is weaker base than aniline.
Reason (R) : –OCH3 group in anisidine exerts –R effect.
(a) A (b) B
(c) C (d) D
AMINES 90
Subjective Type Questions 52. State the equations for the preparation of following
50. Write the structure of the major organic product expected compounds. (Equations need not to be balanced)
from the following reaction. (i) Chlorobenzene from aniline (in two steps).
(ii) n-propyl amine from ethyl chloride (in two steps).
53. How will you bring about the following conversion ?
“4-nitro aniline to 1,2,3-tribromo benzene.”
51. How would you convert ?
Fill in the Blanks
“Aniline to chlorobenzene.”
54. The high melting point and insolubility in organic solvents
of sulphanilic acid are due to its ............... structure.
55. Aniline is ........................ basic then cyclohexylamine
AMINES 91

3. The product(s) of the following reaction sequence is (are)
Objective Questions I
[Only one correct option]
1. In the following reaction (2007)
(2016)
The structure of the major product X is

(a) (b)
(a)
(b)
(c) (d)
(c) [One or more than one correct option]
4. Hydrogen bonding plays a cental role in the following
phenomena : (2014)
(a) Ice floats in water
(b) Higher Lewis basicity of primary amines than tertiary
amines in aqueous solutions.
(d) (c) Formic acid is more acidic than acetic acid.
(d) Dimerisation of acetic acid in benzene.
2. The major product of the reaction is (2015)
5. Correct option(s) for the following sequence of reactions
is(are) (2021)
(a) (b)
(c) (d)
(a) Q = KNO2, W = LiAlH4
(b) R = benzenamine, V = KCN
(c) Q = AgNO2, R = phenylmethanamine
(d) W = LiAlH4, V = AgCN
AMINES 92
Numeric Value Type Questions 9. Assertion (A) : In strongly acidic solutions, aniline becomes
more reactive towards electrophilic reagents.
6. Schemes 1 and 2 describe the conversion of P to Q and R to
Reason (R) :The amino group being completely protonated
S, respectively. Scheme 3 describes the synthesis of T from
in strongly acidic solution, the lone pair of electrons on the
Q and S. the total number of Br atoms in a molecule of T is nitrogen is no longer available for resonance. (2001)
________ (2019) (a) A (b) B
(c) C (d) D
10. Assertion (A) : Aniline on reaction with NaNO2/HCl at 0°C
followed by coupling with -naphthol gives a dark blue
coloured precipitate.
Reason (R) : The colour of the compound formed in the
reaction of aniline with NaNO2/HCl at 0°C followed by
coupling with -naphthol is due to the extended
conjugation. (2008)
(a) A (b) B
(c) C (d) D
7. Consider the reaction sequence from P to Q shown below. 11. How would you bring about the following conversion (in 3
The overall yield of the major product Q from P is 75%. steps) (2000)
What is the amount in grams of Q obtained from 9.3 mL of
Aniline 
 Benzylamine
P? (Use density of P = 1.00 g mL1 , Molar mass of C = 12. There is a solution of p-hydroxybenzoic acid and p-amino
12.0, H = 1.0, O = 16.0 and N = 14.0 g mol–1) (2020) benzoic acid. Discuss one method by which we can separate
them and also write down the confirmatory test of the
functional groups present. (2003)
13. Which of the following is more acidic and why ? (2004)
8. Reaction of x g of Sn with HCl quantitatively produced a

salt. Entire amount of the salt reacted with y g of
nitrobenzene in the presence of required amount of HCl to
produce 1.29 g of an organic salt (quantitatively).
14. Convert (2004)
(Use Molar masses (in g mol–1) of H, C, N, O, Cl and Sn as 1,
12, 14, 16, 35 and 119, respectively).
The value of y is ________. (2021)
Assertion Reason
(A) If both Assertion and Reason are correct and in not more than four steps. Also mention the temperature
Reason is the correct explanation of and reaction conditions.
Assertion.
(B) If both Assertion and Reason are true but 15.
Reason is not the correct explanation of
Assertion. (tertiary alcohol) + other products
(C) If Assertion is true but Reason is false. Find X and Y. Is Y optically active ? Write the intermediate
steps. (2005)
AMINES 93
2
16. The total number of sp hybridised carbon atoms in the Using the following Passage, solve Q. 18 and 19
major product P (a non-heterocycliccompound) of the PARAGRAPH
following reaction is _______. (2023) A trinitro compound, 1, 3,5 tris-(4-nitrophenyl) benzene,
17. The The reaction of 4-methyloct-ene (P, 2.52 g) with HBr in on complete reaction with an excess of Sn/HCl gives major
the presence of (C6H5CO)2O2 gives two isomeric bromides product, which on treatment with an excess of NaNO2/HCl
in a 9 : 1 ratio, with combined yield of 50%. Of these, the at 0°C provides P as the product. P, upon treatment with
entire amount of the primary alkyl bromide was reacted with excess of H2O at room temperature, gives the product Q.
an appropriate amount of diethylamine followed by Bromination of Q in aqueous medium furnishes the product
treatment with eq. K2CO3 to given a non-ionic product S in R. The compound P upon treatment with an excess of
100% yield. phenol under basic conditions gives the product S.
The mass (in mg) of S obtained is __. The molar mass difference between compounds Q and R
–1 is 474 mol–1 and between compounds P and S is 172.5 g
[Use molar mass (in g mol ) : H = 1, C = 12, N = 14, Br = 80]
(2023) mol–1. (2023)
18. The number of heteroatoms present in one molecule of R

is _____.
[Use: Molar mass (in g mol–1): H = 1, C = 12, N = 14, O = 16,
Br = 80, Cl = 35.5
Atoms other than C and H are considered as heteroatoms]
19. The total number of carbon atoms and heteroatoms
present in one molecule of S is _____.
[Use: Molar mass in g mol–1]: H = 1, C = 12, N = 14, O = 16,
Br = 80, Cl = 35.5
Atoms other than C and H are considered as heteroatoms
AMINES

BIOMOLECULES 94
BIOMOLECULES
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BIOMOLECULES
95
Chapter 08
BIOMOLECULES
1. INTRODUCTION 2.1.2 On the basis of Reducing Nature:
Complex organic compounds which govern the common activities

of the living organisms are called biomolecules. Living systems are
made up of various complex biomolecules like carbohydrates,
proteins, nucleic acids, lipids, etc. In addition, some simple molecules
like vitamins and mineral salts also play an important role in the
functions of organisms.
2. CARBOHYDRATES
Carbohydrates are primarily produced by plants and form a very
large group of naturally occurring organic compounds. Some 2.1.3 On the basis of Sweetness:
common examples are cane sugar, glucose, starch etc. Most of
them have a general formula, CxH2yOy and were considered as
hydrates of carbon from where the name carbohydrate was derived.
For example, the molecular formula of glucose (C6H12O6) fits into
this general formula, C6(H2O)6. But all the compounds which fit
into this formula may not be classified as carbohydrates. Rhamnose,
C6H12O5 is a carbohydrate but does not fit in this definition. NOTE
Chemically, the carbohydrates may be defined as optically active
Saccharide came from a Latin word Saccharum which means
polyhydroxy aldehydes or ketones or the compounds which
Sugar
produce such units on hydrolysis. Some of the carbohydrates,
which are sweet in taste, are also called sugars. The most common 2.1.4 On the basis of Number of Carbon atoms:
sugar, used in our homes is named as sucrose whereas the sugar Carbon General Aldehyde Ketone
present in milk is known as lactose. Atoms Term
2.1 Classification of Carbohydrates 3 Triose Aldotriose Ketoriose
Carbohydrates are classified on the basis of their behaviour on 4 Tetrose Aldotetrose Ketotetrose
hydrolysis. They have been broadly divided into following three 5 Pentose Aldopentose Ketopentose
groups: 6 Hexose Aldohexose Ketohexose
2.1.1 On the basis of Functional Group: 7 Heptose Aldoheptose Ketoheptose
2.1.5 On the basis of Number of Product of Hydrolysis:
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BIOMOLECULES
BIOMOLECULES 96
2.1.5.1 Monosaccharides 3.2 Reactions
A carbohydrate that cannot be hydrolysed further to give simpler (A) Oxidation

units of polyhydroxy aldehyde or ketone is called a
monosaccharide. Some common examples are glucose, fructose,
ribose, etc.
2.1.5.2 Oligosaccharides
Carbohydrates that yield two to ten monosaccharide units, on
hydrolysis, are called oligosaccharides. They are further classified
as disaccharides, trisaccharides, tetrasaccharides, etc., depending
upon the number of monosaccharides, they provide on hydrolysis.
Amongst these the most common are disaccharides. The two
monosaccharide units obtained on hydrolysis of a disaccharide
may be same or different. For example, sucrose on hydrolysis gives
one molecule each of glucose and fructose whereas maltose gives
two molecules of glucose only.
2.1.5.3 Polysaccharides
Carbohydrates which yield a large number of monosaccharide units
on hydrolysis are called polysaccharides. Some common examples
are starch, cellulose, glycogen, gums, etc.
3. GLUCOSE (ALDOHEXOSE)
Oxidation Reactions of Glucose
3.1 Preparation of Glucose
(B) Reduction
(A) From Sucrose (Cane Sugar)
If sucrose is boiled with dilute HCl or H2SO4 in alcoholic solution,
glucose and fructose are obtained in equal amounts.
H
C12 H 22 O11  H 2 O  C6 H12 O6  C6 H12 O 6
Sucrose Glu cose Fructose
(B) From Starch

Commercially, glucose is obtained by hydrolysis of starch by
boiling it with dilute H2SO4 at 393 K under pressure.

 C6 H10 O5 n  nH 2 O 
H
393K,2-3 atm
nC6 H12 O6
Starch or Cellulose Glucose
Reduction Reactions of Glucose

NOTE
Reduction with HI gives n-hexane which shows that all the 6
carbons of glucose are arranged in straight chain.
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BIOMOLECULES 97
(C) Oxime Formation follows. The letters ‘D’ or ‘L’ before the name of any compound
indicate the relative configuration of a particular stereoisomer.
This refers to their relation with a particular isomer of
glyceraldehyde. Glyceraldehyde contains one asymmetric carbon
atom and exists in two enantiomeric forms as illustrated.
Oxime Formation
(D) Cyanohydrin Formation
D-Glyceraldehyde L-Glyceraldehyde
All those compounds which can be chemically correlated to (+)
isomer of glyceraldehyde are said to have D-configuration whereas
those which can be correlated to (–) isomer of glyceraldehyde are
said to have L-configuration. For assigning the configuration of
monosaccharides, it is the lowest asymmetric carbon atom (as
shown below) which is compared. As in (+) glucose, –OH on the
Cyanohydrin Formation
lowest asymmetric carbon is on the right side which is comparable
NOTE to (+) glyceraldehyde, so it is assigned D-configuration. For this
Carbonyl C has become chiral so 2 products are obtained comparison, the structure is written in a way that most oxidised
which are diastereomers. carbon is at the top.
(E) Acetylation
3.4 Cyclic Structure of Glucose

Acetylation
Glucose is found to exist in two different crystalline forms which are
(F) Reaction with phenylhydrazine (formation of osazone) named as  and . The -form of glucose (m.p. 419 K) is obtained by
crystallisation from concentrated solution of glucose at 303 K while
the -form (m.p. 423 K) is obtained by crystallisation from hot and
saturated aqueous solution at 371 K.
Both -D-glucose and -D-glucose undergo mutarotation in
aqueous solution. Although the crystalline forms of - and -D
(+)-glucose are quite stable in aqueous solution but each form
slowly changes into an equilibrium mixture of both. This is evident
Reaction with phenylhydrazine from the fact that the specific rotation of a freshly prepared
3.3 Configuration in Monosaccharides aqueous solution of -D(+)-glucose falls gradually from +111° to
+52.5° with time and that of -D(+)-glucose increases from +19.2°
Glucose is correctly named as D(+)-glucose. ‘D’ before the name
to 52.5°. Thus,
of glucose represents the configuration whereas ‘(+)’ represents
dextrorotatory nature of the molecule. It may be remembered that
‘D’ and ‘L’ have no relation with the optical activity of the
compound. The meaning of D– and L– notations is given as
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BIOMOLECULES 98
3.4.1 How to draw a Haworth Projection
A ring of 6 atoms (5 ‘C’ and 1 ‘O’) is drawn in which ‘O’ atom is
placed at right hand top corner as shown below
Carbon atom at the right hand side of oxygen is given number 1.

This spontaneous change in specific rotation of an optically active Then other carbon atoms are given numbers 2, 3 ......... in a clockwise
compound with time, to an equilibrium value, is called mutarotation. fashion. Groups attached to a carbon in Fischer projection lying
It was found that glucose forms a six-membered ring in which – on the right hand side of that carbon are placed below the ring
OH at C-5 is involved in ring formation. This explains the absence and on the left hand side are placed above the ring. But CH2OH
of –CHO group and also existence of glucose in two forms as group of carbon 5 is placed above the plane of ring by convention
shown below. These two cyclic forms exist in equilibrium with
open chain structure.
Cyclic and open chain structure of Glucose

The two cyclic hemiacetal forms of glucose differ only in the
Cyclic and Haworth Projection of a-D-Glucose
configuration of the hydroxyl group at C1, called anomeric carbon
(the aldehyde carbon before cyclisation). Such isomers, i.e., - 4. FRUCTOSE (KETOHEXOSE)
form and -form, are called anomers. The six membered cyclic
structure of glucose is called pyranose structure (– or –), in Fructose also has the molecular formula C6H12O6 and on the basis
analogy with pyran. Pyran is a cyclic organic compound with one of its reactions it was found to contain a ketonic functional group
oxygen atom and five carbon atoms in the ring. The cyclic structure at carbon number 2 and six carbons in straight chain as in the case
of glucose is more correctly represented by Haworth structure. of glucose. It belongs to D-series and is a laevorotatory compound.
It is appropriately written as D-(–)-fructose. Its open chain structure
is as shown
Fructose
It also exists in two cyclic forms which are obtained by the addition
 \ 
Haworth Structure of Glucose of –OH at C5 to the  / C  O 
 
group. The ring, thus formed is a
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five membered ring and is named as furanose with analogy to the 5. DISACCHARIDES
compound furan. Furan is a five membered cyclic compound with
one oxygen and four carbon atoms. The two monosaccharides are joined together by an oxide linkage
formed by the loss of a water molecule. Such a linkage between
two monosaccharide units through oxygen atom is called
glycosidic linkage.
5.1 Sucrose
One of the common disaccharides is sucrose which on hydrolysis
gives equimolar mixture of D-(+)-glucose and
D-(–)-fructose.
These two monosaccharides are held together by a glycosidic

Cyclic Structure of Fructose linkage between C1 of -glucose and C2 of
-fructose. Since the reducing groups of glucose and fructose
The cyclic structures of two anomers of fructose are represented
are involved in glycosidic bond formation, sucrose is a non
by Haworth structures as given.
reducing sugar.
Haworth Structure of Fructose

Comparison of Glucose and Fructose
S.No. Property Glucose Fructose
(i) Molecular formula C6H12O6 C6H12O6 Sucrose
(ii) Nature Polyhydroxy Polyhydroxy Sucrose is a dextrorotaty compound and its hydrolysis produces
aldehyde ketone an equimolar solution of glucose and fructose. This solution is
(iii) Melting point 146°C 102°C laevorotaty because laevo rotation of fructose is greater than
dextro rotation of glucose.
(iv) Optical nature Dextro rotatory Laevo rotatory
Thus, hydrolysis of sucrose brings about a change in the sign of
(v) Tollen’s reagent Silver mirror Silver mirror
rotation, from dextro (+) to laevo (–) and the product is named as invert
(vi) Fehling’s solution Red ppt Red ppt sugar and this phenomenon is called as inversion of sugar.
(vii) Molisch test Violet colour Violet colour 5.2 Maltose
(viii) Phenyl hydrazine Forms osazone Forms osazone Another disaccharide, maltose is composed of two -D-glucose
(ix) Oxidation by Saccharic acid Mixture of units in which C1 of one glucose (I) is linked to C4 of another
conc. HNO3 glycolic acid, glucose unit (II). The free aldehyde group can be produced at C1
of second glucose in solution and it shows reducing properties
Tetaric acid and
so it is a reducing sugar.
Trihydroxy
Gluteric acid
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Maltose
5.3 Lactose
It is more commonly known as milk sugar since this disaccharide
is found in milk. It is composed of -D-galactose and -D-glucose.
Fischer projections of -D-Glucose and -D-Galactose are drawn
below :
We can see that the configurations of all the carbon atoms in -D-
Glucose and -D-Galactose is same except at C-4. Such stereoisomers
which differ in the configuration at only one carbon other than anomeric
carbon are called as epimers and that C atom is called as epimeric
carbon atom. Hence we can say that -D-Glucose and -D-Galactose
are epimers and C-4 is epimeric carbon atom. In lactose, the linkage is
between C1 of galactose and C4 of glucose. Hence it is also a reducing
sugar.
-1,4’-glycosidic linkage
Lactose
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6. POLYSACCHARIDES is found in cereals, roots, tubers and some vegetables. It is a

polymer of -glucose and consists of two components - Amylose
Polysaccharides contain a large number of monosaccharide units and Amylopectin. Amylose is water soluble component which
joined together by glycosidic linkages. They mainly act as the constitutes about 15-20% of starch. Chemically amylose is a long
food storage or structural materials. unbranched chain with 200-1000 -D-(+)-glucose units held by
6.1 Starch C1-C4 glycosidic linkage. Amylopectin is insoluble in water and
constitutes about 80-85% of starch. It is a branched chain polymer
Starch is the main storage polysaccharide of plants. It is the most
of -D-glucose units in which chain is formed by C1-C4 glycosidic
important dietary source for human beings. High content of starch
linkage whereas branching occurs by C1-C6 glycosidic linkage.
Amylose and Amylopectin

6.2 Cellulose
Cellulose occurs exclusively in plants and it is the most abundant
organic substance in plant kingdom. It is a predominant
constituent of cell wall of plant cells. Cellulose is a straight chain
polysaccharide composed only of  -D-glucose units which are
joined by glycosidic linkage between C1 of one glucose unit and
C4 of the next glucose unit.
Cellulose
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6.3 Glycogen NOTE
The carbohydrates are stored in animal body as glycogen. It is
 All the carbohydrates containing CHO group or -
also known as animal starch because its structure is similar to
Hydroxy ketonic group or hemiacetal group are reducing
amylopectin and is rather more highly branched. It is present in
sugars.
liver, muscles and brain. When the body needs glucose, enzymes
break the glycogen down to glucose. Glycogen is also found in  All reducing sugars show the phenomenon of mutarotation.
yeast and fungi.
Carbohydrates - types and characteristics
Carbohydrates Type Reducing/ Units Linkage

Non Reducing
Glucose Monosaccharide Reducing Glucose —
Fructose Monosaccharide Reducing Fructose —
Sucrose Disaccharide Non Reduing -D-Glucose C1 of Glucose
and -D-Fructose and C2 of Fructose
Lactose Disaccharide Reducing -D-Glucose  1, 4’ glycosidic linkage
and -D-Galactose
Maltose Disaccharide Reducing Both are D-Glucose  1, 4’glycosidic linkage
Starch Polysaccharide Non Reducing Amylose + Amylopectin  1, 4’and  1, 6’glycosidic
linkages
Glycogen Polysccharide Non Reducing Amylopectin  1, 4’and  1, 4’glycosidic
Cellulose Polysccharide Non Reducing -D-Glucose  1, 4’glycosidic linkage
7. PROTEINS All -amino acids have trivial names, which usually reflect the
property of that compound or its source. Glycine is so named
The word protein is derived from Greek word, “proteios” which since it has sweet taste (in Greek glykos means sweet) and tyrosine
means primary or of prime importance. All proteins are polymers
was first obtained from cheese (in Greek, tyros means cheese.)
of -amino acids.
7.2 Natural Amino Acids
7.1 Amino Acids
Amino acids are generally represented by a three letter symbol,
Amino acids contain amino (–NH2) and carboxyl (–COOH) sometimes one letter symbol is also used. Structures of some
functional groups. Depending upon the relative position of amino commonly occurring amino acids along with their 3-letter and 1-
group with respect to carboxyl group, the amino acids can be letter symbols are given in Table 2.4.
classified as , , ,  and so on. Only -amino acids are obtained
on hydrolysis of proteins. They may contain other functional
groups also.
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Natural Amino Acids

S.No. Nature of the Characteristic Feature Three letter One letter
Amino Acids of side chain. R symbol of code
(i) Glycine (N) H Gly G
(ii) Alanine (N) — CH3 Ala A
(iii) Valine * (N) (H3C)2CH2— Val V
(iv) Leucine* (N) (H3C)2 CH—CH2— Leu L
H3C — CH2 — CH—
(v) Isoleucine * (N) | Ile I
CH3
HN  C — NH —  CH 2 3 —
(vi) Arginine * (B) | Arg R
NH 2
(vii) Lysine * (B) H2N — (CH2)4— Lys K

(viii) Glutamic acid (A) HOOC — CH2 — CH2— Glu E
(ix) Aspartic acid (A) HOOC — CH2 — Asp D
O

(x) Glutamine (N) Gln Q
H 2 N — C — CH 2 — CH 2 —
O

(xi) Asparagine (A) Asn N
H 2 N — C — CH 2 —
(xii) Threonine * (N) H3C —CHOH— Thr T
(xiii) Serine (N) HO — CH2— Ser S
(xiv) Cysteine (N) HS— CH2— Cys C
(xv) Methionine * (N) H3C—S—CH2—CH2— Met M
(xvi) Phenylalanine * (N) C6H5—CH2— Phe F
(xvii) Tyrosine (N) (p)HO — C6H4—CH2— Tyr Y
(xviii) Tryptophan * (N) Trp W
(xix) Histidine * (B) His H
(xx) Proline (N) Pro P
NOTE
N = Neutral (No. of carboxylic group = No.of amino group)  *Essential amino acids.
B = Basic (No. of carboxylic group < No.of amino group)
A = Acidic (No. of carboxylic group > No.of amino group)  Arginine has highest isoelectric point i.e. 10.8.
 Cysteine has lowest isoelectric point i.e. 5.1.
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7.3 Classification of Amino Acids
Amino acids are classified as acidic, basic or neutral depending
upon the relative number of amino and carboxyl groups in their
molecule.
The amino acids, which can be synthesised in the body, are known
as non-essential amino acids. On the other hand, those which
cannot be synthesised in the body and must be obtained through
diet, are known as essential amino acids.
7.4 Properties of Amino Acids
If an amino acid has an ionizable side chain, its pI is the average of
Amino acids are usually colourless, crystalline solids. These are the pKa values of the similarly ionizing groups (positive ionizing
water-soluble, high melting solids and behave like salts rather to uncharged, or uncharged ionizing to negative). For example,
than simple amines or carboxylic acids. This behaviour is due to
the pI of lysine is the average of the pKa values of the two groups
the presence of both acidic (carboxyl group) and basic (amino
that are positively charged in their acidic form and uncharged in
group) groups in the same molecule.
their basic form. The pI of glutamate, on the other hand, is the
average of the pKa values of the two groups that are uncharged in
their acidic form and negatively charged in their basic form.
In aqueous solution, the carboxyl group can lose a proton and

amino group can accept a proton, giving rise to a dipolar ion
known as zwitter ion. This is neutral but contains both positive
and negative charges. In zwitter ionic form, amino acids show
amphoteric behaviour as they react both with acids and bases.
Except glycine, all other naturally occurring -amino acids are
optically active, since the -carbon atom is asymmetric. These
exist both in ‘D’ and ‘L’ forms. Most naturally occurring amino
acids have L-configuration. L-Amino acids are represented by
writing the –NH2 group on left hand side.
7.4.1 Isoelectric Point
The isoelectric point (pI) of an amino acid is the pH at which it
has no net charge. In other words, it is the pH at which the amount
of negative charge on an amino acid exactly balances the amount
of positive charge.
pI (isoelectric point) = pH at which there is no net charge
The pI of an amino acid that does not have an ionizable side
chain–such as alanine–is midway between its two pKa values. 7.5 Structure of Proteins - Peptide Bond
This is because at pH = 2.34, half the molecules have a negatively Proteins are the polymers of -amino acids and they are connected
charged carboxyl group and half have an uncharged carboxyl to each other by peptide bond or peptide linkage. Chemically,
group, and at pH = 9.69, half the molecules have a positively peptide linkage is an amide formed between –COOH group and –
charged amino group and half have an uncharged amino group.
NH2 group.
As the pH increases from 2.34, the carboxyl group of more
molecules becomes negatively charged; as the pH decreases from
9.69, the amino group of more molecules becomes positively
charged. Therefore at the average of the two pKa values, the
number of negatively charged groups equals the number of
positively charged groups.
Peptide linkage in proteins
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The reaction between two molecules of similar or different amino In -structure all peptide chains are stretched out to nearly
acids, proceeds through the combination of the amino group of maximum extension and then laid side by side which are held
one molecule with the carboxyl group of the other. This results in together by intermolecular hydrogen bonds.
the elimination of a water molecule and formation of a peptide
bond –CO–NH–.
7.6 Classification of Proteins
Proteins can be classified into two types on the basis of their
molecular shape.
(A) Fibrous Proteins
When the polypeptide chains run parallel and are held together
by hydrogen and disulphide bonds, then fibre- like structure is
formed. Such proteins are generally insoluble in water.
Some common examples are keratin (present in hair, wool, silk)
and myosin (present in muscles), etc.
(B) Globular Proteins
This structure results when the chains of polypeptides coil around
to give a spherical shape. These are usually soluble in water.
Insulin and albumins are the common examples of globular
proteins. Structure and shape of proteins can be studied at four
different levels, i.e., primary, secondary, tertiary and quaternary.
(i) Primary Structure
Proteins may have one or more polypeptide chains. Each
polypeptide in a protein has amino acids linked with each other in
a specific sequence and it is this sequence of amino acids that is
- Pleated sheet structure of -Helix structure of
said to be the primary structure of that protein. Any change in
proteins protein
this primary structure i.e., the sequence of amino acids creates a
different protein. (iii) Tertiary Structure
(ii) Secondary Structure The tertiary structure of proteins represents overall folding of the
polypeptide chains i.e., further folding of the secondary structure.
The secondary structure of protein refers to the shape in which a
It gives rise to two major molecular shapes viz. fibrous and
long polypeptide chain can exist. They are found to exist in two
globular. The main forces which stabilise the 2° and 3° structures
different types of structures viz. -helix and -pleated sheet
of proteins are hydrogen bonds, disulphide linkages, van der
structure. These structures arise due to the regular folding of the
Waals and electrostatic forces of attraction.
backbone of the polypeptide chain due to hydrogen bonding
between C = O and –NH– groups of the peptide bond.
-Helix is one of the most common ways in which a polypeptide
chain forms all possible hydrogen bonds by twisting into a right
handed screw (helix) with the –NH group of each amino acid
residue hydrogen bonded to the C = O of an adjacent turn of the
helix.
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(iv) Quaternary Structure 8.1 Chemical Composition of Nucleic Acids
Some of the proteins are composed of two or more polypeptide Complete hydrolysis of DNA (or RNA) yields a pentose sugar,
chains referred to as sub-units. Subunits with respect to each phosphoric acid and nitrogen containing heterocyclic compounds
other is known as quaternary structure. (called bases). In DNA molecules, the sugar moiety is -D-2-
deoxyribose whereas in RNA molecule, it is -D-ribose.
(a) (b)
(a) -D- ribose (b) -D-2deoxyribose
DNA contains four bases viz. adenine (A), guanine (G), cytosine
(C) and thymine (T). RNA also contains four bases, the first three
bases are same as in DNA but the fourth one is uracil (U).
Primary, Secondary, Tertiary, Quaternary Structure of

Protein
7.7 Denaturation of Proteins
Protein found in a biological system with a unique three-
dimensional structure and biological activity is called a native
protein. When a protein in its native form, is subjected to physical
change like change in temperature or chemical change like change
in pH, the hydrogen bonds are disturbed. Due to this, globules
unfold and helix get uncoiled and protein loses its biological
activity. This is called denaturation of protein. The coagulation Bases in DNA and RNA
of egg white on boiling is a common example of denaturation.
8.2 Structure of Nucleic Acids
Another example is curdling of milk which is caused due to the
A unit formed by the attachment of a base to 1’ position of sugar is
formation of lactic acid by the bacteria present in milk. known as nucleoside. In nucleosides, the sugar carbons are
8. NUCLEIC ACIDS numbered as 1’, 2’, 3’, etc. In order to distinguish these from the
bases. When nucleoside is linked to phosphoric acid at 5’-position
Every generation of each and every species resembles its ancestors of sugar moiety, we get a nucleotide.
in many ways. How are these characteristics transmitted from one
generation to the next ? It has been observed that nucleus of a living
cell is responsible for this transmission of inherent characters, also
called heredity. The particles in nucleus of the cell, responsible for
heredity, are called chromosomes which are made up of proteins and
another type of biomolecules called nucleic acids. These are mainly
of two types, the deoxyribonucleic acid (DNA) and ribonucleic acid
(RNA). Since nucleic acids are long chain polymers of nucleotides,
Structure of (a) a nucleoside and (b) a nucleotide
so they are also called polynucleotides.
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Nucleotides are joined together by phosphodiester linkage 8.3 DNA vs RNA

between 5’ and 3’ carbon atoms of the pentose sugar. A simplified DNA vs RNA
version of nucleic acid chain is as shown below
S.No. Deoxyribonucleic Ribonucleic
Acid (DNA) Acid (RNA)
(i) DNA occurs in the RNA occurs in the
nucleus of the cell. cytoplasm of the cell.
Information regarding the sequence of nucleotides in the chain of (ii) The sugar present in The sugar present in
a nucleic acid is called its primary structure. Nucleic acids have a
DNA is RNA is D(-) ribose
secondary structure also. James Watson and Francis Crick gave a
double strand helix structure for DNA. Two nucleic acid chains D-(–)-2-deoxyribose.
are wound about each other and held together by hydrogen bonds (iii) DNA contains cytosine RNA contains cytosine
between pairs of bases. The two strands are complementary to
and thymine as pyrimidine and uracil as pyrimidine
each other because the hydrogen bonds are formed between
specific pairs of bases. Adenine forms hydrogen bonds with bases and guanine and bases and guanine and
thymine whereas cytosine forms hydrogen bonds with guanine. adenine as purine bases. adenine as purine bases.
In secondary structure of RNA, helices are present which are (iv) DNA has double-stranded RNA has single stranded
only single stranded. Sometimes they fold back on themselves to -helix structure. -helix structure.
form a double helix structure. RNA molecules are of three types
(v) DNA undergoes replication. RNA usually does not
and they perform different functions. They are named as
messenger RNA (m-RNA), ribosomal RNA (r-RNA) and transfer undergo replication
RNA (t-RNA). (vi) DNA controls the RNA controls the
transmission of synthesis of proteins.
hereditary effects.
8.4 Biological Functions of Nucleic Acids
DNA is the chemical basis of heredity and may be regarded as the
reserve of genetic information. DNA is exclusively responsible
for maintaining the identity of different species of organisms over
millions of years. A DNA molecule is capable of self duplication
during cell division and identical DNA strands are transferred to
daughter cells. Another important function of nucleic acids is the
protein synthesis in the cell. Actually, the proteins are synthesised
by various RNA molecules in the cell but the message for the
synthesis of a particular protein is present in DNA.
9. ENZYMES
Enzymes are biological catalysts. Chemically all enzymes are
globular proteins. Some important enzymes and their functions
are given
Double strand helix structure for DNA
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Enzymes 10. VITAMINS
S.No. Enzyme Reaction Catalysed
They are generally regarded as organic compounds required in
(i) Invertase Sucrose  Glucose + the diet in small amounts to perform specific biological functions
or sucrase Fructose for normal maintenance of optimum growth and health of the
(ii) Maltase Maltose  2 Glucose organism. Vitamins are designated by alphabets A, B, C, D, etc.
Some of them are further named as sub-groups e.g. B1, B2 , B6, B12,
(iii) Lactase Lactose  Glucose +
etc. Excess of vitamins is also harmful and vitamin pills should
Galactose not be taken without the advice of doctor.
(iv) -Amylase Starch  n × Glucose 10.1 Classification of Vitamins
(v) Emulsin Cellulose  n × Glucose Vitamins are classified into two groups depending upon their
(vi) Urease NH2CONH2  CO2 + 2NH3 solubility in water or fat.
(vii) Carbonic H2CO3  CO2 + H2O (i)Fat soluble vitamins: Vitamins which are soluble in fat and oils
anhydrase but insoluble in water are kept in this group. These are vitamins
(viii) Pepsin Proteins   - Amino acids A, D, E and K. They are stored in liver and adipose (fat storing)
tissues.
(ix) Trypsin Proteins   - Amino acids
(ii) Water soluble vitamins: B group vitamins and vitamin C are
(x) Nucleases DNA or RNA  Nucleotides soluble in water so they are grouped together. Water soluble
(xi) DNA Deoxynucleotide  DNA vitamins must be supplied regularly in diet because they are
polymerase triphosphates readily excreted in urine and cannot be stored
(except vitamin B12) in our body.
(xii) RNA Ribonucleotide  RNA
polymerase triphosphates
Some important Vitamins, their Sources and their Deficiency Diseases

S.No. Vitamin Sources Deficiency diseases
(i) Vitamin- A (Retinol Milk, cod liver oil, butter, carrots, Night blindness, xerophthalmia (i.e, hardening
or eye vitamin) green leaves, tomatoes, eggs, etc. of cornea of eye) and xerosis.
(ii) Vitamin-B1 Pulses, nuts, green vegetables, Beriberi (a disease of nervous system) and
Polished rice, yeast and egg yolk. loss apetite.
(iii) Vitamin-B2 or Milk, meat, green vegetables Inflammation of tongue or dark red tongue
Riboflavin or Lactoflavin and yeast. (glossitis), and cheilosis (cracking or fissuring
the lips and corners of the mouth)
(iv) Vitmain-B6 or Pyridoxine Rice, bran, yeast, meat, fish, egg, Specific dermatitlis called acrodynia, pellagra
or Adermine yolk, maize, spinach and lettuce. (shrivelled skin anaemia and convulsions.
(v) Vitamin- B12 Milk, liver, kidney and eggs. Inflammation of tongue, mouth etc. and
pernicious anaemia
(vi) Vitamin-C Citrous fruits, amla, (oranges, Scurvy and brittleness of bones, swelling
or L- Ascorbic acid lemons), sprouted pulses, and bleeding of gums and lossening of teeth.
geminated.
(vii) Vitamin D Fish liver oil, cod liver oil, milk Rickets (softening and bending of bones) in
(sunshine vitamin) and egss. children, controls Ca and P metabolism.
(viii) Vitamin-E Eggs, milk, fish, wheat germs, oil Sterility (loss of sexual power and
cotton seed oil etc. reproduction)
(ix) Vitamin-K Cabbage, alfalfa, spinach and Haemorrhage and increased
carrot tops. blood clotting time.
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11. LIPIDS 12.2 Peptide Hormones

Peptide Hormones
Biological substances which are insoluble in water are known as
lipids. This characteristic physical property of lipids makes them S. Organ
very different from other biomolecules like carbohydrates, No. Name of Functions
proteins, and nucleic acids. Lipids have extremely varied structure. Secretion
Lipids play important roles in many cellular processes like energy (i) Oxytocin Posterior Control the contraction of
storage, structural support, protection, and communication.
pituitary the uterus after child birth
Common lipid groups are waxes, steroids, triglycerides, and
and releases milk from the
phospholipids.
mammary glands
11.1 Function of Lipids
(ii) Vasopressin Posterior Control the reabsorption
The function of lipids are very diverse.
pituitary of water in the kidney.
(i) Some lipids are used to store energy.
gland
(ii) In addition to serving as energy sources, some lipids
accumulate in tissues around to act as insulation and (iii) Angiotensin II Blood Potent vasoconstrictor i.e.
protection. Plasma contracts the blood vessels
(iii) Other lipids carry chemical messages and help regulate cell of with high blood pressure.
activity from one part of the body to another. persons
12. HORMONES (iv) Insulin Pancreas Controls the metabolism of
glucose, maintains glucose
Hormones are biomolecules which are produced in the ductless
(endocrine) glands and are carried to different parts of the body level in the blood.
by the blood stream where they control various metabolic 12.3 Amine Hormones
processes. These are required in minute quantites and unlike fats Amine Hormones
and carbohydrates these are not stored in the body but are
S. Organ
continuously produced.
No. Name of Functions
12.1 Steroidal Hormones Secretion
Steroidal Hormones
(i) Sex hormones Control the development
S. Organ
(a) Androgens Testes and normal functioning of
No. Name of Functions
Secretion (Testosterone) Androsterone and male sex
(i) Adrenaline or Adrenal It is an amine compound and organs.
Epinephrine medulla was the first hormone to be (b) Estrogens Ovary Control the development
isolated. Prepares animals and
(Estrone, and normal functioning of
humans for emergency in Estradiol,Estriol) female sex organs.
many ways by raising the
(c) Gestogens Corpus Control the development
pulse rate, blood pressure
(Progesterone) luteum and maintenance of
etc. stimulates the breakdown pregnancy
of liver glycogen into blood
glucose and fats into fatty
(ii) Adrenal corex Adrenal Regulate the metabolism
acids during emergency.
These properties make hormones or cortex of fats, proteins and
adrenaline as one of the most corticoids carbohydrates: control the
valuable drugs used in (Cortisone, balance of water and
medicine. Corticosterone minerals in the body.
(ii) Thyroxine Thyroid Controls metabolism of
Aldosterone
gland carbohydrates, lipids and
etc.)
proteins.
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13. TEST FOR BIOMOLECULES group condense with resorcinol to form a chromogen having
cherry-red color.
13.1 Tests for Carbohydrates
13.1.5 Iodine Test
13.1.1 Molisch Test
This test is only given by starch. Starch reacts with iodine
Molisch test is used for detection of all types of carbohydrates,
solution forms complex blue colour solution. On heating the blue
i.e. monosaccharides, disaccharides and polysaccharides.
colour disappears and on cooling the blue colour reappears.
Molisch reagent (1% alcoholic solution of -naphthol) is added
Note:
to the aqueous solution of a carbohydrate followed by conc.
H2SO4 along the sides of the test tube. A violet ring is formed at The appearance of blue colour solution confirms the presence of
starch.
the junction of the two layers.
13.2 Tests for Proteins
13.1.2 Benedict’s Test
13.2.1 Biuret Test
Benedict’s solution contains copper sulfate that provides cupric
ions, Sodium carbonate that makes solution alkaline, and Sodium An alkaline solution of a protein when treated with a few drops of
Citrate that provides citrate ions. 1% CuSO4 solution, produces a violet colouration. The colour is
It is a test for reducing sugars. Carbohydrates having free due to the formation of a coordination complex of Cu+2 with
functional group, that is not involved in a glycosidic bond, give
this test positive. All monosaccharides and reducing and –NH– groups of the peptide linkages.
disaccharides give positive Benedict’s test. This test is negative
for polysaccharides. 13.2.2 Xanthoproteic Test
In the presence of an alkali, reducing sugars undergo When a protein is treated with conc. HNO3 a yellow colour is
tautomerization to form enediols. These enediols reduce the cupric produced. This test is given by a protein which consists of -
ions (Cu+2) to form cuprous ions (Cu+). The cuprous ions from amino acids containing a benzene ring such as tyrosine,
cuprous hydroxide. Upon heating, it is converted to cuprous oxide phenylalanine etc. and the yellow colour is due to the nitration of
that forms precipitates. The citrate ions present in the reagent the benzene ring. An important example of this test is that when
release the cuprous ions slowly for reduction and prevent the conc. HNO3 is spilled on your hands, the skin turns yellow due to
formation of Cu(OH)2 until the oxidation-reduction process is nitration of benzene ring of the amino acids of the proteins present
completed. in your skin.
13.1.3 Barfoed’s Test 13.2.3 Millon’s Test
Barfoed’s reagent contains copper acetate in glacial acetic acid. It Millon’s reagent is a solution of mercurous nitrate and mercuric
is a differentiating test to distinguish between monosaccharides nitrate in nitric acid containing little nitrous acid. When Millon’s
and disaccharides. Barfoed’s test is also based on the reducing reagent is added to aqueous solution of protein, a white ppt. is
ability of sugar. However, sucrose also gives this test positive as formed. This test is given by all proteins containing phenolic -
it undergoes hydrolysis in the presence of an acid. amino acids i.e. tyrosine. As such gelatin which does not contain
Monosaccharides give early positive test while the disaccharides phenolic -amino acids does not give this test.
give late positive test.
13.2.4 Ninhydrin Test
Formation of red precipitates after the initial first 5 minutes
When proteins are boiled with a dilute aqueous solution of
indicates the presence of a monosaccharide. If precipitates are
ninhydrin (2, 2-dihydroxyindane-1,3-dione), a blue-violet colour
formed after 15 minutes, a disaccharide is present in the test
is produced. This test is actually given by all
solution.
-amino acids. Since proteins on hydrolysis give -amino acids,
13.1.4 Seliwanoff’s Test therefore, proteins and peptides also give this test.
Seliwanoff’s reagent contains water, resorcinol and concentrated
HCl This test is used to detect monosaccharides with a ketonic
functional group. It is widely used to differentiate fructose, a keto
sugar, from glucose and galactose. This test involves the formation
of furfural derivatives by monosaccharides with hydrochloric acid.
The furfural derivatives formed by a sugar with ketonic functional
SCAN CODE
BIOMOLECULES
BIOMOLECULES 111
Summary
Reactions of Glucose
Classification of Amino Acids
SCAN CODE
BIOMOLECULES
BIOMOLECULES 112
Structure of Proteins
Chemical Composition of Nucleic Acids
Classification of Vitamins
SCAN CODE
BIOMOLECULES
BIOMOLECULES 113

Carbohydrates 10. What is the structure of L-Glucose ?
1. A disaccharide on hydrolysis gives
(a) Two molecules of the same monosaccharide
(b) One molecule each of two different monosaccharides
(c) Three molecules of the same monosaccharide (a) (b)
(d) Two molecules of the same or one molecule each of the

two different monosaccharides.
2. Glucose is a/an
(a) Aldohexose (b) Aldopentose
(c) Aldotetrose (d) Ketohexose
(c) (d) None of these
3. In polysaccharides, the linkage connecting
monosaccharides is called
(a) Glycosidic linkage (b) nucleoside linkage
11. In fructose, the possible optical isomers are
(c) glycogen linkage (d) peptide linkage
(a) 12 (b) 8
4. Rapid interconversion of a-D- glucose and b-D- glucose in
(c) 16 (d) 4
solution is known as
12. When amylases catalyse the hydrolysis of starch, the final
(a) racemization (b) asymmetric induction
product obtained is chiefly
(c) fluxional isomerization (d) mutarotation
(a) Cellubiose (b) Glucose
5. The reagent which forms crystalline osazone derivative
(c) Maltose (d) Sucrose
when treated with glucose is
(a) Fehling solution (b) Phenylhydrazine 13. D-Glucose HNO
3  (A), Product (A) is

(c) Benedict solution (d) Hydroxylamine
(a) D-Gluconic acid (b) D-Glucitol
6. Lactose is a disaccharide of
(c) D-Fructose (d) D-Glucaric acid
(a) Glucose only (b) Glucose and fructose
14. Acid or enzymatic hydrolysis of sucrose to give an equimolar
(c) Glucose and galactose (d) Galactose only
mixture of glucose and fructose is called
7. The pH of blood is around
(a) Esterification (b) Inversion
(a) 8.0 (b) 6.0
(c) Saponification (d) Insertion
(c) 5.4 (d) 7.4
15. D-Glucose exists in x different forms. The value of x
8. Which of the following is a reducing sugar ? (stereoisomer) is
(a) Glucose (b) Fructose (a) 2 (b) 3
(c) Maltose (d) All of these (c) 4 (d) 5
9. Which of the following is a non-reducing sugar ? 16. All monosaccharides containing five or six carbon atoms
(a) Sucrose (b) Maltose have
(c) Lactose (d) Ribose (a) Open chain structures
(b) Pyranose structures
(c) Furanose structures
(d) May have pyranose or furanose structures
BIOMOLECULES 114
17. Glucose and fructose are 25. Sucrose reacts with acetic anhydride to form
(a) Optical isomers (b) Tautomers (a) Penta-acetate (b) Hexa-acetate
(c) Functional isomers (d) Chain isomers (c) Tetra-acetate (d) Octa-acetate
18. -D- Glucose and -D-glucose differ from each other due to 26. A certain compound gives negative test with ninhydrin and
difference in one carbon with respect to its ? positive test with Benedict’s solution. The compound is
(a) Size of hemiacetal ring (b) Number of OH groups (a) A protein (b) A monosacchride
(c) Configuration (d) Conformation (c) A lipid (d) An amino acid
19. Which of the following represents the anomer of the 27. Glucose and mannose are
compound shown ? (a) Optical isomers (b) Anomers
(c) Epimers (d) Chain isomers
28. Oxidation of glucose with Ag2O gives
(a) D-Gluconic acid (b) L-Glucaric acid
(c) L-Gluconic acid (d) L-Glucaric acid
Amino Acids
(a) (b) 29. The acid showing salt-like character in aqueous solution is
(a) Acetic acid (b) Benzoic acid
(c) Formic acid (d) -Aminoacetic acid
30. Which of the following does not exist as a zwitter ion ?
(c) (d) None of these (a) Glycine (b) Alanine
(c) Sulphanilic acid (d) p-Aminobenzoic acid
20. In lactose, the reducing part is 31. In aqueous solutions, amino acids mostly exist as
(a) Galactose (b) Glucose (a) NH 2  CHR  COOH (b) NH2  CHR  COO
(c) Fructose (d) Mannose
 
21. Which of the following reduces Tollen’s reagent ? (c) N3 N  CHR  COOH (d) H 3 N  CHR  COO
(a) Glucose (b) Fructose
32. Which of the following -amino acids does not contain a
(c) Lactose (d) All chiral carbon ?
22. Glucose reduces (a) Glycine (b) Alanine
(a) Tollen’s reagent (b) Fehling’s solution (c) Phenylalanine (d) Valine
(c) Benedict’s solution (d) All 33. In glycine, the basic group at isoelectric point
23. D-glucose & D-fructose can be differentiated by (a) –NH2 (b) –NH3
(a) Fehling solution (b) Tollens reagent
(c) –COOH (d) COO 
(c) Benedict test (d) Br2/H2O
34. Which statement correctly completes the statement ?
24. For the complex conversion of D-glucose into the
corresponding osazone, the minimum number of equivalents Except for glycine, which is achiral, all the amino acids present
of phenyl hydrazine required is in proteins ..........
(a) two (b) three (a) are chiral, but racemic
(c) four (d) five (b) have the L configuration at their  carbon
(c) have the R configuration at their  carbon
(d) have the S configuration at their  carbon
BIOMOLECULES 115
35. Which amino acid does not contain chiral centre ? 43. When pieces of human hair are heated strongly with soda-
(a) Valine (b) Leucine lime, smell of ammonia can be detected. Which one of the
following conclusion can be drawn from this observation?
(c) Glycine (d) Iso-leucine
(a) Ammonia is present in the human hair
36. In an amino acid, the carboxyl group ionises at pKa1 = 2.34
and ammonium ion at pKa2 = 9.60. The isoelectric point of (b) Ammonium salt is present in hair
the amino acid is at pH (c) Hair contains amino acids
(a) 5.97 (b) 2.34 (d) None of the above
(c) 9.60 (d) 6.97 44. How many amino acids (approx) are involved during the
37. The relation of the isoelectric point for an amino acid, to synthesis of protein?
solubility is (a) 15 (b) 18
(a) the two are not related (c) 20 (d) 91
(b) an amino acid is least soluble at its isoelectric point
Proteins
(c) an amino acid has the maximum solubility at the
45. Proteins are condensation polymers of
isoelectric point
(a) -Amino acids (b) -Amino acids
(d) solubilities of only some amino acids depend on it.
(c) -Hydroxy acids (d) -Hydroxy acids
38. Assume that a particular amino acid has an isoelectric point
of 6.0. In a solution at pH 1.0, which of the following species 46. Proteins are
will predominate ? (a) Polyamides (b) Polyesters
(c) Polyhydric alcohols (d) Polycarboxylic acids
(a) (b) 47. Which of the following contains nitrogen ?
(a) Fats (b) Proteins
(c) Carbohydrates (d) None
(c) (d)
48. The sequence in which the a-amino acids are linked to one
39. At Iso-electric point another in a protein molecule is called its
(a) conc. of cation is equal to conc. of anion (a) Primary structure (b) Secondary structure
(b) Net charge is zero. (c) Tertiary structure (d) Quaternary structure
(c) Maximum conc. of di-polar ion (Zwitter ion) will be present 49. The peptide bond is
(d) All of the above (a) –CONH2 (b) –CONH–
40. The number of amino acids found in proteins that a human (c) –COONH4 (d) –N = C = O
body can synthesize is
50. The bond that determines the secondary structure of a
(a) 20 (b) 10 protein is
(c) 5 (d) 14 (a) Co-ordinate bond (b) Covalent bond
41. Lack of essential amino acids in the diet leads to the disease (c) Hydrogen bond (d) Ionic bond
called 51. The dipeptide glycylalanine contains
(a) Night blindness (b) Pernicious anaemia (a) glycine as C-terminal residue
(c) Kwashiorkor (d) Sickel cell anaemia (b) glycine as N-terminal residue
42. Which of following amino acid has lowest iso-electric point? (c) alanine as N-terminal residue
(a) Glycine (b) Alanine (d) either (a) or (b)
(c) Aspartic acid (d) Lysine
BIOMOLECULES 116
52. The number of tripeptides formed by three different amino (a) ACUUGGGAA (b) TCUUGGGTT
acids are (c) ACUUCCCAA (d) None of the above
(a) Three (b) Four 62. Which of the following statements about RNA is not correct?
(c) Five (d) Six (a) It has a single strand.
53. Mark the wrong statement about denaturation of proteins (b) It does not undergo replication in cytoplasm.
(a) The primary structure of the protein doesn’t change (c) It does not contain any pyridimine base.
(b) Globular proteins are converted into fibrous proteins (d) It controls the synthesis of proteins.
(c) Fibrous proteins are converted into globular proteins 63. Consider the double helix structure of DNA. the base pairs
(d) The biological activity of the protein is destroyed are
Nucleic Acids (a) Part of the back bone structure
54. If one strand of DNA has the sequence ATGCTTGA, the (b) Inside the helix
sequence in the complimentary strand would be (c) Outside the helix
(a) TACGAACT (b) TCCGAACT (d) None of these
(c) TACGTACT (d) TACGTAGT 64. Which of the following statements about DNA is not correct?
55. The sugar present in DNA is (a) It has a double helix structure.
(a) Glucose (b) Deoxyribose (b) It undergoes replication.
(c) Ribose (d) Fructose (c) The two strands in a DNA molecule are exactly similar.
56. Which of the following sets of bases is present both in (d) It contains the pentose sugar, 2-deoxyribose.
DNA and RNA ? 65. Chargaff’s rule states that in an organism
(a) Adenine, uracil, thymine
(a) amount of adenine (A) is equal to that of guanine (G)
(b) Adenine, guanine, cytosine and the amount of thymine (T) is equal to that of
(c) Adenine, guanine, uracil cytosine (C)
(d) Adenine, guanine, thymine (b) amount of adenine (A) is equal to that of cytosine (C)
57. A nucleotide consists of and the amount of thymine (T) is equal to that of guanine
(G)
(a) carbon sugar (b) nitrogen containing base
(c) phosphoric acid (d) all of these (c) amount of all bases are equal
58. In nucleic acids, the nucleotides are linked to one another (d) amount of adenine (A) is equal to that of thymine (T)
through and the amount of guanine (G) is equal to that of
cytosine (C)
(a) Hydrogen bond (b) Peptide bond
66. DNA molecule takes the shape of…I…helix which are
(c) Glycosidic linkage (d) Phosphate groups
59. The pentose sugar in DNA and RNA has the made up of alternate units of …II…and…III….
(a) Open chain structure (b) Pyranose structure (a) I  double II  phosphate III  Sugar ribose
(c) Furanose structure (d) None of the above (b) I  -pleated II  phosphate III  Sugar deoxyribose
60. In nucleic acids, the sequence is (c) I double II  phosphate III  sugar deoxyribose
(a) Phosphate–Base–sugar (d) I -pleated II  phosphate III  sugar ribose
(b) Sugar–Base–phosphate 67. Which of the following match is correct?
(c) Base–sugar–phosphate (a) DNA  -D-3-deoxyribose
(d) Base–phosphate–sugar (b) DNA  -D-1-deoxyribose
61. If the sequence of bases in DNA is TGAACCCTT then the (c) RNA  -D-ribose
sequence of bases in m-RNA is
(d) RNA  -D-3-deoxyribose
BIOMOLECULES 117
Enzymes 74. Which one of the following chemical units is certainly to be
found in enzyme ?
68. Enzymes in the living systems
(a) Provide energy
(b) Provide immunity (a) (b)
(c) Transport oxygen
(d) Catalyse biological processes
69. Enzymes take part in a reaction and
(a) decrease the rate of a chemical reaction
(c) (d)
(b) increase the rate of a chemical reaction
(c) both (a) and (b)
(d) None of these
Lipids and Hormones
70. Enzymes are made up of
75. The number of molecules of ATP produced in the lipid
(a) edible proteins metabolism of a molecule of palmitic acid is
(b) proteins with specific structure (a) 56 (b) 36
(c) nitrogen containing carbohydrates (c) 130 (d) 86
(d) carbohydrates 76. The chemical messengers produced in the ductless glands
71. The function of enzymes in the living system is to are
(a) transport oxygen (a) Vitamins (b) Lipids
(b) provide immunity (c) Hormones (d) Antibodies

77. Which of the following hormones contains iodine ?
(c) catalyse biochemical reactions
(a) Insulin (b) Thyroxine
(d) provide energy
(c) Adrenaline (d) Testosterone
72. The enzyme which catalyse the oxidation of one substrate
with simultaneous reduction of another substrate are called 78. Insulin is a
as…I…enzyme. The enzyme ends with the name of (a) Steroid hormone (b) Peptide hormone
…II…Identify. I and II for the above blanks from the options (c) Amine hormone (d) None of the above
given below.
79. Which of the following is not an amine hormone?
(a) I  reductioxidase II  ase
(a) Norepinephrine (b) Adrenaline
(b) I  oxidoreductase II  ase
(c) Thyroxine (d) Oxytocin
(c) I  oxidoreductase II  ese
80. The hormone which controls the processes like burning of
(d) I  reductoxidese II  ese fats, proteins and carbohydrates to liberate energy in the
73. Enzymes are needed only in ……quantity for the progress body is
of reaction. (a) cortisone (b) thyroxine
Select the appropriate word to fill the blank. (c) adrenaline (d) insulin
(a) small (b) large
(c) Both (a) and (b) (d) None of these
BIOMOLECULES 118
EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. Out of the following, which type of interaction is responsible 5. Match List-I with List-II:
for the stabilisation of  -helix structure of proteins? List - I List - II
(2021-02-24/Shift-1) A Sucrose (i)  -D-Galactose and  -D-Glucose
(a) Ionic bonding (b) Vander Waals forces
B Lactose (ii)  -D-Glucose and  -D-Fructose
(c) Hydrogen bonding (d) Covalent bonding
C Maltose (iii)  -D-Glucose and  -D-Glucose
2. Which of the glycosidic linkage between galactose and
(2021-02-26/Shift-2)
glucose is present in lactose? (2021-02-25/Shift-1)
(a) A – (iii), B – (i), C – (ii)
(a) C-1 of galactose and C-4 of glucose
(b) A – (i), B – (iii), C – (ii)
(b) C-1 of galactose and C-6 of glucose
(c) A – (iii), B – (ii), C – (i)
(c) C-1 of glucose and C-4 of galactose
(d) A – (ii), B – (i), C – (iii)
(d) C-1 of glucose and C-6 of galactose
6. Seliwanoff test and Xanthoproteic test are used for the
3. Which of the following is correct structure of  -anomer of
identification of _______ and _______ respectively.
maltose? (2021-02-25/Shift-2)
(2021-02-26/Shift-2)
(a) Ketoses, aldoses (b) Proteins, ketoses
(c) Aldoses, ketoses (d) Ketoses, proteins
(a)
7. Which among the following pairs of Vitamins is stored in
our body relatively for longer duration?
(2021-03-16/Shift-1)
(a) Thiamine and Vitamin A
(b) (b) Thiamine and Ascorbic acid
(c) Ascorbic acid and Vitamin D
(d) Vitamin A and Vitamin D
8. The secondary structure of protein is stabilised by
(2021-03-16/Shift-2)
(c)
(a) glycosidic bond (b) Hydrogen bonding
(c) Peptide bond (d) Van der Waals forces
9. C12 H 22 O11  H 2 O 
 C6 H12 O6  C6 H12 O6
Enzyme A
Sucrose Glu cos e Fructose
C6 H12 O 6 
Enzyme B
 2C 2 H 5 OH  2CO 2
Glu cos e
(d)
In the above reactions, the enzyme A and enzyme B
respectively are : (2021-03-17/Shift-2)
4. Which of the following vitamin is helpful in delaying the (a) Invertase and Amylase
blood clotting ? (2021-02-26/Shift-1) (b) Invertase and Zymase
(a) Vitamin E (b) Vitamin C (c) Amylase and Invertase
(c) Vitamin K (d) Vitamin B (d) Zymase and Invertase
BIOMOLECULES 119
10. A non-reducing sugar “A” hydrolyses to give two reducing 14. Thiamine and pyridoxine are also known respectively as:
mono saccharides. Sugar A is: (2021-03-18/Shift-1) (2021-07-22/Shift-2)
(a) Sucrose (b) Glucose (a) Vitamin B2 and Vitamin E (b) Vitamin E and Vitamin B2
(c) Fructose (d) Galactose (c) Vitamin B6 and Vitamin B2 (d) Vitamin B1 and Vitamin B6
11. Deficiency of vitamin K causes : (2021-03-18/Shift-2) 15. The water-soluble protein is: (2021-07-25/Shift-1)
(a) Increase in blood clotting time (a) Fibrin (b) Albumin
(b) Increase in fragility of RBC’s (c) Myosin (d) Collagen
(c) Decrease in blood clotting time 16. Which one of the following is correct structure for cytosine?
(d) Cheilosis (2021-07-25/Shift-2)
12. The correct structure of Rhumann’s Purple, the compound
formed in the reaction of ninhydrin with proteins is:
(2021-07-20/Shift-1)
(a) (b)
(a)
(b) (c) (d)
17. Compound A gives D-Galactose and D-Glucose on

hydrolysis. The compound A is: (2021-07-27/Shift-2)
(c)
(a) Amylose (b) Sucrose
(c) Maltose (d) Lactose
18. Which one among the following chemical tests is used to
distinguish monosaccharide from disaccharide?
(2021-07-27/Shift-1)
(d)
(a) Seliwanoff’s test (b) Iodine test
(c) Barfoed test (d) Tollen’s test
13. Identify the incorrect statement from the following
(2021-07-20/Shift-1)
(a) Amylose is a branched chain polymer of glucose
(b) Starch is a polymer of -D glucose
(c) -Glycosidic linkage makes cellulose polymer
(d) Glycogen is called as animal starch
BIOMOLECULES 120
22. Which one of the following tests used for the identification
of functional groups in organic compounds does not use
copper reagent? (2021-08-27/Shift-2)
(a) Barfoed’s test

19.
(b) Seliwanoff’s test
(c) Benedict’s test
The compound ‘A’ is a complementary base of __________ (d) Biuret test for peptide bond
in DNA strands. (2021)
23. Hydrolysis of sucrose gives : (2021-08-27/Shift-2)
(a) Uracil (b) Guanine
(c) Adenine (d) Cytosine (a)  -D-(–)-Glucose and  -D-(–)-Fructose
20. Given below are two statements: One is labelled as Assertion (b)  -D-(+)-Glucose and  -D-(–)-Fructose
(A)and the other is labelled as Reason (R).
(c)  -D-(–)-Glucose and  -D-(+)-Fructose
Assertion (A) : Sucrose is a disaccharide and a non-
reducing sugar. (d)  -D-(+)-Glucose and  -D-(–)-Fructose
Reason (R) : Sucrose involves glycoside linkage between
24. Which one of the following compounds contains  -C1–C4
C1 of  -Glucose and C2 of  -fructose.
glycosidic linkage ? (2021-08-31/Shift-1)
Choose the most appropriate answer from the options given
below. (2021-08-26/Shift-2) (a) Lactose (b) Sucrose
(a) Both (A) and (R) are true but (R) is not the true explanation (c) Maltose (d) Amylose
of (A) 25. Which of the following is NOT an example of fibrous
(b) (A) is false but (R) is true protein? (2021-08-31/Shift-2)
(c) (A) is true but (R) is false (a) Keratin (b) Albumin
(d) Both (A) and (R) are true and (R) is true explanation of (c) Collagen (d) Myosin
(A)
21. Out of following isomeric forms of uracil, which one is

present in RNA? (2021-08-27/Shift-1)
(a) (b)
(c) (d)
BIOMOLECULES 121
26. A polysaccharide ‘X’ on boiling with dil H2SO4 at 393

K under 2 – 3 atm pressure yields ‘Y’. ‘Y’ on
treatment with bromine water gives gluconic acid. ‘X’
contains  -glycosidic linkages only. Compound ‘X’
is : (JEE Main 2022)
(a) starch (b) cellulose (b)
(c) amylose (d) amylopectin
List I List II
A) Zymase I. Stomach
(c)
B) Diastase II. Yeast
C) Urease III. Malt
D) Pepsin IV. Soyabean
(a) A → II; B → III; C → I; D → IV
(b) A → II; B → III; C → IV; D → I
(c) A → III; B → II; C → IV; D → I (d)
(d) A → III; B → II; C → I; D → IV 31. Stability of  -Helix structure of proteins depends
28. Which one of the following is a water soluble vitamin, upon (JEE Main 2022)
that is not excreted easily? (JEE Main 2022) (a) dipolar interaction
(a) Vitamin B2 (b) Vitamin B1 (b) H-bonding interaction
(c) Vitamin B6 (d) Vitamin B12 (c) van der Waals forces
29. Given below are two statements. (d)  -stacking interaction
Statement I: Maltose has two α-D-glucose units 32. When sugar 'X' is boiled with dilute H2SO4 in
linked at C1 and C4 and is a reducing sugar. alcoholic solution, two isomers 'A' and 'B' are formed.
Statement II: Maltose has two monosaccharides: α-D- 'A' on oxidation with HNO3 yields saccharic acid
glucose and β-D-glucose linked at C1 and C6 and it is a whereas 'B' is laevorotatory. The compound 'X' is:
non-reducing sugar. (JEE Main 2022)
In the light of the above statements, choose the correct (a) Maltose (b) Sucrose
answer from the options given below. (c) Lactose (d) Strach
(JEE Main 2022) 33. Sugar moiety in DNA and RNA molecules
(a) Both Statement I and Statement II are true. respectively are (JEE Main 2022)
(b) Both Statement I and Statement II are false. (a)  -D-2-deoxyribose,  -D-deoxyribose
(c) Statement I is true but Statement II is false. (b)  -D-2-deoxyribose,  -D-ribose
(d) Statement I is false but Statement II is true.
(c)  -D-ribose,  -D-2-deoxyribose
30. L-isomer of a compound ‘A’ (C4H8O4) gives a positive
test with [Ag(NH3)2]+. Treatment of ‘A’ with acetic (d)  -D-deoxyribose,  -D-2-deoxyribose
anhydride yields triacetate derivative. Compound ‘A’ 34. The structure of protein that is unaffected by heating is
produces an optically active compound (B) and an (JEE Main 2022)
optically inactive compound (C) on treatment with (a) secondary structure
bromine water and HNO3 respectively. Compound (A) (b) tertiary structure
is: (JEE Main 2022) (c) primary structure
(d) quaternary structure
35. During the denaturation of proteins, which of these
structures will remain intact? (JEE Main 2022)
(a) Primary (b) Secondary
(c) Tertiary (d) Quaternary
(a)
BIOMOLECULES 122
36. Glycosidic linkage between C1 of  -glucose and Choose the correct answer from the options given
C2 of  -fructose is found in (JEE Main 2022) below: (JEE Main 2022)
(a) maltose (b) sucrose (a) (A)-(IV), (B)-(I), (C)-(II), (D)-(III)
(c) lactose (d) amylose (b) (A)-(IV), (B)-(III), (C)-(II), (D)-(I)
37. Which of the following is reducing sugar? (c) (A)-(III), (B)-(I), (C)-(IV), (D)-(II)
(JEE Main 2022) (d) (A)-(I), (B)-(III), (C)-(IV), (D)-(II)
40. For the below given cyclic hemiacetal (X), the correct
pyranose structure is: (JEE Main 2022)
(a)
(b)
(a)
(c)
(b)
(d) (c)
38. Animal starch is the other name of :
(JEE Main 2022)
(a) amylose (b) maltose
(c) glycogen (d) amylopectin
39. Match List-I with List-II
List-I List-II (d)
(A) Glucose + HI (I) Gluconic acid
(B) Glucose + Br2 water (II) Glucose pentacetate
(C) Glucose + acetic
(III) Saccharic acid
anhydride
(D) Glucose + HNO3 (IV) Hexane
BIOMOLECULES 123
41. The formulas of A and B for the following reaction 48. Match items of Column I with those of Column II.
sequence are (JEE Main 2022) Column-I Column-II
(P) (i)   D   – 
Fructofuranose
(a) A = C7H14O8, B = C6H14

(b) A = C7H13O7, B = C7H14O
(c) A = C7H12O8, B = C6H14 (Q) (ii)   D   – 
(d) A = C7H14O8, B = C6H14O6 Fructofuranose
42. Given below are two statements. One is labelled as
Assertion A and the other is labelled as Reason R.
Assertion A: Amylose is insoluble in water.
Reason R: Amylose is a long linear molecule with
more than 200 glucose units.
In the light of the above statements, choose the correct (iii)   D    
answer from the options given below.
Glucopyranose
(JEE Main 2022)
(a) Both A and R are correct and R is the correct
(R)
explanation of A.
(iv)   D    
(b) Both A and R are correct and R is NOT the
Glucopyranose
correct explanation of A.
(c) A is correct but R is not correct. (S)
Correct match is (JEE Main 2023)
(d) A is not correct but R is correct.
(a) P → iv, Q → iii, R → i, S → ii
43. In alanylglycylleucylalanylvaline, the number of (b) P → i, Q → ii, R → iii, S → iv
peptide linkages is ____ (JEE Main 2022) (c) P → iii, Q → iv, R → ii, S → i
44. A protein 'A' contains 0.30% of glycine (molecular (d) P → iii, Q → iv, R → i, S → ii
49. Number of cyclic tripeptides formed with 2 amino
weight 75). The minimum molar mass of the protein
acids A and B is: (JEE Main 2023)
'A' is ______ × 103 g mol–1 [nearest integer] (a) 2 (b) 3
(JEE Main 2022) (c) 5 (d) 4
50. Following tetrapeptide can be represented as
45. How many of the given compounds will give a
positive Biuret test ____ ?
Glycine, Glycylalanine, Tripeptide, Biuret
(JEE Main 2022)
46. The number of oxygens present in a nucleotide formed
from a base, that is present only in RNA is_____.
(JEE Main 2022)
47. In a linear tetrapeptide (Constituted with different
amino acids), (number of amino acids) - (number of
(F, L, D, Y, I, Q, P are one letter codes for amino
peptide bonds) is______. (JEE Main 2022)
acids) (JEE Main 2023)
(a) FIQY (b) FLDY
(c) YQLF (d) PLDY
BIOMOLECULES 124
51. A protein ‘X’ with molecular weight of 70,000 u, on

hydrolysis gives amino acids. One of these amino acid
is (JEE Main 2023)
(a)
(c)
(b)
(d)
(c)
54. The correct representation in six membered pyranose
form for the following sugar [X] is
(JEE Main 2023)
(d)
52. Which of the following artificial sweeteners has the
highest sweetness value in comparison to cane sugar?
(JEE Main 2023)
(a) Aspartame (b) Sucralose
(c) Alitame (d) Saccharin
53. Compound A, C5 H10O5 , given a tetraacetate with
Ac2 O and oxidation of A with Br2  H 2 O gives an
acid, C5 H10 O6 . Reduction of A with HI gives
isopentane. The possible structure of A is :
(JEE Main 2023)
(a)
(a)
(b)
(b)
BIOMOLECULES 125

List I List II
Enzymatic Reaction Enzyme
A. Sucrose → Glucose I. Zymase
and Fructose
B. Glucose → ethyl II. Pepsin
alcohol and CO2
(c)
C. Starch → Maltose III. Invertase
D. Proteins → Amino IV. Diastase
acids
(a) A - III, B - I, C - II, D - IV
(d) (b) A - I, B - II, C - IV, D - III
55. Match List I and List II (c) A - I, B - IV, C - III, D - II
List I List II (d) A - III, B - I, C - IV, D - II
Test Functional group/Class of 58. Match List I with List II
Compound List I List II
(A) Molisch's Test (I) Peptide Vitamin Deficiency disease
(B) Biuret Test (II) Carbohydrate A. Vitamin A I. Beri – Beri
(C) Carbylamine Test (III) Primary amine B. Thiamine II. Cheilosis
(D) Schiff s Test (IV) Aldehyd C. Ascorbic acid III. Xeropthalmia
Choose the correct answer from the options given D. Riboflavin IV. Scurvy
below: (JEE Main 2023) Choose the correct answer from the options given
(a) (A) – I, (B) – II, (C) – III, (D) – IV below: (JEE Main 2023)
(b) (A) – III, (B) – IV, (C) –I, (D) – II (a) A - III, B - I, C - IV, D – II
(c) (A) – II, (B) – I, (C) – III, (D) – IV (b) A - IV, B - I, C - III, D – II
(d) (A) – III, (B) – IV, (C) –II, (D) – I (c) A - IV, B - II, C - III, D - I
56. Given below are two statements : one is labelled as (d) A - III, B - II, C - IV, D – I
Assertion (A) and the other is labelled as Reason (R).
List I (Natural Amino List II (One Letter Code)
Assertion (A):  -halocarboxylic acid on reaction acid)
with dil. NH 3 gives good yield of  -amino (A) Arginine (I) D
(B) Aspartic acid (II) N
carboxylic acid whereas the yield of amines is very
(C) Asparagine (III) A
low when prepared from alkyl halides. (D) Alanine (IV) R
Reason (R): Amino acids exist in zwitter ion form in Choose the correct answer from the options given
aqueous medium. below: (JEE Main 2023)
(a) A – I, B – III, C – IV, D – II
In the light of the above statements, choose the correct (b) A – III, B – I, C – II, D – IV
answer from the options given below : (c) A – IV, B – I, C – II, D – III
(JEE Main 2023) (d) A – IV, B – I, C – III, D – II
60. Sulphur (S) containing amino acids from the following
(a) Both (A) and (R) are correct and (R) is the correct
are:
explanation of (A). (a) isoleucine (b) cysteine (c) lysine (d) methionine (e)
(b) Both (A) and (R) are correct but (R) is not the glutamic acid (JEE Main 2023)
(a) a, d (b) b, c, e
correct explanation of (A).
(c) b, d (d) a, b, c
(c) (A) is correct but (R) is not correct.
(d) (A) is not correct but (R) is correct.
BIOMOLECULES 126

List I List II
(Natural amino acid) (One letter code)
A. Glutamic acid I. Q
B. Glutamine II. W
C. Tyrosine III. E
D. Tryptophan IV. Y
Choose the correct answer from the options given (d)
below: (JEE Main 2023) 65. Which is not true for arginine? (JEE Main 2023)
(a) A-IV, B-III, C-I, D-II (a) It is a crystalline solid.
(b) A-III, B-IV, C-I, D-II (b) It has high solubility in benzene.
(c) A-III, B-I, C-IV, D-II (c) It is associated with more than one pK a values
(d) A-II, B-I, C-IV, D-III (d) It has a fairly high melting point.
62. The one that does not stabilize 2 and 3 structures of
D      Glyceraldehyde   i HCN
proteins is (JEE Main 2023)
66.  ii  H O / H   iii  HNO

2 3
(a) –O–O–linkage (b) –S–S–linkage The products formed in the above reaction are
(c) van der Waals forces (d) H-bonding (JEE Main 2023)
63. In Carius tube, an organic compound ‘X’ is treated (a) One optically inactive and one meso product.
with sodium peroxide to form a mineral acid ‘Y’. (b) Two optically inactive products
The solution of BaCl2 is added to ‘Y’ to form a (c) Two optically active products
precipitate ‘Z’ ‘Z’ is used for the quantitative (d) One optically active and one meso product
estimation of an extra element. ‘X’ could be 67. The naturally occurring amino acid that contains only
(JEE Main 2023) one basic functional group in its chemical structure is
(a) Cytosine (b) Methionine (JEE Main 2023)
(c) Chloroxylenol (d) A nucleotide (a) lysine (b) arginine
64. L-isomer of tetrose X (C4 H 8 O4 ) gives positive (c) histidine (d) asparagine
68. Uracil is base present in RNA with the following
Schiff's test and has two chiral carbons. On
structure. % of N in uracil is _______.
acetylation, ‘X’ yields triacetate. ‘X’ also undergoes
following reactions (JEE Main 2023)
A 
HNO3
 X  NaBH 4
 B
Chiral compound
X is
Given: Molar mass N  14 g mol –1 ; O  16 g mol –1 ;

C  12 g mol –1 ; H  1 g mol –1 ; (JEE Main 2023)
69. Total number of tripeptides possible by mixing of
(a) valine and proline is _______ (JEE Main 2023)
70. A short peptide on complete hydrolysis produces 3
moles of glycine (G), two moles of leucine (L) and
two moles of valine (V) per mole of peptide. The
number of peptide linkages in it are _______.
(JEE Main 2023)
71. Number of compounds from the following which will
not produce orange red precipitate with Benedict
(b)
solution is ________
Glucose, maltose, sucrose, ribose, 2-deoxyribose,
amylose, lactose (JEE Main 2023)
72. In an oligopeptide named Alanylglycylphenyl alanyl
isoleucine, the number of sp 2 hybridised carbons is
_____. (JEE Main 2023)
(c)
BIOMOLECULES 127

Objective Questions I [Only one correct option]
1. “Carbohydrate that cannot be hydrolysed further to give 7. What does ‘D’ and (  ) signifies in D – (  ) – glucose?
simpler unit of polyhydroxy aldehyde or ketone”. Name the
(a) D represent conformation and (  ) represents the
type of carbohydrates.
laevorotatory nature of molecule
(a) Monosaccharide (b) Oligosaccharide
(b) D represent configuration and (  ) represent the
(c) Polysaccharide (d) All of these dextrorotatory nature of molecule
2.  and  form of glucose are (c) D represent conformation and (  ) represent the
(a) at equilibrium (b) the anomers dextrorotatory nature of molecule
(d) D represent configuration and () represent the
(c) the cyclic structures (d) all of these
laevorotatory nature of molecule
3. Which of the following form/s osazone with
8. I. Pyran is a cyclic organic compound with one oxygen
phenylhydrazine?
atom and five carbon atom.
II. The cyclic structure of glucose is correctly
(c) Maltose (d) All the three above represented by Haworth structure.
O
|| III. Five membered cyclic structure of glucose is called
4. NH 2  CH  C  NH  CH 2  CO2 H pyranose structure.
|
CH3 Which of the following statements) is/are true?
Identify the amino acid obtained by hydrolysis of the above Choose the correct option.
compound. (a) I and III (b) I and II
(a) Glycine (b) Alanine
(c) Only III (d) I, II and III
9. I. Disaccharides on hydrolysis with dilute acid gives three
5. On hydrolysis sucrose will give molecules of same or different monosaccharides.
(a) one molecule of glucose II. Disaccharides are formed by the loss of water with an
(b) two molecule of glucose oxide likage.
(c) one molecule of glucose and fructose III. The oxide linkage in the disaccharide is called glycosidic
linkage.
(d) one molecule of glucose and maltose
Choose the incorrect statement about disaccharide and
6. Name the reagent and condition required for the following
select the most appropriate option.
reaction.
(a) Only I (b) Only II
(c) Only III (d) Only II and III
10. Name the components(s) that constitute(s) the starch.
(a) Amylose (b) Amylopectin
(a) HF,  (b) HCl, 
(c) HBr,  (d) HI, 
BIOMOLECULES 128
11. What is the product formed when D-glucose is treated with
Br2 water?
(a) (b)
(a) (b)
(c) (d) None of these
(c) (d)
17. The pKa values for the three ionizable groups X, Y and Z of
glutamic acid are 4.3, 9.7 and 2.2 respectively
12. Name the enzyme that catalyses the reaction given below.
 
?
C12 H 22 O11   2C6 H12 O 6
maltose glucose
(a) Talose (b) Lactose The isoelectric point for the amino acid is
(c) Pepsin (d) Maltase (a) 7.00 (b) 3.25
13. Which of the following statement(s) is/are correct regarding (c) 4.95 (d) 5.95
vitamins ?
HgSO4 (1)NH3  HCN
(a) They ae designated by A, B, C, D 18. HC  CH A  B ;
H 2SO 4 (2)H3O
(b) They are further named as B1, B2, B6 and B12…
Product (B) of above reaction is
(c) Vitamins pills should not be taken without the advice of
doctor (a) Glycine (b) Alanine
(d) All of the above (c) Valine (d) Leucine
14. Which one of the following does not constitute the nucleic 19. Stereoisomers of aldoheptose is (x) and stereoisomers of
acid ? ketoheptose is (y). Ratio of x/y is
(a) Uracil (b) Ribose sugar 1 2

(a) (b)
(c) Phosphoric acid (d) Guanidine 2 1
4 1
15. Which L-sugar on oxidation gives an optically active dibasic (c) (d)
acid (2 COOH groups) ? 1 4
20. Find iso-electric point of given amino acid
(a) (b)
(a) 3.3 (b) 5.9

(c) 9.6 (d) 11.8
21. Find iso-electric point of the given amino acid
(c) (d)
16. Among the three compounds shown below, two yield the
same product on reaction with warm HNO3. The exception
is
BIOMOLECULES 129
(d) All of the above
26. Which of the following statements are corect?
(a) 5.5 (b) 6.5 (a) Hydrolysis of sucrose with dilute acid yields an
(c) 3 (d) 5 equimolar mixture of D-Glucose and D-fructose.
22. Identify the monosaccharide units in the given structure. (b) Acidic hydrolysis of sucrose is accompanied by a
change in optical reaction.
(c) In sucrose, the glycosidic linkage is between C-1
glucose and C-2 of fructose.
(d) Aqueous solution of sucrose exhibits mutarotation.
27. Which of the following carbohydrate is a disaccharide?
(a) I   -D-glucose, II   -D-fructose (c) Maltose (d) Lactose
(b) I   -D-fructose, II   -D-glucose 28. Which of the following do not undergo hydrolysis :
(a) glucose (b) fructose
(c) I   -D-fructose, II   -D-glucose
(c) galactose (d) sucrose
(d) I   -L-glucose, II   -L-fructose 29. Starch molecules are polymer with repeating glucose units.
Select the correct statement(s).
23.
(a) Glucose units are joined through  -glycosidic linkage
(b) The branches of amylopectin are linked to the chain

with alpha -1,6’- glycosidic linkages.
(c) The linear linkages of amylopectin are formed by  -1, 6-

glycosidic bond.
(d) Amylose has an unbranched skeleton of glucose

Name the linkage which is present in the above figure.
molecules with  -1, 4-glycosidic linkages.
(a)  -linkage (b)  -linkage
30.  -D-Glucopyranose and  -D-Glucopyranose are
(c)  -linkage (d)  -linkage
(a) Anomers (b) Epimer
24. Which one of the following amino acid does not give purple (c) Diastereomers (d) Enantiomers
colour in the ninhydrin test?
Numeric Value Type Questions
(a) Aspartic acid (b) Glycine
31. The number of chiral carbon atoms in  -D-glucose is.
(c) Proline (d) Lysine
32. Glucose molecule reacts with ‘X’ number of molecules
25. Which of the following statement(s) is/are true ?
of phenylhydrazine to yield osazone. The value of X is:
(a) Every individual has unique fingerprints and it occur at
33. What is the maximum number of tripeptides which can be
the tips of fingers
obtained from the 20 naturally occurring amino acids
(b) A sequence of bases on DNA is also unique for a person
and information regarding this is called fingerprinting
(c) Fingerprints can be altered by the surgery
BIOMOLECULES 130
34. 39. Assertion (A) : The sucrose mixture is laevorotatory.
Reason (R) : Sucrose on hydrolysis gives dextrorotatory
glucose ( 52.5º ) and laevorotatory of fructose ( 92.4º ).
(a) A (b) B
(c) C (d) D
40. Assertion (A) : Sucrose is called an invert sugar.
Reason (R) : On hydrolysis, sucrose bring the change in
Number of stereoisomers of product (P) is- the sign of rotation from dextro (+) to laevo (–).
(a) A (b) B
Assertion Reason
(c) C (d) D
(A) If both Assertion and Reason are correct and
Reason is the correct explanation of Assertion. 41. Assertion (A) : Cellulose is not digestable in the human
body.
(B) If both Assertion and Reason are true but
Reason (R) : The human system contain cellulose enzyme
Reason is not the correct explanation of which hydrolyse cellulose into glucose.
Assertion.
(a) A (b) B
(C) If Assertion is true but Reason is false.
(c) C (d) D
(D) If Assertion is false but Reason is true. 42. Assertion (A) : Amino acids react with acid and base both.
35. Assertion (A) : Oligosaccharides are classified as Reason (R) : In Zwitter ionic form, amino acids show the
disaccharides, trisaccharides, tetrasaccharides
amphoteric behavior.
Reason (R) : It depends upon the number of
(a) A (b) B
monosaccharides produced on hydrolysis.
(c) C (d) D
(a) A (b) B
43. Assertion (A) : All naturally occurring  -amino acids except
(c) C (d) D
glycine are optically active.
36. Assertion (A) : Acetic acid is a carbohydrate.
Reason (R) : Most naturally occurring amino acids have L-
Reason (R) : Acetic acid fits into general formula C 2  H 2 O  y . configuration.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
37. Assertion (A) : Glucose on acetylation gives pentaacetate. 44. Assertion (A) :  -helix structure of proteins is in the shape
of right handed screw.
Reason (R) : It contains five OH group.
Reason (R) : There is hydrogen bond between the
(a) A (b) B  NH group of each amino acid to the  O of an adjacent
(c) C (d) D turn of the helix.
38. Assertion (A) : Glucose does not form the hydrogen (a) A (b) B
bisulphate addition product. (c) C (d) D
Reason (R) : Glucose is not so reactive to form the product
with NaHSO3 .
(a) A (b) B
(c) C (d) D
BIOMOLECULES 131
45. Assertion (A) : There is the coagulation of egg white on 51. Assertion (A) : D-(+) glucose is dextrorotatory in nature
boiling. Reason (R) : ‘D’ represents its dextrorotatory nature
Reason (R) : When a protein in its native form is subjected
(a) A (b) B
to physical change like change in temperature or chemical
change the hydrogen bonds are disturbed and protein loses (c) C (d) D
its biological activity. This is called denaturation of protein. 52. Assertion (A) : Rhamnose is not a carbohydrate
(a) A (b) B Reason (R) : It contains optically active polyhydroxy

aldehydes or ketones or the compounds which produce
(c) C (d) D such units on hydrolysis.
46. Assertion (A) : The term vitamine is replaced by vitamin Choose the most appropriate choice from the given choices
now days.
below.
Reason (R) : Vitamine came from vital + amine and it was
identified that vitamine did not contain amino groups. (a) A (b) B
(a) A (b) B (c) C (d) D

53. Assertion (A) :
(c) C (d) D
47. Assertion (A) : Vitamin A, D, E and K are stored in liver and
adipose tissue.
Reason (R) : Vitamins are soluble in fats and oils.
(a) A (b) B
(c) C (d) D
48. Assertion (A) : Vitamin B and C must be supplied regularly
in the diet. This compound does not form oxime.
Reason (R) : Vitamins B and C are soluble in water which Reason (R) : Glucose pentaacetate doesn’t have a free –
are readily excreted through urine and cannot be stored OH group at C1 and so can’t be converted to the open
(except vitamin B12) in our body. chain form to give –CHO group and hence doesn’t form
(a) A (b) B the oxime.
(a) A (b) B
(c) C (d) D
49. Assertion (A) : The two strands of DNA are complementary (c) C (d) D
to each others. 54. Assertion (A) : DNA is responsible for maintaining the
Reason (R) : Adenine forms hydrogen bonds with guanine identity of different species of organisms over millions of
and thymine forms hydrogen bonds with cytosine. years.
(a) A (b) B Reason (R) : DNA molecule is capable of self duplication

during cell division and identical DNA strands are
(c) C (d) D transferred to daughter cell.
50. Assertion (A) : When RNA is hydrolysed, there is no (a) A (b) B
relationship among the quantities of different bases
(c) C (d) D
obtained.
Reason (R) : RNA molecules are of three types (mRNA,
rRNA, tRNA) and they perform different functions.
(a) A (b) B
(c) C (d) D
BIOMOLECULES 132
Match the Following 56. Match the column I with their names given in the column II
and select the correct option from the codes given below.
Each question has two columns. Four options are
Column - I Column - II
given representing matching of elements from
Column-I and ColumnII. Only one of these four
options corresponds to a correct matching.For A. 1.  -D-(+)-glucopyranose
each question, choose the option corresponding
to the correct matching.
55. Match the following Column I with product given in the
Column II and select the correct option from the codes given B. 2.  -D-(+)-glucopyranose
below.
A. 1. C. 3. Pyran
(a) A  1, B  2, C  3 (b) A  2, B  1, C  3
B. 2.
(c) A  3, B  1, C  2 (d) A  3, B  2, C  1
57. Match the following amino acid in Column I with their
characteristic feature of side chain given in the Column II
and select the appropriate option from the codes given
C. 3.
below.
A  1, B  2, C  3 A  1, B  3, C  2
A  2, B  3,C  1 A  2, B  1, C  3 A. Asparagine (Asn, N) 1.
B. Proline (Pro, P) 2. HOOC  CH 2  CH 2 
C. Glutanic acid (Glu, E) 3. HO  CH 2 
D. Serine (Ser, S) 4. H 2 N  COCH 2 
(a) A  4, B  1, C  2, D  3
(b) A  4, B  2, C  1, D  3
(c) A  4, B  3, C  1, D  2
(d) A  4, B  1, C  3, D  2
BIOMOLECULES 133
58. Match the following enzymes given in Colmum I with the 60. Match the following structure of base given in column I
reactions they catalyse given in Column II and select the with their name given in the Coloumn II and select the correct
correct option from the Choices given below: option from the codes given below
Column - I Column - II Column - I Column - II
(Enzymes) (Reactions)
A. Invertase 1. decomposition of urea into
NH3 and CO2 A. 1. Thymine (T)
B. Maltase 2. Conversion of glucose into

ethyl alcohol
C. Pepsin 3. Hydrolysis of maltose into
glucose B. 2. Guanine (G)
D. Urease 4. Hydrolysis of cane sugar
E. Zymase 5. Hydrolysis of proteins into peptides
(a) A  4, B  1, C  5, D  3, E  2
(b) A  4, B  3,C  5, D  1, E  2 C. 3. Cytosine (C)
(c) A  4, B  1, C  3, D  5, E  2
(d) A  4, B  5, C  1, D  3, E  2
59. Match the vitamins given in Column I with their deficiency D. 4. Ademine (A)
disease given in column II and selct the correct option from
the codes given below.
(Vitamins) (Diseases)
A. Vitamin B12 1. Increased blood clotting time E.
B. Vitamic C 2. Pernicious anaemia
C. Vitamin D 3. Increased fragility of RBCs and
muscular weakness (a) A  5, B  3, C  2, D  1, E  4
D. Vitamin E 4. Scurvy (b) A  5, B  1, C  2, D  3, E  4
E. Vitamin K 5. Rickets and Osteomalacia
(c) A  2, B  3, C  1, D  5, E  4
(a) A  1, B  2, C  4, D  3, E  5
(d) A  5, B  3, C  1, D  2, E  4
(b) A  2, B  4, C  5, D  3, E  1
(c) A  2, B  5, C  3, D  4, E  1
(d) A  1, B  2, C  3, D  4, E  5
BIOMOLECULES 134
Paragraph Type Questions Use the following passage, to anwers Q. 65 to Q. 67
Use the following passage, to anwers Q. 61 to Q. 64 Passage
Passage
It has been observed that there is a strong need to promote
Carbohydrates are those substances that contain a carbon health and independence through dietary approaches in
atom, an hydrogen atom, and a oxygen atom in the ratio of an individual’s life. With an aging population, people are
1:2:1 and are present in food. These organic compounds less worried about their health and lifestyle which should
act as a source of energy for the body. For ages, people not be the case. Of all the macronutrients, it has been seen
have been consuming carbohydrate-rich foods. The that protein is the most satiating. Proteins are straight chain
carbohydrates present in food are consumable and called amino acids that are important macronutrients ( along with
dietary carbohydrates. Dietary carbohydrates are those that carbohydrates and fats ) that helps in the development of
can be metabolically transformed directly into glucose. muscles, boosts metabolism, increases fat burning, lowers
Chemically, the carbohydrates may be defined as optically blood pressure, etc. Protein sources include animal meat,
active polyhydroxy aldehydes or ketones or the compounds eggs, milk, cheese, soybeans, etc. However, excess
which produce such units on hydrolysis. Carbohydrates consumption of animal meat protein is an environmental
are generally optically active because they have one or threat and hence, in recent years, alternate substitutes of
more chiral carbon atoms. Some of the sweet carbohydrates protein like vegan protein are becoming a choice of
are also called sugars. The most common sugar used in our individuals.
homes is sucrose, whereas the sugar present in milk is
65. Organic molecules containing an amino group and a
lactose.
carboxylic acid group are called-
61. The formula of carbohydrates is
(a) Amines (b) Amylopectin
(a) Cx(H2O)y (b) CxHxOy
(c) Amino acids (d) Nitriles
(c) C2xHyOy (d) CxH2yOy
66. Proteins are:
62. Carbohydrates break down into which of the following
substances? (a) Linear citric acid chains
(a) Phosphoric acids (b) Glucose (b) Branched amino acid chain
(c) Linoleic acid (d) Glutaric acid (c) Linear chain amino acids
63. Household sugar granules are also called- (d) Globular maleic acid chains
(a) Glucopyranose (b) Lactose
67. Which of the following is not an amino acid?
(c) Sucrose (d) Galactose
(a) Alanine (b) Cyanocobalamin
64. Carbohydrates have one or more chiral carbon atoms. This
(c) Cysteine (d) Asparagine
makes them-
(a) An alkyl group (b) Naturally less abundant
(c) Coloured (d) Optically active

BIOMOLECULES 135
Use the following passage, to anwers Q.68 to Q.70 68. The preparation of glucose from sucrose and starch requires
which of the following substances?
Passage
(a) Low pressure (b)Higher surface area
For many medical conditions, glucose has been
(c) Dilute acids (d) 1000 K temperature
administered in patients for a long time. Diseases like
hypoglycemia, hyperkalemia, etc. are treated by 69. The hybridization of the carbonyl carbon in glucose is-
administering glucose in patients. Thus, it was necessary (a) sp3 (b) sp3d2
to manufacture glucose in larger quantities. This gave rise
(c) sp2 (d) d2sp3
to the discovery of laboratory methods of preparation of
70. The commercial preparation of glucose involves which of
glucose. Some of which are-
the following starting materials?
From sucrose: Boiling sucrose with dilute hydrochloric
(a) Mannose (b) Fructose
acid or sulphuric acid in an alcoholic solution leads to the
(c) Raffinose (d) Cellulose
formation of glucose and fructose. The reaction is-

C12 H 22O11  H 2 O 
H
 C6 H12 O 6  C6 H12 O6
Sucrose Glucose Fructose
Sucrose is also called cane sugar.

From starch: When starch is hydrolyzed by boiling it with
dilute sulphuric acid at 393 K under pressure, it leads to the
formation of glucose. This technique is mostly used for the
commercial preparation of glucose.
 C6 H10O5   nH 2O 

H
393 K:2  3atm
 nC6 H12O6
Starch or cellulose Glucose
BIOMOLECULES 136
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

Objective Questions I
[Only one correct option]
1. Two forms of D-glucopyranose, are called (2005)
4. The correct statement about the following disaccharide is
(a) enantiomers (b) anomers
(2018)
(c) epimers (d) diastereomers
2. Cellulose upon acetylation with excess acetic anhydride/
H2SO4 (catalytic) gives cellulose triacetate whose structure
is (2008)
(a) (a) Ring (a) is pyranose with -glycosidic link

(b) Ring (a) is furanose with -glycosidic link
(c) Ring (b) is furanose with -glycosidic link
(d) Ring (b) is pyranose with -glycosidic link
(b)
5. The correct statement(s) about the following sugars X and
Y is (are) (2009)
(c)
(d)
3. The total number of basic groups in the following form of

lysine is (2010)
(a) X is a reducing sugar and Y is a non-reducing sugar

(b) X is a non-reducing sugar and Y is a reducing sugar
(c) The glucosidic linkages in X and Y are  and 
(a) 0 (b) 1 respectively
(c) 2 (d) 3 (d) The glucosidic linkages in X and Y are  and 
respectively
BIOMOLECULES 137
6. Which of the following statements(s) is(are) true? z1 , z 2 and z3 respectively, then what
(2019)
is z1 + z 2 + z3 ? (2020)
(a) The two six-membered cyclic hemiacetal forms of D-(+)-
glucose are called anomers. Assertion Reason
(b) Hydrolysis of sucrose gives dextrorotatory glucose and (A) If both Assertion and Reason are correct and
laevorotatory fructose reason is the correct explanation of Assertion.
(c) Monosaccharides cannot be hydrolysed to give
(B) If both Assertion and Reason are true but
reason is not the correct explanation of
polyhydroxy aldehydes and ketones. Assertion.
(d) Oxidation of glucose with bromine water gives (C) If Assertion is true but Reason is false.
glutamic acid. (D) If Assertion is false but Reason is true.
7. Given (2021) 9. Assertion (A) : Glucose gives a reddish-brown precipitate
with Fehling’s solution.
Reason (R) : Reaction of glucose with Fehling’s solution
gives CuO and gluconic acid. (2007)
(a) A (b) B
(c) C (d) D
The compound(s), which on reaction with HNO3 will give 10. Write the structure of alanine at pH = 2 and pH = 10.
the product having degree of rotation,
(2000)
[ ]D  52.7 is (are)
11. Give the structures of the products in the following reaction

H
Sucrose A  B (2000)
12. Aspartame, an artificial sweetener, is a peptide and has the

(a) (b)
following structure (2001)
CH2C6H5
|
H 2 N  CH  CONH  CH  COOCH 3
(c) (d) |
CH2 COOH
(i) Identify the four functional groups.
(ii) Write the Zwitter ionic structure.
Numeric Value Type Questions (iii) Write the structures of the amino acids obtained from
the hydrolysis of aspartame.
8. The structure of a peptide is given below (iv) Which of the two amino acids is more hydrophobic ?
13. Following two amino acids lysine and glutamine form
dipeptide linkage. What are two possible dipeptides ?
(2003)
H 2 N  CH  COOH H 2 N  CH  COOH
| |
If the absolute values of the net charge of the peptide at
CH 2 CH 2 CH 2 CH 2 NH 2 CH 2 CH 2 COOH
pH = 2, pH = 6, and pH = 11 are
BIOMOLECULES 138
14. The structure of D-glucose is as follows : (2004)
(d)
17. A disaccharide X cannot be oxidised by bromine water.

(a) Draw the structure of L-glucose. The acid hydrolysis of X leads to a laevorotatory solution.
(b) Give the reaction of L-glucose with Tollen’s reagent. The disaccharide X is (2023)
15. Which of the following disaccharide will not reduce Tollen’s (a)
reagent ? (2005)
(a)
(b)
(b)
16. Treatment of D-glucose with aqueous NaOH results in a

mixture of monosaccharides, which are (2022)
(c)
(a)
(d)
(b)
(c)
BIOMOLECULES 139
Note:
BIOMOLECULES

p-BLOCK ELEMENTS (GROUP 15 -18)
Chapter 09 141
p-Block Elements (Group 15 -18)
1. INTRODUCTION 1.3 Ionisation Enthalpy

Group 15 includes nitrogen phosphorus, arsenic, antimony and Ionisation enthalpy decreases down the group due to gradual
bismuth. As we go down the group, there is a shift from non- increase in atomic size. Because of the extra stable half- filled p-
metallic to metallic through metalloidic character. Nitrogen and orbital electronic configuration and smaller size, the ionisation
phosphorus are non-metal, arsenic and antimony metalloid and enthalpy of the group 15 element is much greater than of group
bismuth is a typical metal. 14 elements in the corresponding periods. The order of successive
1.1 Electronic Configuration ionisation enthalpies, as expected is iH1 < iH2 < iH3
The valence shell electronic configuration of these element is
ns2 np3. The s orbital in these element is completely filled and p 2. PHYSICAL PROPERTIES OF GROUP 15
orbitals are half- filled, making their electronic configuration extra ELEMENTS
stable. All the elements of this group are polyatomic. Dinitrogen is a
1.2 Atomic and Ionic Radii diatomic gas while all others are solids. Metallic character
Covalent and ionic radii increase down the group. There is a increases down the group. Nitrogen and phosphours are non-
considerable increase in covalent radius from N to P. However, metals, arsenic and antimony metalloids and bismuth is a metal.
from As to Bi only a small increase in covalent radius is observed.
This is due to the presence of completely filled d and f orbitals in
heavier members.
Atomic & Physical Properties of Group 15 Elements
Element N P As Sb Bi
Atomic Number 7 15 33 51 83
Atomic Mass 14.01 30.97 74.92 121.76 208.98
Electronic configuration [He]2s 2p 2 3
[Ne]3s 3p 2 3
[Ar]3d 4s 4p
10 2 3
[Kr]4d 5s 5p
10 2 3
[Xe]4f145d106s26p3
Covalent Radius/pm 70 110 120 140 150
Ionic Radius/pm 171a 212a 222a 76b 103b
a = M3–, b = M+3
Ionization enthalpy I 1402 1012 947 834 703
/(kJ mol )
–1
II 2856 1903 1798 1595 1610
III 4577 2910 2736 2443 2466
Electronegativity 3.0 2.1 2.0 1.9 1.9
3. CHEMICAL PROPERTIES OF GROUP 15 increases (due to inert pair effect) down the group. Nitrogen
ELEMENTS exhibits +1, + 2, + 4 oxidation states also when it reacts with
Chemical Properties: Oxidation States and trends in a chemical oxygen. Phosphours also shows + 1 and + 4 oxidation states in
reactivity: some oxoacids.
The common oxidation states of these elements are – 3 , + 3 and In the case of nitrogen , all oxidation states from +1 to +4 tend to
+ 5. The tendency to exhibit – 3 oxidation state decreases down disproportionate in acid solution. For example,
the group, bismuth hardly forms any compound in –3 oxidation
3 HNO2  HNO3 + H2O + 2 NO
state. The stability of + 5 oxidation state decreases down the
group. The only well characterised Bi (V) compound is BiF5. The
stability of + 5 oxidation state decreases and that of +3 state
SCAN CODE
p-BLOCK ELEMENTS (GROUP 15 -18) 142
Similarly , in case of phosphorus nearly all intermediate oxidation
Properties of Hydrides of Group 15 Elements
states disproportionate into +5 and –3.
Nitrogen is restricted to a maximum covalency of 4 since only
four (one s and three p) orbitals are available for bonding. The Property NH3 PH3 AsH3 SbH3 BiH3
heavier elements have vacant d orbitals in the outermost shell Melting point/K 195.2 139.5 156.7 185 –
which can be used for bonding (covalency) and hence , expand Boiling point/K 238.5 185.5 210.6 254.6 290
their covalence as in PF6– . (E-H) Distance/ 101.7 141.9 151.9 170.7 –
Anomalous properties of nitrogen: Nitrogen differs from the rest pm
of the members of this group due to its smaller size, high HEH angle 107.8 93.6 91.8 91.3 –
electronegativity , high ionisation enthalpy and non – availability
fH–/kJ mol–1 –46.1 13.4 66.4 145.1 278
of d orbitals. Nitrogen has unique ability to form p – p multiple
dissH–(E–H)/ –46.1 13.4 66.4 145.1 278
bonds with itself and with other elements having small size and
high electronegativity (e.g., C ,O). Heavier elements of this group kJ/mol–1 389 322 297 255 –
do not form p – p bonds as their atomic orbitals are so large
3.2 Reactivity Towards Oxygen
and diffuse that they cannot have effective overlapping. Thus,
All these elements form two types of oxides: E2O3 and E2O5. The
nitrogen exists as a diatomic molecule with a triple bond (one s oxide in the higher oxidation state of the element is more acidic
and two p) between the two atoms. Consequently , its bond than that of lower oxidation state. Their acidic character decreases
enthalpy (941.1 kJ mol –1) is very high. On the contrary, down the group. The oxides of the type E2O3 of nitrogen and
phosphours are purely acidic, that of arsenic and antimony
phosphorus, arsenic and antimony form single bond (P - P, As- amphoteric and those of bismuth is predominantly basic.
As, Sb-Sb) while Bi forms metallic bonds in elemental state.
However , the single N – N bond is weaker than the single P – P 3.3 Reactivity Towards Halogens
bond because of high interelectronic repulsion of the non – These elements react to form two series of halides: EX3 and EX5.
Nitrogen does not form pentahalide due to non– availability of
bonding electrons, owing to the small bond length. As a result the d– orbitals in its valence shell. Pentahalides are more covalent
the catenation tendency is weaker in nitrogen. Another factor than trihalides. All the trihalides of these elements except those
which affects the chemistry of nitrogen is the absence of d orbitals of nitrogen are stable. In case of nitrogen , only NF3 is known to
be stable. Trihalides except BiF3 are predominantly covalent in
in its valence shell. Besides restricting its covalency to four , nature.
nitrogen cannot form d – p bonds as the heavier elements can
e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphours and 3.4 Reactivity Towards Metals
arsenic can form d – p bond also with transition metals when These elements react with metals to form their binary compounds
their compounds like P(C2H5)3 and As(C6H5)3 act as ligands. exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride)
Ca3P2 (calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2
(zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
3.1 Reactivity Towards Hydrogen
All the elements of Group 15 form hydrides of the type EH3 where
E = N , P, As, Sb or Bi. Some of the properties of these hydrides 4. GENERAL PROPERTIES AND COMPONDS OF
are shown in Table. The hydrides show regular gradation in their NITROGEN
properties. The stability of hydrides decreases from NH3 to BiH3 4.1 NITROGEN (N2)
which can be observed from their bond dissociation enthalpy.
Preparation:
Consequently, the reducing character of the hydrides increases.
(i) By treating an aqueous solution of ammonium chloride with
Ammonia is only a mild reducing agent while BiH3 is the strongest
sodium nitrate. It is laboratory method of preparation.
reducing agent amongst all the hydrides. Basicity also decreases
in the order NH4Cl(aq) + NaNO2(aq)  N2(g) + H2O () + NaCl(aq)
NH3 > PH3 > AsH3 > SbH3  BiH3. (ii) By heating ammonium dichromate:

(NH4)2Cr2O7  N2  + 4H2O + Cr2O3
(iii) By oxidation of ammonia
(iv) 2NH3 + 3NaOCl  N2 + 3NaCl + 3H2O
(v) 2NO + 2Cu  2CuO + N2

(red, overheated) (Black)
SCAN CODE
(vi) Cl2 passed into liquor NH3 (ii) for manufacture of NH3 by the Haber’s process.
(iii) for manufacture of HNO3 by the Birkeland-Eyde process.
3Cl2 + 2NH3  N2 + 6HCl
(iv) for manufacture of nitrolim.
6NH3 + 6HCl  6NH4Cl
4.2 Compounds of Nitrogen
3Cl2 + 8NH3  N2 + 6NH4Cl
4.2.1 Ammonia:
In this method NH3 conc. should not be lowered down
Preparation:
beyond a particular limit.
(i) By the action of any base or alkali on any ammonium salt :
3Cl2 + NH3  NCl3 + 3HCl 
NH4Cl + NaOH  NH3 + NaCl + H2O
(Trimendously explosive) 
Industrial Methods of Preparation: (NH4)2SO4 + 2NaOH  2NH3 + Na2SO4 + 2H2O
(i) From liquefied air by fractional distillation: The bp of N2 is – 
NH4NO3 + NaOH  NH3 + NaNO3 + H2O
196oC and that of oxygen is –183oC and hence they can be 
separated. (NH4)3PO4 + 3NaOH  3NH3 + Na3PO4 + 3H2O
(ii) From producer gas from furnaces: Producer gas is a mixture 
(NH4)2SO4 + CaO  2NH3 + CaSO4 + H2O
of CO and N2. When the mixture of CO and N2 is passed over
This is a general method and is used as a test for ammonium
heated CuO, the CO gas is oxidized to CO2 which is absorbed
salts.
in alkalies & N2 remains which is collected in gas cylinders.
Properties: (ii) By the hydrolysis of metal nitrides like AlN or Mg3N2.
(i) N2 is a colourless, odourless gas insoluble in water. AlN + NaOH + H2O  NaAlO2 + NH3
(ii) It is non-polar covalent and neutral molecule. (iii) From oxides of nitrogen: When oxides of nitrogen are mixed
(iii) It is neither combustible nor a supporter of combustion. with H2 and the mixture is passed over heated platinum
(iv) It is absorbed by heated Mg and Al. The nitrides formed catalyst, NH3 gas is evolved.
thus react with water to form NH3. 2NO + 5H2  2NH3 + 2H2O
3Mg + N2  Mg3N2 (+ 6H2O)  3Mg(OH)3 + 2NH3 2NO2 + 7H2  2NH3 + 4H2O
2Al + N2  2AlN (+ 6H2O)  2Al(OH)3 + 2NH3 (iv) From organic amides: When an organic amide is heated with
NaOH solution ammonia is evolved.
(v) Reaction with H2: At 200 atm and 500oC, and in the presence
of iron catalyst and molybdenum promoter, N2 combines with 
CH3CONH2 + NaOH  CH3COONa + NH3
H2 reversibly to form ammonia. The process is called Haber’s
(v) From nitrates and nitrites: When a metal nitrate or nitrite is
Process and is the industrial method of manufacturing
heated with zinc powder and concentrated NaOH solution
ammonia. The reaction is exothermic.
ammonia is obtained. The reactions are
N2 + 3H2  2NH3
NaNO3 + 7NaOH + 4Zn  4Na2ZnO2 + NH3 + 2H2O
(vi) Reaction with oxygen: When air free from CO2 and moisture
is passed over an electric arc at about 2000 K, nitric oxide is NaNO2 + 3Zn + 5NaOH  3Na2ZnO2 + H2O + NH3
formed. This reaction is endothermic. Industrial Methods of Preparation:
N2 + O2  2NO (i) Haber’s process:
(vii) Reaction with CaC2 and BaC2: At 1100oC, these carbides react 500 C, 200atm
with N2 forming CaCN2 and Ba(CN)2 respectively. N2 + 3H2            2NH3
Iron oxide  K O &Al O
2 2 3

CaC2 + N2 +  CaCN2 + C (nitrolim, a fertilizer) (ii) From destructive distillation of coal: When coal is heated at
 a high temperature in an iron retort and the distillate is bubbles
BaC2 + N2 +  Ba(CN)2 in water, three substances are obtained:
CaCN2 reacts with H2O in the soil to produce NH3 gas. NH3 (a) Tarry black pitch, (b) Liquor ammonia & (c) Coal gas
gas is converted by the nitrating bacteria present in soil into The liquor ammonia is a concentrated solution of ammonia and
nitrates. (The nitrates are readily absorbed by the plants and ammonium salts. When heated it gives out ammonia. When all
meet their requirement of the element nitrogen.) the free NH3 is obtained, the residual liquid is heated with Ca(OH)2
Uses when ammonium salts get decomposed to liberate further quantity
(i) for providing an inert atmosphere during many industrial of ammonia.
processes where presence of air or O2 is to be avoided.
SCAN CODE
(iii) Cyanamide process:
MCl 2  2NH 4 OH  M  OH  2  2NH 4 Cl
CaO + 2C + N2 2000ºC CaCN + CO  white 
 
2  
CaCN2 + 3H2O  CaCO3 + 2NH3 (M = Mg, Ca, Sr, Ba, Ra, Sn, Pb)
Properties: (viii) When NH4OH solution is added to AgNO3 solution, a brown
(i) Colourless gas lighter than air. Being basic in nature turns ppt. is obtained
red litmus blue. It acts as a Lewis base
2AgNO3  2NH 4 OH  Ag 2 O  2NH 4 NO 3  H 2 O
(ii) Highly soluble in water. The solution is called ammonium  brown 
 
hydroxide solution.  
Brown ppt of silver oxide formed dissolves in excess ammo-

(iii) Na + NH3 
 NaNH2 + 1/2 H2 nium hydroxide forming a soluble complex
Amides decompose back with water to form NH3 and NaOH. Ag2O + 2NH4OH  [Ag(NH3)2]OH + 2H2O
Pt ,550ºC 4NO + 6H O
(iv) 4NH3 + 5O2  (ix) 2NH3 + CO2 + H2O  (NH4)2CO3
 2
(Ostwald’s process of manufacturing HNO3) high pressure

2NH3 + CO2   NH2CONH2 (urea) + H2O
(v) When Cl2 is bubbled in liquor ammonia, nitrogen gas is 
formed. Uses:
8NH3 + 3Cl2  6NH4Cl + N2 (i) Used as a refrigeration fluid.
With excess of Cl2 it is converted to an explosive substance, (ii) For the production of ammonium fertilizers such as ammonium
nitrogen trichloride. sulphate, ammonium phosphate, ammonium nitrate, urea etc.
(iii) For removing grease because NH4OH dissolves grease.
NH3 + 3Cl2  NCl3 +3HCl
(iv) For manufacture of HNO3 by the Ostwald process.
(vi) Cupric oxide and PbO are reduced to metal when NH3 is
(v) As a laboratory reagent.
passed over heated CuO and PbO.
(vi) In the production of artificial rayon, silk, nylon etc.
3CuO + 2NH3  3Cu + 3H2O + N2
4.2.2 Oxides of Nitrogen:
3PbO + 2NH3  3Pb + 3H2O + N2 Nitrogen forms a number of oxides, N2O, NO, N2O3, NO2 or N2O4
M  NO3  2  2NH 4 OH  M  OH  2  2NH 4 NO3 and N2O5, and also very unstable NO3 and N2O6. All these oxides
(vii)  white  of nitrogen exhibit p-p multiple bonding between nitrogen and
 
 
oxygen.
Oxides of Nitrogen
Name Formula Colour Remarks

Nitrous oxide N2O Colourless (g) Neutral ,+ 1 oxidation state
Nitric oxide NO Colourless (g) Neutral ,+ 2 oxidation state
Dinitrogen trioxide N2O3 Dark blue (s) Acidic ,+ 3 oxidation state
Nitrogen dioxide NO2 Brown (g) Acidic , + 4 oxidation state
Dinitrogen tetroxide N2O4 Colourless (s) Extensively dissociated to NO2 as gas and partly
dissociated as liquid, acidic, + 4 oxidation state
Dinitrogen pentoxide N2O5 Colourless (s) Unstable as gas; ionic solid NO+2,
NO3– , acidic, +5 oxidation state
Preparation:
(i) N2O is obtained generally by heating NH4NO3 with caution. these two oxides.
(iii) NO2 can be prepared by reduction of concentrated HNO3
NH4NO3  N2O + 2H2O
with Cu or by heating heavy metal nitrates.
(ii) N2O3 is obtained as an intense blue liquid or a pale blue solid
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O ;
on cooling an equimolar mixture of NO and NO2 to 250 K.
673 K
NO + NO2  N2O3 2Pb(NO3)2  2PbO + 4NO2 + O2
On warming, its colour fades due to its dissociation into
SCAN CODE
(iv) N2O5 is an anhydride of HNO3. It is best prepared by Properties:
dehydrating HNO3 by P4O10 at low temperatures. (i) It is an unstable, weak acid which is known only in aqueous
250K  2N O + 4HPO solution.
4HNO3 + P4O10  2 5 3
(ii) On trying to concentrate, the acid decomposes as given
Properties: below.
Oxides of nitrogen are all oxidizing agents, N2O even supporting 3HNO2  HNO3 + 2NO + H2O
the combustion of S and P. NO which is thermally more stable,
(iii) Nitrous acid and nitrites are good oxidizing agents and
supports the combustion of Mg and P but not of S. Sulphur flame
convert iodides to iodine, ferrous salts to ferric, stannous to
is not hot enough to decompose it.
stannic and sulphites to sulphates eg.
N2O is isoelectronic with CO2 and also has a linear structure.
2KI + 2HNO2 + 2HCl  2H2O + 2NO + 2KCl + I2
However, unlike CO2, N2O has a small dipole moment.
(iv) With strong oxidizing agents like KMnO4 nitrous acid and
NO has a total of 15 electrons. It is impossible for all of them to be
nitrites function as reducing agents and get oxidized to
paired and hence this is an odd electron molecule. In the gaseous
NO3- ions:
state, it is paramagnetic. However, the liquid and the solid states
are diamagnetic because loose dimmers are formed canceling out 2KMnO4 + 5KNO2 + 6HCl2MnCl2 + 5KNO3 + 3H2O + 2KCl
the magnetic effects of unpaired electrons. (v) Nitrite ion is a good coordinating agent. Both nitrogen and
• N2O : oxygen have lone pairs capable of forming coordinate bond
with metal ions. Nitrite ion can coordinate either through N
(a) Reduction : Cu(hot) + N2O  CuO + N2
or through O.(It is an ambidentate ligand) This generates
(b) Oxidation: 2KMnO4 + 3H2SO4 + 5N2O  K2SO4 + linkage isomerism. Analogous organic derivatives are also
2MnSO4 + 3H2O + 10NO known, the nitrites, RONO and the nitro compounds RNO2
(c) Supporter of combustion : Mg + N2O  MgO + N2 where R is any alkyl or aryl group.
• NO : 4.2.3.2 Nitric Acid (HNO3):
(a) Supporter of combustion : S + 2NO  SO2 + N2 Preparation:
(b) Oxidising properties (Reduction of NO) : (i) Laboratory method:
Pt  black 2NH + 2H O
5H2 + 2NO  NaNO3 + H2SO4  NaHSO4 + HNO3
 3 2
(ii) HNO3 is now almost exclusively manufactured by the
(c) Reducing properties (oxidation of NO) : Ostwald process. In this process NH3 is catalytically oxidized
2NO + X2  2NOX to NO over a Pt-Rh catalyst at 1200K.
N2O3 : It is anhydride of HNO2 : 2HNO2  N2O3 + H2O 4NH3 + 5O2  4NO + 6H2O H = –904 kJ
NO2 : It behaves both like HNO2 and HNO3. It behaves like About 96 to 98 % of NH3 is converted into NO. The mixture
HNO2 as a reducing agent and like HNO3 as an oxidising is then diluted with air. NO combines with O2 to give NO2
agent according to following reactions respectively. which is absorbed in water to give HNO3 and NO, which is
2KMnO4 + 3H2SO4 + 10NO2 + 2H2O  K2SO4 + 2MnSO4 then recycled.
+ 10HNO3 2NO + O2  2NO2
SO2 + H2O + NO2  H2SO4 + NO 3NO2 + H2O  2HNO3 + NO
 Nitric acid can be concentrated to 68 % by distillation, when
N2O5 : 2N2O5  2N2O4 + O2
a constant boiling mixture is formed. More concentrated
4.2.3 Oxyacids of Nitrogen: acid can be made by distilling the mixture with concentrated
sulphuric acid.
4.2.3.1 Nitrous Acid (HNO2): Properties:
Preparation: (i) Pure nitric acid is colourless liquid (bp 359oC). It is a strong
(i) By acidifying an aqueous solution of a nitrite acid and is almost completely dissociated into ions in
Ba(NO3)2 + H2SO4  2HNO2 + BaSO4 solution.
(ii) By passing an equimolar mixture of NO and NO2 into water: (ii) Thermal stability
NO + NO2 + H2O  2HNO2 
4HNO3  2H2O + 4NO2 + O2
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(iii) Oxidising properties Mg + 2HNO3  Mg(NO3)2 + H2
Mn + 2HNO3  Mn(NO3)2 + H2
2HNO3 (conc.)  H2O + 2NO2 + [O]
• As concentrated nitric acid (80%) behaves as an oxidizing
2HNO3 (dilute)  H2O + 2NO + 3[O] agent and metals such as Al, Fe, Cr etc are rendered passive
due to the formation of a tenacious layer of insoluble oxide
(a) Oxidises H2S to sulphur
on the metal surface.
H2S + 2HNO3 (conc.)  2H2O + 2NO2 + S  • Noble metals such as Au, Pt, Rh, and Ir are not attacked by
nitric acid. However a 1:3 mixture of conc.
3H2S + 2HNO3 (dilute)  4H2O + 2NO + 3S
HNO3 and conc. HCl known as aqua regia dissolves Au and
(b) Oxidises SO2 to H2SO4 Pt as it contains free(atomic) chlorine:
SO2 + 2HNO3 (conc.)  H2SO4 + 2NO2  HNO3 + 3HCl  2H2O + 2Cl + NOCl
Au + 3Cl + HCl  HAuCl4
3SO2 + 2H2O + 2HNO3 (dilute)  3H2SO4 + 2NO Pt + 4Cl + 2HCl  H2PtCl6
Similarly oxidises ferrous salts to ferric salts, halogen acids Brown Ring Test:
to respective halogens. 2HNO3 + 3H2SO4 + 6FeSO4  3Fe2(SO4)3 + 2NO + 4H2O
(iv) Reaction with non-metals. FeSO4 + NO + 5H2O  [Fe(H2O)5 NO]SO4
C + 4HNO3  H2CO3 + H2O + 4NO2
5. GENERAL PROPERTIES AND COMPOUNDS OF
S + 6HNO3  H2SO4 + 2H2O + 6NO2
PHOSPHORUS
2 + 10HNO3  2HO3 + 4H2O + 10NO2 ; It is a very reactive non-metal. It catches fire in air. It occurs in
nature in the form of stable phosphates. (Animal bones also
P + 5HNO3  H3PO4 + H2O + 5NO2
contain calcium phosphate (58 %)).
These reactions are given with conc. HNO3 .
Allotropic forms of Phosphorus:
(v) Reaction with metals: Metals that are more electropositive
(i) White or yellow phosphorus (P4):
than hydrogen
Preparation:
(a) Action on zinc or Fe :

2Ca3(PO4)2 + 10C + 6SiO2  6CaSiO3 + 10CO + P4(s)
Zn + 4HNO3 (conc.)  Zn(NO3)2 + 2H2O + 2NO2
Properties: It is white-to-transparent and soft waxy solid. Its mp
4Zn + 10HNO3 (dil.)  4Zn(NO3)2 + 5H2O + N2O and bp are 44°C and 287°C respectively. It is soluble in CS2 but
insoluble in water. It glows in dark due to slow oxidation producing
4Zn + 10HNO3 (v.dil.)  4Zn(NO3)2 + NH4NO3 + 3H2O
yellowish-green light.
4Mg + 10HNO3 (v.dil.)  4Mg(NO3)2 + NH4NO3 + 3H2O P4 + 5O2  P4O10
(b) Action on tin : White phosphorus is poisonous. It turns yellow after some time;
it is called yellow phosphorus. It undergoes oxidation in the
Sn + 4HNO3 (conc.)  H2SnO3 + 4NO2 + H2O presence of air which slowly raises its temperature and due to its
low ignition temperature (~ 30ºC) after a few moments it catches
4Sn + 10HNO3 (dil.)  4Sn(NO3)2 + NH4NO3 + 3H2O
fire spontaneously.
(c) Action on lead :
Pb + 4HNO3 (conc.)  Pb(NO3)2 + 2NO2 + 2H2O
3Pb + 8HNO3 (dil.)  3Pb(NO3)2 + 2NO + 4H2O

Metals which are less electropositive than hydrogen.
(i) Action on copper Structure of white phosphorus
Cu + 4HNO3 (conc.)  Cu(NO3)2 + 2NO2 + 2H2O (ii) Red phosphorus:
Preparation: When white phosphorus is heated in the atmosphere
3Cu + 8HNO3 (v.dil)  3Cu(NO3)2 + NO + 4H2O
of CO2 or coal gas at 573 K red phosphorus is prodouced. This
red phosphorus may still contain some white phosphours which
SCAN CODE
is removed by boiling the mixture with NaOH where white but on heating.
phosphorus is converted into PH3 gas but red phosphorus remains (ii) Action of non-metals: When heated with non-metals
inert. phosphorus forms compounds PX3, PX5, P2S3 and P2S5.
P4 + 3NaOH + 3H2O  PH3(g) + 3NaH2PO2 2P + 3X2  2PX3
It is also prepared by heating white phosphorus with a few crys 2P + 5X2  2PX5 (where X = Cl, Br, and I.)
tals of iodine catalyst at 250oC under high pressure in absence of (iii) Action with metals: Alkali metals when heated with white
air. phosphorus in vacuum produce alkali metal phosphide, which
Properties : It is a red crystalline solid. It is less reactive than react with water to form phosphine gas.
white phosphorus and does not dissolve in liquid CS2. It does not 
3M + P  M3P
catch fire at room temperature because its ignition temperature is
260oC. 
M3P + 3H2O  3MOH + PH3 {where M = Na, K etc.}
It is a polymeric substance forming linear chains like this.
(iv) Action of NaOH: When white phosphorus is heated with
NaOH solution, phosphine gas is evolved.
P4 + 3NaOH + 3H2O  3NaH2PO2 + PH3

(v) Action of conc. HNO3 : When heated with conc. HNO3,
phosphorus is oxidized to H3PO4.
Structure of Red phosphorus
(iii) Black phosphorus: It has two forms -black phosphorus P + 5NHO3  H3PO4 + 5NO2 + H2O
and -black phosphorous (vi) Action of conc. H2SO4: When heated with conc. H2SO4
(a) -black phosphorous phosphorus is oxidized to H3PO4.
insulated  
2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
P(red) 
tube803K P(-black)
Conversion of white phosphorus to red phosphorus and red phos-
-black phosphorous structure is not definite and is non phorus to white phosphorus.
conductor of electricity. Heat in presence of 2 catalyst at 250oC and high pressure in ab-
(b) -black phosphorous sence of air
473 K White phosphorus  Red phosphorus


P(white) High 
pressure P(-black) Heat above 250°C in presence of inert gas and condense in water
-black phosphorous is an electrical conductor resembling 5.1 Compounds of Phosphorus
graphite in this respect and also in its flakiness and luster. It 5.1.1 Phosphine:
is insoluble in CS2. It has a layered structure like graphite.
Preparation:
(i) By heating white phosphorus with NaOH solution in
presence of coal gas. Phosphine gas is collected by the
downward displacement of water.

P4 + 3NaOH + 3H2O  3NaH2PO2 + PH3
Coal gas is used to prevent oxidation of phosphine. The phsophine
gas is contaminated with a combustible gas P2H4. It is separated
from PH3 by passing the gaseous mixture through a freezing mixture
Structure of Black phosphorus whereupon P2H4 condenses to a liquid and PH3 is collected by the
Chemical Properties of Phosphorus: downward displacement of air. Pure PH3 does not burn in air.
(i) Action of air: White phosphorus burns in air to form (ii) By the action of alkalies on phosphonium salts:
phosphorus trioxide and pentoxide.

P4 + 5O2  2P2O5 PH4I + NaOH  NaI + PH3 + H2O
P4 + 3O2  2P2O3 (iii) By the action of dil. HCl or dil. H2SO4 on metal phosphides.
Red and other forms of phosphorus also burn in air or oxygen Na3P + 3HCl  3NaCl + PH3
SCAN CODE
(ii) It dissolves in cold water to form phosphorus acid. It is thus
AlP + 3HCl  AlCl3 + PH3 the anhydride of phosphorus acid.
2Na3P + 3H2SO4  3Na2SO4 + 2PH3 P2O3 + 3H2O  2H3PO3
Properties: (iii) It dissolves in hot water liberating PH3
(i) It is a colourless gas with a smell of rotten fish and is neutral 2P2O3 + 6H2O  3H3PO4 + PH3
to litmus paper, It is heavier than air and only slightly soluble (iv) It slowly gets oxidized in air to form P2O5
in water, It is a poisonous gas and acts as a Lewis base. P2O3 + O2  P2O5
(ii) Action of chlorine: It reacts with Cl2 to form PCl5. 5.1.2.2 Phosphorus Pentoxide (P2O5) :
PH3 + 4Cl2  PCl5 + 3HCl Preparation : It is obtained by burning phosphorus in air.
Similar reaction occurs between heated phosphine and Br2 P4 + 5O2  P4O10
and I2 vapours. Properties:
(iii) Reaction with hydrogen halides: When PH3 is bubbled in (i) It is a white powder acidic in nature and is the anhydride of
solution of HX, phosphonium halides are formed. orthophosphoric acid. Its empirical formula is P2O5 and its
PH3 + HX  PH4X molecular formula is P4O10.
(iv) Action on CuSO4 solution: When PH3 is bubbled in acidic (ii) It sublimes on heating at 250oC.
solution of copper sulphate, a black precipitate of copper (iii) Action of water: It dissolves in water with hissing sound
phosphide is formed. forming metaphosphoric acid and finally orthophosphoric
3CuSO4+2PH3 Cu3P2 {black} + 3H2SO4 acid.
(v) Reaction with AgNO3 solution: When PH3 gas is bubbled in
P4O10 + 2H2O  4HPO3 , HPO3 + H2O  H3PO4
a solution of AgNO3, a yellow precipitate of silver phosphide,
(iv) Dehydrating power: It dehydrates conc. H2SO4 and conc.
Ag3P, is first formed which later decomposes to black Ag.
HNO3 to SO3 and N2O5 respectively.
3AgNO3 + PH3  Ag3P (yellow) + 3HNO3
distillation  2HPO + N O
2HNO3 + P2O5  3 2 5
Ag3P + 3AgNO3 + 3H2O  6Ag + 3HNO3 + H3PO3
(vi) Reaction with mercuric chloride solution: When mercuric distillation  2HPO + SO
H2SO4 + P2O5  3 3
chloride solution is treated with PH3 gas, a brownish black
precipitate of mercuric phosphide is formed. Uses:
(i) For drying acidic gases
3HgCl2 + 2PH3  Hg3P2(brownish-black) + 6HCl
(ii) As a dehydrating agent
Samples of PH3 can be dried using quick lime, or NaOH sticks.
(iii) For the preparation of SO3 and N2O5
It cannot be dried by conc. H2SO4 because of its reaction
with it. (iv) For the preparation of phosphoric acid
Uses: 5.1.3 Oxy-Acids of Phosphorus
It is used in making smoke signals and producing smoke 5.1.3.1 Phosphorus Acid (H3PO3)
screens in battle-fields. Preparation:
5.1.2 Oxides of Phosphorus (i) By dissolving P2O3 in water:
5.1.2.1 Phosphorus Trioxide (P2O3) P2O3 + 3H2O  2H3PO3
Preparation: It is prepared by burning phosphorus in a limited (ii) By hydrolysis of PCl3 with water:
supply of oxygen when gaseous P4O10 and P4O6 are formed. On
lowering the temperature using a condenser, P4O6 remains in PCl3 + 3H2O  H3PO3 + 3HCl
gaseous form whereas P4O10 condenses as a solid which is stopped The solution containing H3PO3 and HCl is heated to 180oC
by glasswool. On passing the remaining gaseous mixture through and HCl gas is driven out. The resulting solution on
freezing mixture, it converts into colourless crystals of P 4O6. crystallization gives white crystals of H3PO3.
Properties: Properties:
(i) It is colourless crystalline solid having mp 23.8 C and bp
o (i) It is a white crystalline solid, soluble in water and having
178oC. melting point of 74oC.
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(ii) It is a weak acid and a reducing agent

PCl5 + 4H2O  H3PO4 + 5HCl
(iii) When neutralized with bases or alkalies, it forms neutral salts
called phosphites which are unstable. (iii) By heating white phosphorus with conc. HNO3:
H3PO3 + 3NaOH  Na3PO3 + 3H2O P + 5HNO3  H3PO4 + 5NO2 + H2O
Its basicity is 2 because it has only two replaceable H atoms. Properties:
The third H atom is not replaceable because it is not (i) Pure orthophosphoric acid is a white crystalline solid highly
connected to oxygen. soluble in water having melting point of 42oC. It is a weak

(iv) 4H3PO3  3H3PO4 + PH3 (Disproportionation) acid. It forms two acid salts and one normal salt.NaH2PO4 is
sodium dihydrogen phosphate,Na 2HPO 4 is disodium
(v) H3PO3 + 3PCl5  PCl3 + 3POCl3 + 3HCl hydrogen phosphate & Na3PO4 is sodium orthophosphate.
(vi) It is a strong reducing agent: (ii) Action of heat:
2AgNO3 + H3PO3 + H2O  2Ag + 2HNO3 + H3PO4 220ºC H P O (pyrophosphoric acid)
H3PO4  4 2 7
2HgCl2 + H3PO3 + H2O  Hg2Cl2 + 2HCl + H3PO4 316ºC HPO (metaphosphoric acid)
H4P2O7  3
5.1.3.2 Orthophosphoric Acid (H3PO4) (iii) Neutralization with alkalies or bases:
Preparation:
NaOH  NaOH 
(i) By heating calcium phosphate with conc. H2SO4 H3PO4  
H O NaH2PO4 (pri. phosphate) H O
2 2
Ca3(PO4)2 + 3H2SO4  2CaSO4 + 2H3PO4 NaOH 

CaSO4 is insoluble. Solution of H3PO4 is separated from NaHPO4 (sec. phosphate) H O Na3PO4
2
CaSO4. It is then concentrated by evaporating it at 180oC (tert. phosphate)
and dehydrated by conc. H 2SO 4 placed in a vacuum
•   NaPO + H O
NaH2PO4 
dessicator cooled by freezing mixture. White crystals of 3 2
H3PO4 are thus formed.

(ii) By hydrolysis of PCl5:
Oxoacids of Phosphorus
Name Formula Oxidation Characteristic Preparation

State of Bonds and their
Phosphorus Number
Hypophosphorous H3PO2 +1 One P–OH, Two P – H, One P =O White P4 + alkali
(Phosphinic)
Orthophosphorous H3PO3 +3 Two P – OH, One P – H, One P = O P 2O 3 + H 2O

(Phosphonic)
Pyrophosphorous H4P2O5 +3 Two P – OH, Two P – H, Two P = O PCl3 + H3PO3
Hypophosphoric H4P2O6 +4 Four P – OH, Two P = O, One P – P Red P4 + alkali
Orthophosphoric H3PO4 +5 Three P – OH, One P = O P4O10 + H2O
SCAN CODE
Name Formula Oxidation Characteristic Preparation

State of Bonds and their
Phosphorus Number
Pyrophosphoric H4P2O7 +5 Four P – OH heat phosphoric acid
Two P = O
One P – O – P
Metaphosphoric (HPO3)n +5 Three P – OH Phosphorous acid + Br2, heart in
Three P = O a scaled cube
Three P – O – P
Oxoacids of Phosphorus
6. USES OF GROUP 15 ELEMENTS 7.Introduction of Group 16 Elements

(i) The main use of dinitrogen is in the manufacture of ammonia
(Oxygen Family)
and other industrial chemicals containing nitrogen, (e.g.,
calcium cyanamide). It also finds use where an inert Oxygen, sulphur, selenium, tellurium and polonium constitute
atmosphere is required (e.g., in iron and steel industry, inert group 16 of the periodic table. This is sometimes known as group
diluent for reactive chemicals). Liquid dinitrogen is used as of chalcogens. The name is derived from the Greek word for brass
a refrigerant to preserve biological materials, food items and and points to the association of sulphur and its congeners with
in cryosurgery. copper. Most copper minerals contain either oxygen or sulphur
and frequently the other members of the group.
(ii) Ammonia is used to produce various nitrogenous fertilisers
(ammonium nitrate, urea, ammonium phosphate and Occurrence :Oxygen is the most abundant of all the elements on
ammonium sulphate) and in the manufacture of some the earth. Oxygen forms about 46.6% by mass of earth’s crust .
inorganic nitrogen compounds, the most important one being Dry air contains 20.946% oxygen by volume.
nitric acid. Liquid ammonia is also used as a refrigerant. However, the abundance of sulphur in the earth’s crust is only
0.03-0.1%. Combined sulphur exists primarily as sulphates such
as gypsum CaSO4.2H2O, epsom salt MgSO4 .7H2O, baryta BaSO4
SCAN CODE
and sulphides such as galena PbS, zinc blende ZnS, copper pyrites 7.4 Electron Gain Enthalpy
CuFeS2 . Traces of sulphur occur as hydrogen sulphide in Because of the compact nature of oxygen atom, it has less negative
volcanoes. electron gain enthalpy than sulphur.
7.1 Electronic Configuration 7.5 Electronegativity
The elements of group 16 have six electrons in the outermost Next to fluorine, oxygen has the highest electronegativity value
shell and have ns2 np4 general electronic configuration. amongst the elements. Within the group, electronegativity
7.2 Atomic and Ionic Radii decrease with an increase in atomic number. This implies that the
Due to increase in the number of shells , atomic and ionic radii metallic character increase from oxygen to polonium.
increase from top to bottom in the group. The size of oxygen 8. PHYSICAL PROPERTIES OF GROUP 16 ELEMENTS
atoms is however, exceptionally small. Oxygen and sulphur are non-metal, selenium and tellurium
7.3 Ionisation Enthalpy metalloids, whereas polonium is a metal. Polonium is radioactive
Ionisation enthalpy decrease down the group. It is due to increase and is short lived (Half-life 13.8 days). All these element exhibit
in size. However, the element of this group have lower ionisation allotropy. The melting and boiling points increase with an increase
enthalpy values compared to those of group 15 in the in atomic number down the group. The larger difference between
corresponding periods. This is due to the fact that group 15 element the melting and boiling points of oxygen and sulphur may be
have extra stable half-filled p orbitals elelctronic configurations. explained on the basis of their atomicity.
Physical Properties of Group 16
Element Oxygen (O) Sulphur (S) Selenium (Se) Teryllium (Te)

Atomic Number 8 16 34 52
Atomic Mass 16 32.06 78.96 127.6
Electronic configuration [He]2s22p4 [Ne]3s23p4 [Ar]3d104s24p4 [Kr]4d105s25p4
Covalent Radius/pm 74 103 119 142
Ionic Radius X /pm
–2
140 184 198 221
Ionization enthalpy (KJ mol ) I
–1
1314 1000 941 869
Ionization enthalpy (KJ mol–1) II 3388 2251 2045 1790
Electronegativity 3.5 2.44 2.48 2.01
Density/[g cm (293 K)]
–3
1.32 2.06 4.19 6.25
Melting point/K 54 393 490 725
Boiling point/K 90 718 958 1260
9. CHEMICAL PROPERTIES OF GROUP 16 ELEMENTS Anomalous behaviour of oxygen: The anomalous behaviour of
oxygen, like other member of p-block present in second period is
The elements of group 16 exhibit a number of oxidation states.
due to its small size and high electronegativity. One typical example
The stability of -2 oxidation state decreases down the group.
of effects of small size and high electronegativity is the presence
Polonium hardly shows -2 oxidation states. Since electronegativity
of strong hydrogen bonding in H2O which is not found in H2S.
of oxygen is very high, it shows only negative oxidation states as
-2 except in the case of OF2 where its oxidation states is + 2. Other The absence of d orbitals in oxygen limits its covalency to four
elements of the group exhibit + 2 + 4 + 6 oxidation states but + 4 and in practice, rarely exceeds two. On the other hand, in case of
and + 6 are more common. Sulphur, selenium and tellurium usually other elements of the group, the valence shell can be expanded
show + 4 oxidation in their compounds with oxygen and +6 and covalence exceeds four.
oxidations state with fluorine. The stability of +6 oxidation state 9.1 Reactivity with Hydrogen
decreases down the group and stability of + 4 oxidation state All the elements of group 16 form hydrides of the type H2E (E = S,
increases (inert pair effect). Bonding in + 4 and + 6 oxidation Se., Te, Po). Some properties of hydrides are given in Table. Their
states are primarily covalent. acidic character increases from H2O to H2Te. The increase in
SCAN CODE
acidic character can be explained in terms of decrease in bond (H- 9.2 Reactivity with Oxygen
E) dissociation enthalpy down the group. Owing to the decrease All these elements form oxides of the EO2 and EO3 types where E
in bond (H-E) dissociation enthalpy down the group, the thermal = S, Se, Te or Po. Ozone (O3) and sulphur dioxide (SO2) are gases
stability of hydrides also decreases from H2O to H2Po. All the while selenium dioxide (SeO2) is solid. Reducing property of dioxide
hydrides except water possess reducing property and this decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an
character increases from H2S to H2Te. oxidising agent. Besides EO2 type sulphur, selenium and tellurium
also form EO3 type oxide (SO3, SeO3, TeO3). Both types of oxides
are acidic in nature.
Properties of Hydrides of Group 16 Elements
Property H 2O H2S H 2 Se H2Te

m.p./K 273 188 208 222
b.p./K 373 213 232 269
H-E distance/pm 96 134 146 169
HEH angle (°) 104 92 91 90
fH/kJ mol–1 –286 –20 73 100
diss H(H–E)/kJ mol–1 463 347 276 238
Dissociation constanta 1.8×10–16 1.3×10–7 1.3×10–4 2.3×10–3
9.3 Reactivity Toward Halogens

(ii) high electronegativity and
Elements of group 16 form a larger number of halides of the type
(iii) non-availability of d-orbitals.
EX6, EX4 and EX2 where E is an element of the group and X is an
halogen. The stabilities of the halides decrease in the order F > Cl Preparation:
> Br > l. Amongst hexahalides, hexafluorides are the only stable (a) Dioxygen
halides. All hexafluorides are gaseous in nature. They have (i) By thermal decomposition of oxides of metals.
octahedral structure. Shulphur hexafluoride SF\6 is exceptionally 450 C  2 Hg + O
2 HgO 
stable for steric reasons. 2
Amongst terrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid 350 C  4 Ag + O
2 Ag2O  2
These fluorides have sp3d hybridisation and thus, have trigonal
bipyramidal structure in which one of the equatorial position is   Mn O + O
3 MnO2  3 4 2
occupied by a lone pair of electrons. This geometry is also regarded   6 PbO + O
2 Pb3O4 
as see - saw geometry. 2
All elements except selenium form dichlorides and dibromides. (ii) By thermal decomposition of oxygen rich compounds.
These dihalides are formed by sp3 hybridisation and thus have   2NaNO + O
2 NaNO3  2 2
tetrahedral structure. The well known monohalides are dimeric in
nature, Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These   2 KCl + 3O (laboratory method)
2 KClO3  2
dimeric halides undergo disproportionation as given below:
  4 K CrO + 2 Cr O + 3O
4 K2Cr2O7 
2Se2Cl2  SeCl4 + 3Se. 2 4 2 3 2
10. GENERAL PROPERTIES AND COMPOUNDS 2 KMnO4    K MnO + MnO + O

2 4 2 2
OF OXYGEN (iii) By the action of conc. H2SO4 on MnO2.

10.1 Dioxygen (O2)
2 MnO2 + 2H2SO4  2 MnSO4 + 2H2O + O2
It differs from the remaining elements of the VIth group because of
(iv) By the action of water on Na2O2.
the following properties.
(i) small size 2 Na2O2 + 2 H2O  4 NaOH + O2
SCAN CODE
(v) By the action of conc. H2SO4 on KMnO4 or K2Cr2O7.

Cr2O3 + 2 NaOH  Na2Cr2O4 + H2O
4 KMnO4 + 6 H2SO4  2 K2SO4 + 4MnSO4 + 6H2O + 5O2
Cr2O3 + 3 H2SO4  Cr2(SO4)3 + 3 H2O
2 K2Cr2O7 + 8H2SO4  2 K2SO4 + 2Cr2(SO4)3 + 8H2O + 10.2.4 Mixed Oxides
3O2
(vi) By Brins process: They behave as mixture of two simple oxides, e.g., Pb3O4
(2PbO + PbO2), Fe3O4 (FeO + Fe2O3), Mn3O4 (2 MnO + MnO2)
500 C  2BaO
2 BaO + O2(air)  2 10.2.5 Peroxides
800 C  2 BaO + O
2 BaO2 
They react with dilute acids and form H2O2, e.g., Na2O2, K2O2,
2 BaO2 etc.
(vii) From air: Oxygen is obtained by liquification of air and then
Na2O2 + H2SO4  Na2SO4 + H2O2
its fractional distillation.
They react with water forming O2 .
Properties: Colourless , odourless and tasteless gas. It is para-
magnetic and exhibits allotropy. Three isotopes of oxygen are Na2O2 + H2O  2NaOH + 1/2O2
16 17 18 10.2.6 Dioxides
8O , 8O and 8O . Oxygen does not burn but is a strong
supporter of combustion. Like peroxide, they contain excess of oxygen but do not yield
H2O2 with dil. acids e.g. PbO2, MnO2 etc.
Uses:
They evolve Cl2 with conc. HCl and O2 with conc. H2SO4.
Oxygen mixed with helium or CO2 is used for artificial respiration,
Liquid oxygen is used as oxidising agent in rocket fuels and Oxy- MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O;
gen is used for production of oxy-hydrogen or oxy-acetylene
2MnO2 + 2H2SO4  2MnSO4 + O2 + 2H2O
flames employed for cutting and welding.
10.2.7 Super Oxides
10.2 Oxides They contain O2– ion, e.g., KO2 , RbO2 and CsO2. These oxides
10.2.1 Acidic Oxides react with water forming H2O2 and O2
They dissolve in water forming oxyacids , e.g., CO2, SO2 , SO3, 10.2.8 Sub Oxides
N2O5 , N2O3 , P4O6 , P4O10, Cl2O7, CrO3 , Mn2O7 , V2O5.
They contain less oxygen than expected from the normal valency
Cl2O7 + H2O  2 HClO4 of the elements e.g., C3O2, N2O, Pb2O, Hg2O etc.
Mn2O7 + H2O  2 HMnO4
C3O2  O  C
sp
CCO
sp sp
10.2.2 Basic Oxides 10.3 Ozone (O3)

They either dissolve in water to form alkalies or combine with Preparation:It is prepared by passing silent electric discharge
acids to form salts and water or combine with acidic oxides to through pure and dry oxygen
form salts; e.g., Na2O, CaO. CuO, FeO, BaO etc. 3O2 2O3 H = + 142 kJ/mole
Mixture obtained contains 5-10% ozone by volume and this mix-
Na2O + H2O  2 NaOH
ture is called ozonised oxygen. The apparatus used for this is
CaO + H2O  Ca(OH)2 called as ozoniser.
Properties :
CuO + H2SO4  CuSO4 + H2O (i) Pale blue gas which forms a blue liquid on cooling and on
10.2.3 Neutral Oxides solidification forms violet black crystals. It has a strong fish-
They neither combine with acids nor with the bases to form salts like smell and is slightly soluble in water but more in turpen-
e.g., CO, N2O, NO etc. tine oil, glacial acetic acid or CCl4. O3 molecule is diamag-
netic but O3– is paramagnetic.
10.2.4 Amphoteric Oxides
(ii) Oxidising agent :
These can combine with acids as well as bases e.g., ZnO, Al2O3,
BeO, Sb2O3, Cr2O3, PbO etc. O3 + 2H+ + 2e-  O2 + H2O ; SRP = + 2.07 v
(In acidic medium)
PbO + 2 NaOH  Na2 PbO2 + H2O
O3 + H2O + 2e-  O2 + 2OH– ; SRP = + 1.24 v
PbO + H2SO4  PbSO4 + H2O
(In alkaline medium)
SCAN CODE
Therefore, ozone is a strong oxidising agent in acidic me- (ii) Tailing of mercury
dium. Pure mercury is a mobile liquid but when brought in contact
(a) It oxidises – to I2 (from neutral solution of K) with O3 its mobility decreases and it starts sticking to glass
surface forming a type of tail due to the dissolution of Hg2O
O3  O2   O
(mercury sub-oxide) in Hg.
2Kl  H 2 O   O   2KOH  l 2 2 Hg + O3  Hg2O + O2
2Kl  H 2 O   2KOH  O 2  l2 Uses:
• Alkaline K is oxidised to potassium iodate & periodate. (i) As a germicide and disinfectant for sterilising water and im-
K + 3O3  KO3 + 3O2 proving the atmosphere of crowded places.
(ii) For detecting the position of double bond in the unsatur-
K + 4O3  KO4 + 4O2 ated organic compounds.
(b) It oxidises moist S, P, As into their oxy acids.
(iii) In mfg. of artificial silk, synthetic camphor, KMnO4 etc.
O3  O2 + [O] × 3 11. GENERAL PROPERTIES AND COMPOUNDS
S + 3 [O]  SO3 OF SULPHUR
Sulphur Allotropic Froms: Sulphur forms numerous allotropes
SO3  H 2 O  H 2SO 4
of which the yellow rhombic ( - sulphur) and monoclinic ( -
S  3O3  H 2 O  H 2SO 4  3O 2 sulphur) forms are the most important. The stable forms at room
(c) It oxidises H2S to S temperature is rhombic sulphur, which transfroms to monoclinic
sulphur when heated above 369 K.
H2S + O3  H2O + S  (yellow) Rhombic Sulphur (- sulphur): This allotrope is yellow in colour
(iii) Reaction with Silver: , m.p. 385.8 K and specific gravity 2.06. Rhombic sulphur crystals
Silver articles become black in contact with ozone. are formed on evaporating the solution of roll sulphur in CS2. It is
insoluble in water but dissolved to some extent in benzene, alcohol
Ag + O3  Ag2O  (black) + O2 and ether. It is readily soluble in CS2 .
(iv) Reaction with H2O2 : Monoclinic Sulphur ( - sulphur): Its m.p. is 393 K and specific
gravity 1.98. It is soluble in CS2. This form of sulphur is prepared
O3  H 2 O 2  2O 2  H 2 O by melting rhombic sulphur in a dish and cooling till crust is
Oxidising Reducing formed. Two holes are made in the crust and the remaining liquid
agent agent
poured out. On removing the crust, colourless needle shaped
It is supported by the fact that SRP of ozone is higher (+2.07) crystals of  - sulphur are formed. It is stable above 369 K and
than SRP of hydrogen peroxide (+1.77). Therefore , ozone is transforms into  - sulphur below it . Conversely, - sulphur is
stronger oxidising agent than hydrogen peroxide. stable below 369 K and transfroms into  - sulphur above this. At
(v) Bleaching Action: 369 K both the forms are stable. This temperature is called transition
O3 also bleaches coloured substances through oxidation temperature.
(vi) Ozonolysis: Both rhombic and monoclinic sulphur have S8 molecules these S8
Alkenes, alkynes react with ozone forming ozonides. molecules are packed to give different crystal structures. The S8
ring in both the forms is puckered and has a crown shape. The
Zn  H O molecular dimensions are given in figure.
CH2 = CH2 + O3   2 2HCHO
 ZnO
Tests for Ozone
(i) A filter paper soaked in a alcoholic benzidine
becomes brown when brought in contact with O3 (this is not

shown by H2O2)
SCAN CODE
Ag2S2O3 + H2O  Ag2S  (Black) + H2SO4
If hypo is in excess, then soluble complex is formed.
2Na2S2O3 + AgNO3  Na3[Ag(S2O3)2] + NaNO3
This reaction is utilized in photography where hypo is used
as fixer.
(b) Reaction with FeCl3: It develops a pink or violet colour which
soon vanishes according to following reaction.
Fe3+ + 2S2O32–  [Fe(S2O3)2]– (Pink or violet)
[Fe(S2O3)2]– + Fe3+  2Fe2+ + S4O62–
(c) Reaction with AuCl3 (Soluble in water):
AuCl3 + Na2S2O3  AuCl  + Na2S4O6 + 2HCl
AuCl + Na2S2O3  Na3 [Au(S2O3)2] + NaCl
(d) Reaction with CuCl2 :
2 CuCl2 + 2Na2S2O3  2CuCl  + Na2S4O6 + 2 NaCl
CuCl + Na2S2O3  Cu2S2O3  + 2 NaCl
(a) S8 ring in rhombic sulphur and (b) S6 form 3 Cu2S2O3 + 2 Na2S2O3  Na4 [Cu6(S2O3)5]
Uses:
Several other modifications of sulphur containing 6-20 sulphur
(i) As an ‘antichlor’ to remove excess of chlorine from
atoms per ring have been synthesised in the last two decades. In
bleached fabrics.
cyclo- S6, the ring adopts the chair form and the moleculatr
(ii) In photography as fixer.
dimension are as shown in fig. (b) At elevated temperatures
(iii) As a reagent in iodometric and iodiometric titrations.
(~ 1000 K ), S2 is the dominant species and is paramagnetic like O2.
11.1.2 Hydrogen Sulphide (H2S)
11.1 Compounds of Sulphur
Preparation:
11.1.1 Sodium Thiosulphate (Na2S2O3 .5H2O)
Preparation: (i) FeS + H2SO4  FeSO4 + H2S
It is prepared in kipp’s apparatus
boiled (ii) Preparation of pure H2S gas
(i) Na2SO3 + S in absence of air Na2S2O3
Sb2S3 (pure) + 6 HCl (pure)  2 SbCl3 + 3 H2S
(ii) Na2CO3 + 2SO2 (excess) + H2O  2NaHSO3 + CO2 Properties:
2NaHSO3 + Na2CO3  2Na2S2O3 + H2O + CO2 (i) Colourless gas with rotten egg smell
(iii) Na2S + Na2SO3 + I2  Na2S2O3 + 2 NaI (ii) Moderately soluble in water but solubility decreases with
Properties: increasing temperature.
(i) It is a colourless crystalline substance soluble in water which (iii) Reducing Agent:
loses water of crystallisation on strong heating Acts as a strong reducing agent as it decomposes evolv-
(ii) As antichlor: It removes the chlorine from the surface of ing hydrogen.
fibres (while dyeing) according to following reaction. (a) H2S + X2  2 HX + S
Na2S2O3 + Cl2 + H2O  Na2SO4 + 2HCl + S (b) moisture  H O + S
H2S + SO2  2
Therefore, it is known as antichlor
(c) It also reduces KMnO4  Mn2+
(iii) Reaction with HCl :
H2SO4  SO2 & K2Cr2O7  Cr3+
Na2S2O3 + HCl  2NaCl + SO2 + S + H2O (iv) Acidic Nature: Its aquesous solution acts as a weak
This test is used for distinction between S2O32- and SO32- dibasic acid according to following reaction
ions as SO32- ions give only SO2 with HCl.
H 2S HS + H+ S2- + 2H+
(iv) Complex formation reactions :
Therefore, It forms two series of salts as given below
(a) Reaction with silver salts (AgNO3 , AgCl, AgBr or AgI):
NaOH + H2S  NaHS + H2O
Na2S2O3 + 2AgNO3  Ag2S2O3  (white) + 2 NaNO3 NaOH + NaHS  Na2S + 2H2O
SCAN CODE
(v) Formation of Polysulphides: They are obtained by (vi) Reducing Nature :
passing H2S gas through metal hydroxides. H2O + SO2  H2SO3
Ca(OH)2 + H2S  CaS + 2H2O H2SO3 + H2O  H2SO4 + 2H
CaS + 4 H2S  CaS5 + 4H2 Reducing character is due to the liberation of nascent hy-
Tests for H2S: drogen
(i) Turns acidified lead acetate paper black (a) Reduces halogens to corresponding halides
(ii) Gives violet or purple colouration with sodium nitropruside SO2 + 2H2O  H2SO4 + 2H
solution. 2H + Cl2  2HCl
Uses: ––––––––––––––––––––––––––––––––
(i) As a loboratory reagent for the detection of basic radicals in
SO2 + 2H2O + Cl2  H2SO4 + 2HCl
qualitative analysis.
(b) Reduces acidified iodates to iodine
(ii) As reducing agent.
2KIO3 + 5SO2 + 4H2O  K2SO4 + 4H2SO4 + I2
11.1.3 Sulphur Dioxide
It also reduces acidified KMnO4  Mn2+ (decolourises),
Preparation:
Acidified K2Cr2O7  Cr3+ (green coloured solution) &
(i) Burn
S + O2 or air   SO2 Ferric Sulphate  Ferrous sulphate
  3SO + 2H O (vii) Oxidising nature: Acts as oxidising agent with strong
(ii) S + 2H2SO4 (conc.)  2 2 reducing agent
(iii) By heating Cu or Ag with conc. H2SO4
moisture  2H O + 3S
(a) 2H2S + SO2 
Cu + H2SO4  CuSO4 + 2H2O + SO2 2
(iv) By reaction of metal sulphites with dil.HCl (b) 2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
Na2SO3 + 2HCl  2NaCl + SO2 + H2O (c) 2Hg2Cl2 + SO2 + 4HCl  2HgCl2 + 2H2O + S
Similarly bisulphites also give SO2 with dil. HCl (d) 2CO + SO2  2CO2 + S
NaHSO3 + HCl  NaCl + SO2 + H2O (e) 2 Fe + SO2  2FeO + FeS
(v) By heating sulphides in excess of air (viii) Bleaching Action:
2 ZnS + 3O2  2ZnO + 2SO2 SO2 + 2H2O  H2SO4 + 2H
 This is due to the reducing nature of SO2
(vi) CaSO4 (gypsum) + C 
1000C 2 CaO + SO2 + CO2 
Coloured matter + H   colourless matter..
Air oxidation
By this method SO2 is obtained in large scale
Properties: Therefore, bleaching is temporary
(i) Colourless gas with burning sulphur smell. Uses:
(ii) It is heavier than air and is highly soluble in water (i) Used in manufacture of H2SO4 & paper from wood pulp.
(iii) Neither burns nor helps in burning but burning magnesium (ii) As a bleaching agent for delicate articles like wool, silk and
and potassium continue to burn in its atmosphere. straw.
3Mg + SO2  2 MgO + MgS (iii) Used in refining of petroleum and sugar.
4K + 3SO2  K2SO3 + K2S2O3 11.1.4 Sulphur Trioxide (SO3)
(iv) Acidic Nature : Acidic oxide and thus dissolve in water form- Preparation:
ing sulphurous acid. (i) 6H2SO4 + P4O10  6SO3 + 4H3PO4
SO2 + H2O  H2SO3 P4O10 is dehydrating agent
(v) Addition Reaction:
  Fe O + 3SO
(ii) Fe2(SO4)3  2 3 3
Sun light SO Cl (sulphuryl chloride)
SO2 + Cl2   2 2
pt
 2SO
(iii) 2SO2 + O2 
platinised 3
 SO
SO2 + O2  Properties:
Asbests 3
(i) Acidic Nature: Dissolves in water forming sulphuric acid

PbO2 + SO2  PbSO4
SO3 + H2O  H2SO4
SCAN CODE
(ii) H2SO4 + SO3  H2S2O7 (oleum) NaHSO4 + NaOH  Na2SO4 (sodium sulphate) + H2O
(iii) SO3 + HCl  SO2(OH) Cl (chlorosulphuric acid) (b) Decomposes carbonates and bicarbonates into carbon
(iv) Oxidising Nature : dioxide
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2
100C
(a) 2SO3 + S  3SO2 NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(b) 5SO3 + 2P  5SO2 + P2O5 (c) Displaces more volatile acids from their metal salts.
(c) SO3 + PCl5  POCl3 + SO2 + Cl2 2NaCl + H2SO4  Na2SO4 + HCl
(d) SO3 + 2HBr  H2O + Br2 + SO2 2NaNO3 + H2SO4  Na2SO4 + 2HNO3
Uses: CaF2 + H2SO4  CaSO4 + 2HF
(i) Used in manufacture of H2SO4 and oleum. (v) Oxidising Nature: H2SO4 acts as a strong oxidising agent
(ii) Used as a drying agent for gases.
H2SO4  H2O + SO2 + [O]
11.1.5 Sulphuric Acid (H2SO4) (a) Non-metals (carbon, sulphur etc) are oxidised to their oxides.
Preparation: H2SO4  H2O + SO2 + O] × 2
(i) 2FeSO4 . 7H2O  dist. Fe O + H SO + SO + 13H O C + 2[O]  CO2
2 3 2 4 2 2
(ii) Lead Chamber Process (Industrial method) : ––––––––––––––––––––––––––––––––––––

2SO2 + O2 (air) + 2H2O + [NO] (catalyst)  2H2SO4 + C + 2H2SO4  CO2 + 2SO2 + 2H2O
[NO] (catalyst) ––––––––––––––––––––––––––––––––––––
Acid obtained is 80% pure and is known as brown oil of 2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
vitriol (b) Metals (copper, silver, mercury etc.) are oxidised to their
(iii) Contact process (Industrial method) : oxides which then combine with acid to form corresponding
sulphates.
catalyst
 2SO3
O2 + 2SO2  H2SO4  H2O + SO2 + [O]
The commonly used catalysts are platinum, ferric oxide or Cu + [O]  CuO
vanadium pentoxide. V2O5 is preferred as it is cheaper and is CuO + H2SO4  CuSO4 + H2O
not poisoned by impurities –––––––––––––––––––––––––––––––––
H2SO4 (58%) + SO3  H2S2O7 (oleum) Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
Sulphuric acid of any desired concentration can be obtained (c) Iodine is liberated from KI
from oleum by dilution with water.
2 KI + H2SO4  K2SO4 + 2HI
H2S2O7 + H2O  2H2SO4
H2SO4  H2O + SO2 + [O]
Oxidation of sulphur dioxide is reversible and exothermic.
According to Le-chatelier principle, the favourable condi- 2 HI + [O]  I2 + H2O
tions for the greater yield of sulphur trioxide are. –––––––––––––––––––––––––––––––––––––
(a) An excess of air- SO2 and oxygen are taken in 2:3 molecular 2 KI + 2H2SO4  K2SO4 + SO2 + I2 + 2H2O
proportion Here HI is oxidised to I2. Similarly bromine is liberated from
(b) Low tempt-optimum tempt. 450°C KBr
(c) Higher pressure-one atmosphere (vi) Dehydrating agent: Sulphuric acid acts as a powerful
Properties : dehydrating agent because it has a great affinity for water
(i) A colourless syrupy liquid (it is H-bonded) H SO
2 4
(ii) It fumes strongly in moist air and is highly corrosive in (a) C12H22O11 (cane sugar)    
–11H O 12C
nature. 2
440C H O + SO

(iii) Thermal decomposition : H2SO4  COOH H SO
 2 3 (b) | 2 4
 CO + CO2 + H2O
COOH 
(iv) Acidic Nature: It is a strong dibasic acid and ionises as
H2SO4 H+ + HSO4– 2H+ + SO42–
(a) Forms two series of salts
NaOH + H2SO4  NaHSO4 (sodium bisulphate) + H2O
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(vii) Miscellaneous reactions:
(a) Sulphonation of aromatic compounds 13. INTRODUCTION OF GROUP 17 ELEMENTS:
THE HALOGEN FAMILY
Fluorine, chlorine, bromine, iodine and astatine are members of
Group 17. These are collectively known as the halogens (Greek
halo means salt and genes born i.e., salt producers). The halogens
are highly reactive non-metallic elements.
Benzene Benzene sulphonic acid
(b) Reaction with PCl5:
13.1 Electronic Configuration
All these elements have seven electrons in their outermost shell
(ns2 np5) which is one electron short of the next noble gas.
+ POCl3 + HCl 13.2 Atomic and Ionic Radii
The halogens have the smallest atomic radii in their respective
Chlorosulphonic acid periods due to maximum effective nuclear charge . Atomic and
ionic radii increase from fluorine to iodine due to increasing number
of quantum shells.
+ 2 POCl3 + 2HCl 13.3 Ionisation Enthalpy
They have little tendency to lose electron. Thus they have very
high ionisation enthalpy. Due to increase in atomic size, ionisation
Sulphury chloride
enthalpy decreases down the group.
(c) K4[Fe(CN)6] + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + 13.4 Electron Gain Enthalpy
3(NH4)2SO4 + 6CO
Halogen have maximum negative electrons gain enthalpy in the
(d) 3KClO3 + 3H2SO4   3 KHSO4 + HClO4 + 2ClO2 + H2O corresponding period. This is due to the fact that the atoms of
(e) H2SO4 + P2O5  2HPO3 + SO3 these elements have only one electron less than stable noble gas
Uses : configurations. Electron gain enthalpy of the elements of the group
(i) For the manufacture of fertilizer such as ammonium sulphate becomes less negative down the group. However, the negative
and super phosphate of lime. electron gain enthalpy of fluorine is less than that of chlorine. It is
(ii) As an important laboratory reagent. due to small size of fluorine atom. As a result, there are strong
(iii) In storage batteries. interelectronic repulsions in the relatively small 2p orbitals of
(iv) In leather, textile, paper and dyeing industries. fluorine and thus, the incoming electron does not experience much
attraction.
12. USES OF GROUP 16 ELEMENTS 13.5 Electronegativity
Sulphur dioxide is used (i) in refining petroleum ans sugar (ii) in They have very high electronegativity. The electronegativity
bleaching wool and silk and (iii) as an anti-chlor, disinfectant and decreases down the group. Fluorine is the most electronegative
preservative. Sulphuric acid, sodium hydrogen sulphite and element in the periodic table.
calcium hydrogen sulphite (industrial chemicals) are manufactured
from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve
a number of organic and inorganic chemicals.
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Physical Properties of Halogens
Element F Cl Br I
Atomic Number 9 17 35 53
Atomic Mass 19 35.45 79.90 126.90
Electronic configuration [He]2s 2p 2 5
[Ne]3s 3p 2 5
[Ar]3d 4s 4p
10 2 5
[Kr]4d105s25p5
Covalent Radius/pm 64 99 114 133
Ionic Radius X /pm
–
133 184 196 220
Ionization enthalpy /(kJ mol–1) 1680 1256 1142 1008
Electron gain enthalpy/(kJ/mol–1) –333 –349 –325 –296
Distance X-X/pm 143 199 229 266
Enthalpy of dissociation 158.8 242.6 192.8 151.1
(X2)/kJ mol–1
Electronegativity 4 3.2 3.0 2.7
Melting point/K 54.4 172 265.8 386.6
Boiling point/K 84.9 239.0 335.5 458.2
exhibits only – 1 oxidation state.

14. PHYSICAL PROPERTIES OF GROUP 17
All the halogens are highly reactive. They react with metals and
ELEMENTS non-metals to form halides. The reactivity of the halogens de-
Fluorine and chlorine are gases, bromine is a liquid and iodine is creases down the group.
a solid. Their melting and boiling points steadily increase with
The ready acceptance of an electron is the reason for the strong
atomic number. All halogen are coloured. This is due to absorp-
oxidising nature of halogens. F2 is the strongest oxidising halo-
tion of radiations in visible region which results in the excitation
of outer electrons to higher energy level. By absorbing different gen and it oxidises other halide ions in solution or even in the
quanta of radiation, they display different colours. For example, solid phase. The decreasing oxidising ability of the halogen in
F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour. aqueous solution down the group is evident from their standard
Fluorine and chlorine react with water. Bromine and iodine are electrode potentials. Fluorine oxidises water to oxygen whereas
only sparingly soluble in water. But are soluble in organic sol- chlorine and bromine react with water to form corresponding
vents such as chloroform, carbon tetrachloride, carbon disulphide hydrohalic and hypohalous acids. The reactions of iodine with
and hydrocarbons to give coloured solutions.Except the smaller water is non- spontaneous . I– can be oxidised by oxygen in acidic
enthalpy of dissociation of F2 compared to that of Cl2 whereas X- medium; just the reverse of the reaction observed with fluorine.
X bond dissociation enthalpies from chlorine onwards show the
2F2(g) + 2H2O()  4H+ (aq) + 4F– (aq) + O2(g)
expected trend: Cl – Cl > Br – Br > I – I . A reason for this anomaly
is the relatively larger electrons- electron repulsion among the X2(g) + H2O ()  HX(aq) + HOX (aq)
lone pairs in F2 molecule where they are much closer to each other (where X = Cl or Br)
than in case of Cl2. –
4I (aq) + 4H (aq) + O2(g)  2 I2 (s) + 2H2O ()
+
15. CHEMICAL PROPERTIES OF GROUP 17 ELEMENTS Standard Reduction Potential (SRP)

Oxidation states and trends in chemical reactivity: All the halo-
gens exhibit –1 oxidation state. However, chlorine, bromine and X2 + 2e–  2X–
iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also. The higher
F2 + 2e–  2F– ° = + 2.87 V ;
oxidation states of chlorine, bromine and iodine are realised mainly
when the halogens are in combination with the small and highly Cl2 + 2e–  2Cl– ° = + 1.36 V
electronegative fluorine and oxygen atoms e.g., in interhalogens,
oxides and oxoacids. Br2 + 2e –  2Br – ° = + 1.09 V;;
The fluorine atom has no d orbitals in its valence shell and there-
fore cannot expand its octet. Being the most electronegative, it
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2 + 2e–  2– ° = + 0.54 V ones.

Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive
 More the value of the SRP, more powerful is the (algebraically)
oxidising agents and tend to explode. ClO2 is used as a bleaching
oxidising agent. Hence the order of oxidising power is
agent for paper pulp and textiles and in water treatment.
F2 > Cl2 > Br2 > 2
The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen
Since SRP is the highest for F2 (among all elements of P.T.), it
oxides and exist only at low temperature. They are very powerful
is a strogenst oxidising agent.
oxidising agents.
 F2 is more powerful oxidising agent than O3 [Inspite of 3 ‘O’s
The iodine oxides, I2O4, I2O5, I2O7 are insoluble solids and decom-
in O3 ]
pose on heating. I2O5 is very good oxidising agent and is used in
the estimation of carbon monoxide.
NOTE
Electrode potential values would be the monitoring parameter 15.3 Reactivity Towards Metals
in solution phase because they are experimental (based on the Halogen react with metals to form metal halides. For e.g., bromine
correct situation). reacts with magnesium to give magnesium bromide.
Hydration energy of X– 15.4 Reactivity of Halogen Towards other Halogens
Smaller the ion, higher is the hydration energy Halogens combine amongst themselves to form a number of com-
F– Cl – Br – – pounds known as interhalogen of the types AB, AB3, AB5 and
AB7 where A is a larger size halogen and and B is smaller size
515 kJ/mol 381 347 305
halogen.
Anomalous behaviour of fluorine: The anomalous behviour of
fluorine is due to its small size, highest electronegativity, low F- F 16. GENERAL PROPERTIES AND COMPOUNDS OF
bond dissociation enthalpy, and non availability of d orbitals in HALOGENS
valence shell. Most of the reactions of fluorine are exothermic 16.1 Fluorine (F2)
(due to the small and strong bond formed by it with other elements). Preparation
It forms only one oxoacid while other halogen form a number of (i) Electrolytic method: Electrolyte : Molten KHF2 (1 part) + HF
oxoacids. Hydrogen fluoride is liquid (b.p. 293 K) due to strong (5 part)
hydrogen bonding. Other hydrogen halides are gases.
Anode : Carbon
15.1 Reactivity Towards Hydrogen Cathode : Steel
They all react with hydrogen to give hydrogen halides but affinity Vessel : Metal
for hydrogen decreases from fluorine to iodine. They dissolve in
On Electrolysis
water to form hydrohalic acids. The acidic strength of these acids
varies in the order : HF < HCl < HBr < HI. The stability of these Cathode : 2H+ + 2e–  H2(g)
halides dereases down the group due to decrease in bond (H–X)
dissociation enthalpy in the order : Anode : 2F–  F2 + 2e–
H – F > H – Cl > H –Br > H – I . The F2 gas thus evolved must be free from HF which is more
corrosive than fluorine.
15.2 Reactivity Towards Oxygen
In order to make flourine free from HF, the gas is passed
Halogens form many oxides with oxygen but most of them are
through NaF which absorbs HF.
unstable. Fluorine forms two oxides OF2 and O2F2. However, only
OF2 is the thermally stable at 298 K. These oxide are essentially  Anode of carbon should be free from graphite because F2
oxygen fluorides because of the higher electronegativity of reacts with graphite easily to form a polymeric substance
flurorine than oxygen . Both are strong fluorinating agents. O2F2 known as graphite fluoride.
oxidises plutonium to PuF6 and the reactions is used in removing There should be no moisture present in the vessel otherwise
plutonium as PuF6 from spent nuclear fuel. fluorine will react with water.
Chlorine, bromine and iodine form oxides in which the oxidation 3H2O + 3F2  6HF + O3 , 2F2 + 2H2O  4HF + O2
states of these halogen range from + 1 to + 7. A combination of
kinetic and thermodynamic factors lead to the generally decreas-  It is not possible to prepare fluorine by electrolysis of aq.
ing order of stability oxides formed by halogens, I > Cl > Br. The solution of NaF or KF. It is because when aq. solution of KF
higher oxides of halogens tend to be more stable than the lower is subjected to electrolysis, there will be following two
oxidation in competition at anode,
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H2O  1/2O2 + 2H+ + 2e– SOP = – 1.23 v (ix) Reaction with H2 :
and H2 + F2  2 HF or H2 F2
– 
F 1/2F2 + e –
SOP = – 2.87v
This reactions occurs even in dark
As a matter of rule that substance will be oxidise whose SOP
is higher therefore water gets oxidise at anode and not F–. 16.2 Chlorine (Cl2)
Properties: Preparation:
(i) Diatomic, Pale green-yellow gas which appears to be almost (i) Common Method (Cl2 , Br2 , 2) :
colourless. 
2 NaX + 3H2SO4 (conc.) + MnO2 (oxidising agent) 
(ii) Oxidising Character: It is the most powerful oxidising agent. X2 + MnSO4 + 2NaHSO4 + 2H2O
F2 + 2NaX  2NaF + X2 4H+ + MnO2 + 2X–  X2 + Mn+2 + 2H2O
(X = Cl, Br, )
(ii) Only for Cl2 :
(a) It can oxidise all other halide ions into halogen molecules
(a) NaCl + HNO3  NaNO3 + HCl × 3
5 7
(b) It can oxidise Cl O 3 into Cl O 4 and IO3– to IO4–
HNO3 + 3HCl  NOCl + Cl2 + 2H2O
F2 + ClO + H2O  2F + ClO4 + 2H
3
– – – +
––––––––––––––––––––––––––––––––––––
(iii) Reaction with NaOH Solution : With dilute alkali forms
3NaCl + 4 HNO3  3 NaNO3 + NOCl (nitrosyl chloride)
oxygen difluoride and with concentrated alkali O2.
2F2 + 2 NaOH (dil)  OF2 (g) + 2 NaF + H2O 2NOCl + O2  2NO2 + Cl2 ;
2F2 + 4 NaOH (conc.)  O2 (g) + 4 NaF + 2H2O NO2 + H2O  HNO3 (to be recycled)
(iv) Reaction with NH3 : (Distinction from other halogens) (b) When Cl2 is used for the chlorination of hydrocarbon the
byproduct is HCl. The HCl is catalytically oxidised into H2O
2NH3 + 3F2  N2 + 6 HF & Cl2 using copper powder mixed with rare earth chlorides.
Other halogens form explosive NX3. with conc. NH3 (liquor Cu powder  rare earth
ammonia) 4 HCl + O2 
Chloride
 2H O + 2Cl
2 2
(v) Reaction with H2S :

OCl
H2S + F2  SF6 + 2 HF (c) Ca / + 2HCl  CaCl2 + Cl2 + H2O
\
Cl
(vi) Reaction with SiO2 : It attacks glass at about 100 C. 0
(iii) Manufacture of Chlorine :

SiO2 (s) + 2F2 (g)  SiF4 (g) + O2 (g)
(a) Deacon’s Process: By oxidation of hydrogen chloride gas
The reaction is slow with dry F2 . by atmospheric oxygen in the presence of CuCl2 (catalyst)
(vii) Reaction with H2O : at 723 K.
2H2O + 2F2  4 HF + O2 CuCl

4 HCl + O2  2  2 Cl2 + 2 H2O
sometime a little amount of O3 also forms
(b) Electrolytic Process : Chlorine is obtained by the electrolysis
3H2O + 3F2  6HF + O3 of brine (concentrated NaCl solution). Chlorine is liberated
(viii) Reaction with Xe: at anode. It is also obtained as a by–product in many
chemical industries.
NaX (aq)  Na+ (aq) + X– (aq)
Anode : 2X–  X2 + 2e–
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Properties: SO32– + Coloured material  SO42– + Reduced coloured
(i) It is a greenish–yellow gas with pungent and suffocating
material (colourless)
odour. It is about 2–5 times heavier than air. It can be liquefied
into greenish–yellow liquid which boils at 239 K. It is soluble O of air
Reduced Coloured material (colourless) 
2 
in water.
Coloured material
(ii) At low temperature it forms a hydrate with water having
formula Cl2 . 8H2O which is infact a clathrate compound. (vii) Reaction with NaOH:
Common to Br2 , 2 & Cl2 (but with F2 it is different, OF2 or O2
(iii) H2 + Cl2 
(a zero order reaction) 2HCl (g) , is obtained)
(a) 2 NaOH (cold & dilute) + Cl2  NaCl + NaClO + H2O
[H2 + Br2  2HBr is not a zero order reaction]
(b) 6 NaOH (hot & concentrated) + 3 Cl2  5 NaCl +
(iv) Reaction with NH3 (common for Cl2 & Br2) :
NaClO3 + 3 H2O
(a) 8 NH3 + 3 Cl2  N2 + 6 NH4 Cl (viii) Reaction with Hypo Solution:
(b) NH3 + 3Cl2  NCl3 + 3 HCl This reaction is common with Cl2 & Br2 but with 2 it is
different.
(excess)
(v) Reaction with Alkali Metal Halides (KX) :  0
Na 2S2 O3  H 2 O  Cl2  Na 2SO 4  2HCl   S
2 KBr + Cl2  2KCl + Br2  colloidal 
 
 
2K + Cl2  2 KCl + 2 In this reaction thiosulphate ions undergo

 Cl2 can oxidise both Br &  but Br2 can oxidise  only.
– – – disproportionation into SO42– and S. Cl2 is reduced to Cl– .
 F2 is not used in aqueous reaction since it itself reacts with (ix) Reaction with dry Slaked Lime, Ca(OH)2: It gives bleaching
water. powder.
(vi) Oxidising & Bleaching Properties: Chlorine water on 2 Ca(OH)2 + 2 Cl2  Ca(OCl)2 + CaCl2 + 2 H2O
standing loses its yellow colour due to the formation of HCl
(x) Reaction with Metals & non–Metals : Forms corresponding
and HOCl. Hypochlorous acid (HOCl) so formed, gives
chlorides.
nascent oxygen which is responsible for oxidising and
bleaching properties of chlorine. 2 Al + 3 Cl2  2 AlCl3
(a) It oxidises ferrous to ferric, sulphite to sulphate, sulphur 2 Na + Cl2  2 NaCl
dioxide to sulphuric acid and iodine to iodic acid. P4 + 6 Cl2  4 PCl3
2 FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2 HCl S8 + 4 Cl2  4 S2Cl2
Na2SO3 + Cl2 + H2O  Na2SO4 + 2 HCl  It has great affinity for hydrogen. It reacts with compounds
SO2 + 2 H2O + Cl2  H2SO4 + 2 HCl containing hydrogen to form HCl.
I2 + 6 H2O + 5 Cl2  2 HIO3 + 10 HCl H2 + Cl2  2 HCl
(b) It is a powerful bleaching agent ; Bleaching action is due to H2S + Cl2  2 HCl + S
oxidation. Uses : Cl2 is used
Cl2 + H2O  2 HCl + O (i) for bleaching woodpulp (required for the manufacture of
Coloured substance + O  Colourless substance paper and rayon). bleaching cotton and textiles,
It bleaches vegetable or organic matter in the presence of (ii) in the manufacture of dyes, drugs and organic compounds
moisture. Bleaching effect of chloride is permanent. such as CCl4 , CHCl3 , DDT, refrigerants, etc.
 But the bleaching action of SO2 is temporary because it takes (iii) in the extraction of gold and platinum.
place through reduction. (iv) in sterilising drinking water and
(v) preparation of poisonous gases such as phosgene (COCl2),
SO2 + 2 H2O  H2 SO4 + 2 H
tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).
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16.3 Bromine (Br2) KF3 cannot be formed similarly since F does not have ‘d’ orbitals. So
Preparation: sp3d hybridisation is not possible with F.
(i) Common Method: (ii) It is soluble in organic solvents like CHCl3, CCl4 etc. to get
violet solutions.
 Br + MnSO +
2 NaBr + 3H2SO4 (conc.) + MnO2  2 4 (iii) Reaction with Hypo: iodometric titrations
2NaHSO4 + 2H2O 2.5
(ii) From Sea-Water: NaCl is main component but NaBr is also S2 O32– (thiosulphate ions) + 2  S4 O 62 
present in some quantity in sea water. Cl2 gas is passed (tetrathionate ions) + 2–
through sea water when vapours of bromine are evolved. This reaction is the basis of iodometric (direct 2 titration)
2 Br (aq) + Cl2  2Cl (aq.) + Br2
– – titration, which is carried out for the estimation of iodine
using starch indicator.
Properties:
(iv) Reaction with KClO3 or KBrO3:
(i) Reddish brown liquid, fairly soluble in water. It also forms
hydrate like Cl2 
2 KClO3 + 2  2 KIO3 + Cl2
(Br2 . 8H2O)  Clathrate compound  2KIO + Br
2 KBrO3 + 2  3 2
(ii) Rest reactions are same as with Cl2 (v) Reaction with Ozone (dry) :
16.4 Iodine (I2) 22 (s) + 3O3 (g)  4O9 (s)
Preparation:
4O9 is an ionic compound consisting of 3+ & O3–)3 indicative
(i) Common Method : of metallic character of  (low .E, low E.N.)

2Na + 3H2SO4 (conc.) + MnO2  2 + MnSO4 + With NaOH there is common reaction as with Cl2 and Br2 . With H2
there is reversible reaction.
2NaHSO4 + 2H2O
16.5 Hydra Acids (Halogen Acids)
(ii) From Caliche or Crude Chile Salt Petre : The main source
of iodine is NaO3 (sodium iodate) which is found in nature HCl, HBr & HI :
with NaNO3 (chile saltpetre). NaO3 is present in small amount. Preparation:
After crystallisation of NaNO3 , the mother liquor left contains (i) By direct combination of elements:
NaO3 (soluble). To this solution NaHSO3 is added where
H2 + Cl2  2HCl
upon 2 is precipitated.
Pt 2HBr
H2 + Br2 
(iii) From Sea-Weeds : Sea-weeds are dried and burnt in shallow
pits, ash left is called kelp. Ash on extraction with hot water Pt , 450 C 2H
H2 + 2  
dissolves out chlorides, carbonates, sulphates and iodides
of sodium and potassium. The solution on concentration (ii) By heating a halide with acid :
seperates out all leaving behind iodide in the solution. NaCl + H2SO4  NaHSO4 + HCl
Solution is mixed with MnO2 and concentrated H2SO4 in iron
retorts. Liberated iodine is condensed in series of earthen- NaHSO4 + NaCl  Na2SO4 + HCl
ware known as aludels.
For HCl we use H2SO4 as an acid, while for HBr and H we
2Na+ MnO2 + 3H2SO4 2NaHSO4 + MnSO4 + 2 + 2H2O use H3PO4.
(iv) 2K+ Cl2  2KCl + 2 (a) HCl cannot be dried over P2O5 (P4O10) or quick lime since
(v) 2K+ H2O2  2KOH + 2 they react with gas chemically.
(vi) CuSO4 + 2K  K2SO4 + Cu2 ; CaO + 2HCl  CaCl2 + H2O
This 2 gets dissolved into K forming 3 , since 3– ions are yellow,
therefore solution develops yellow colour. P4O10 + 3HCl  POCl3 + 3HPO3
Properties : HCl is, hence dried by passing through conc. H2SO4 .
(i) It is a dark violet solid, undergoes sublimation, least soluble (b) HBr (or H) cannot be prepared by heating bromide (iodide)
(among halogens) in water but much more soluble in K(aq.) with conc. H2SO4 because HBr and H are strong reducing
due to formation of K3 agents and reduce H2SO4 to SO2 and get themselves oxidised
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to bromine and iodine respectively.
(vii) Reducing Property and Stability of Hydracids:
KX + H2SO4  KHSO4 + HX HCl: It is quite stable and hence is oxidised by strong
oxidising agents like MnO2, KMnO4, K2Cr2O7, PbO2, Pb3O4.
H2SO4 + 2HX  SO2 + X2 + 2H2O (X = Br or )
(i) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2
Hence, HBr and H are prepared by heating bromides and
iodides respectively with conc. H3PO4 . (ii) 2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2
3KBr(K) + H3PO4  K3PO4 + 3HBr (H)
(iii) K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2
Properties:
(iv) PbO2 + 4HCl  PbCl2 + 2H2O + Cl2 ;
(i) These are colourless, pungent smelling gases with acidic
tastes. (v) Pb3 O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(ii) It is heavier than air, can be liquified to colourless liquids.
Therefore, HCl is a weak reducing agent.
(iii) These are neither combustible nor supporter of combustion.
HBr : It is not very stable and hence more easily oxidised or
(iv) When perfectly dry, they have no action on litmus, but in
acts as a strong reducing agents. In addition to above
presence of moisture, they turn blue litmus red, showing
reducing properties of HCl, it also reduces H2SO4 to SO2
acidic nature. Among HX, H is the strongest and HF is the
which is not done by HCl.
weakest acid.
(v) These are quite soluble in water. H2SO4 + HBr  SO2 + Br2 + 2H2O
HCl ionises as below. Aqueous HBr on exposure to atmospheric oxygen is oxidised
HCl(g) + H2O ()  H3O (aq) + Cl (aq) Ka = 10
+ – 7 to bromine (yellow)
It aqueous solution is called hydrochloric acid. High value 4HBr + O2  2 Br2 + 2H2O
of dissociation constant (Ka) indicates that it is a strong acid
H : It is least stable hydrogen halide. It is readily oxidised
in water.
and thus acts as a powerful reducing agent.
When three parts of concentrated HCl and one part of
In addition to reaction shown by HCl, it shows following
concentrated HNO3 are mixed, aqua regia is formed which is
reactions also.
used for dissolving noble metals, e.g., gold, platinum.
(a) H2SO4 + 2H  SO2 + 2 + H2O ;
Au + 4 H+ + NO3– + 4 Cl–  AuCl4– + NO + 2 H2O
H2SO4 + 6H  S + 32 + 4H2O;
3 Pt + 16 H+ + 4 NO3– + 18 Cl–  3 PtCl62– + 4 NO + 8 H2O
H2SO4 + 8H  H2S + 42 + 4H2O ;
(v) Reaction with metals oxides, hydroxides and bicarbonates
(b) 2HNO3 + 2H  2NO2 + 2 + 2H2O
Zn + 2HCl  ZnCl2 + H2 (c) 2HNO2 + 2H  2NO + 2 + 2H2O
(d) HO3 + 5H  32 + 2H2O
MgO + 2HCl  MgCl2 + H2O
(e) K2S2O8 + 2H  K2SO4 + 2 + H2SO4
NaOH + HCl  NaCl + H2O (f) 2FeCl3 + 2H  2FeCl2 + 2 + 2HCl
(g) Aqueous solution of acid, if exposed to O2 is oxidised to
CaCO3 + 2HCl  CaCl2 + H2O + CO2
iodine.
(vi) Reaction with salts, HCl decomposes salts of weaker acids.
4H + O2  22 + 2H2O
NaHCO3 + HCl  NaCl + CO2 + H2O
(viii) Reaction with Ammonia:
Na2S + 2HCl  2NaCl + H2S
NH3 + HX  NH4X (white fumes) (where X = Cl, Br, )
Na2SO3 + 2HCl  2NaCl + SO2 + H2O (ix) Action of Halogens:
Na2S2O3 + HCl  2NaCl + SO2 + H2O + S (a) Cl2 is liberated from HCl by F2 alone.
F2 + HCl  2HF + Cl2
2NaNO2 + 2HCl  2NaCl + NO + NO2 + H2O
(b) Br2 is liberated from HBr by F2 and Cl2 (not by 2)
SCAN CODE
2HBr + F2 / Cl2  2HF (2HCl) + Br2 Na2SiO3 + 6HF  Na2 SiF6 + 3H2O;
(c) 2 is liberated from H by F2, Cl2 and Br2 CaSiO3 + 6HF  CaSiF6 + 3H2O
2H + F2 (Cl2, Br2)  2HF (HCl, HBr) + 2
SiO2 + 4HF  SiF4 + 2H2O
(x) Detection of Cation:
SiF4 + 2HF  H2 SiF6
HCl : AgNO3 + HCl  AgCl (white) + HNO3
This action of HF on silica (silicates) is used for etching
(CH3COO)2 Pb + 2HCl  PbCl2(white) + 2CH3COOH glass. The glass surface to be etched is coated with wax, the
design, is scratched on glass through wax coating this is
HBr : AgNO3 + HBr  AgBr (pale yellow) + HNO3 then treated with 40% solution.
(CH3COO)2 Pb + 2HBr  PbBr2  (white) + 2CH3COOH Properties:

(i) It is colourless, corrosive liquid with pungent smell with
H: AgNO3 + H  Ag (bright yellow) + HNO3 high boiling point due to hydrogen bonding.
(ii) Dry HF does not attack metals under ordinary conditions
(CH3COO)2 Pb + 2H  Pb2 (yellow) + 2CH3COOH
(except K), but in presence of water, it dissolves metals with
(xi) Formation of Aqua-regia : 3 parts of conc. HCl and 1 part of liberation of hydrogen gas.
conc. HNO3 is known as aqua-regia. This is used for 16.7 Oxy-Acids of Chlorine
dissolving noble metals like Au (Gold) and Pt (Platinum). 16.7.1 Hypo-Chlorous Acid [HClO]
3HCl + HNO3  NOCl + 2H2O + 2Cl (reactive) ; Preparation:
Au + 3Cl  AuCl3 (i) The acid is known only in solution, It is obtained by shaking
precipitate of HgO with chlorine water.
Uses:
2HgO + 2Cl2 + H2O  Hg2OCl2 + 2HClO
(i) HCl is used in preparation of Cl2, chlorides, aqua regia,
(ii) Commercially, it is obtained by passing CO 2 through
glucose, (from corn starch), medicines, laboratory reagents,
suspension of bleaching powder and then distilling.
cleaning metal surfaces before soldering or electroplating. It
is also used for extracting glue from bones and purifying 2CaOCl2 + H2O + CO2  CaCl2 + CaCO3 + 2HClO
bone black. Properties:
(ii) HBr is used as laboratory reagent for preparing bromo (i) It is a weak acid. Its concentrated solution is yellow in colour
derivatives like sodium bromides and potassium bromide. while dilute solution is colourless. It is unstable and
These are used in medicines as sedatives. decomposes.
(iii) H is used as reducing agent in organic chemistry.
2HClO  2HCl + O2
16.6 Hydrofluoric Acid [H2 F2, HF] (ii) It dissolves magnesium with evolution of hydrogen.
Preparation : H2 and F2 combine with each other very violently Mg + 3HClO  Mg(ClO)2 + H2
(even in dark) to form HF. So simple reaction cannot be used for
(iii) With alkalies, it forms salts called hypochlorites.
its preparation, special methods are employed for its preparation.
(iv) It acts as a powerful oxidising and bleaching agent. This is
(i) Laboratory Method: Anhydrous HF is obtained by heating
due to release of nascent oxygen easily.
dry potassium hydrogen fluoride in a copper retort con-
nected with copper condenser. HClO  HCl + O
 16.7.2 Chlorous Acid [HClO2]

KHF2  KF + HF
Preparation:It is obtained in aqueous solution when barium
(ii) Industrial Method : HF is prepared by heating fluorspar chlorite suspension in water is treated with H2SO4 . The insoluble
(CaF2) with conc H2SO4. barium sulphate is filtered off.
CaF2 + H2SO4  CaSO4 + 2HF Ba(ClO2)2 + H2SO4  BaSO4 + 2HClO2
 Aqueous HF being corrosive to glass, is stored in wax lined Properties:
bottles or vessel made of copper or monel. (i) The freshly prepared solution is colourless but it soon
In glass or silica bottles, it attacks them as follows: decomposes to ClO2 which makes the solution yellow.
SCAN CODE
5 HClO2  4 ClO2 + HCl + 2H2O to the presence of impurities.

(ii) On long standing, it undergoes auto–oxidation into calcium
(ii) The acid undergoes auto-oxidation.
chlorate and calcium chloride.
2HClO2  HClO + HClO3 6 CaOCl2  Ca(CIO3)2 + 5 CaCl2
(iii) The acid liberates iodine from K CoCl
(iii) 2 CaOCl2  2  2 CaCl + O
4K + HClO2 + 2H2O  4KOH + HCl + 22
2 2
(iv) In presence of a little amount of a dilute acid, it loses oxygen.

16.7.3 Chloric Acid [HClO3]
Preparation: This acid is only known in solution. The acid is 2 CaOCl2 + H2SO4  CaCl2 + CaSO4 + 2 HClO
preapred by the action of the dilute H2SO4 on barium chlorate.
HClO  HCl + O
Ba (ClO3)2 + H2SO4  BaSO4+ 2HClO3.
On account of the liberation of nascent oxygen, it shows
Properties: Concentrated acid is colourless and pungent smelling oxidising and bleaching properties.
liquid. It decomposes in light. However, it is stable in dark. It acts
(a) Oxidising properties
as a strong oxidising and bleaching agent in light. Organic
substances like paper, cotton, wool, etc., catch fire in contact with CaOCl2 + H2S  CaCl2 + H2O + S
the acid.
16.7.4 Per-Chloric Acid [HCIO4] CaOCl2 + 2 KI + 2 HCl  CaCl2 + 2 KCl + H2O + I2
Preparation: It is the most stable oxy-acid of chlorine. Anhydrous 3 CaOCl2 + 2 NH3  3 CaCl2 + 3 H2O + N2
HClO4 is obtained by doing distillation of KCIO4 (potassium
It oxidises NO2– to NO3– , AsO33– to AsO43– and Fe2+ to Fe3+
perchlorate), with 96-97.5% H2SO4 under low pressure at 90-160°C.
(in acidic medium)
KCIO4 + H2SO4  KHSO4 + HCIO4 (b) Bleaching action
An aqueous solution of the acid is obtained by reacting barium
perchlorate with calculated quantity of dilute H2SO4. The insoluble Coloured matter + [O]  colourless product.
barium sulphate is removed by filtration. (v) When bleaching powder reacts with dilute acids or CO2 it
Ba(CIO4)2 + H2SO4  BaSO4  + 2HClO4 liberates chlorine which is known as available chlorine.
Properties: CaOCl2 + 2 HCl  CaCl2 + H2O + Cl2

(i) Anhydrous HClO4 is a colourless liquid which turns dark on
keeping. It fumes in moist air. CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
(ii) It is one of the strongest acid and ionises as follows : CaOCl2 + CO2  CaCO3 + Cl2
HClO4  H+ + ClO4–  HNO3 is a strong oxidising acid to be avoided, here.
(iii) It dissolves most of the metals.
Some Important order
Zn + 2HClO4  Zn(ClO4)2 + H2 (a) Acid strength:
(iv) It is an oxidising agent and explodes in contact with organic
matter. (i) H > HBr > HCl > HF
(v) 2HClO4 + P2O5  2HPO3 + Cl2O7 (ii) HOCl > HOBr > HO
(iii) HClO4 > HClO3 >HClO2 > HClO
16.8 Bleaching Powder (CaOCl2.H2O)
(b) Oxidising power :
Bleaching powder is also called calcium chlorohypochlorite
because it is considered as a mixed salt of hydrochloric acid and (i) F2 > Cl2 > Br2 > 2 (According to electrode potential)
hypochlorous acid. (ii) BrO4– > IO4– > ClO4–
Ca(OCl)Cl (iii) HClO4 < HClO3 < HClO2  HClO
Preparation: (c) Order of disproportionation:
40C
Ca(OH)2 + Cl2   Ca(OCl)Cl + H2O 3 XO–  2X– + XO3– (hypohalite ion)
Properties O– > BrO– > ClO–
(i) It is a pale yellow powder. It has a strong smell of chlorine. It
is soluble in water but a clear solution is never formed due
SCAN CODE
17. INTERHALOGEN COMPOUNDS intensity of colour increases with increase in the molecular
We know that halogen atoms have different electronegativity. weight of the compounds.
Due to this difference in electronegativity the halogen atoms (iii) All interhalogens are covalent molecules and are diamagnetic
combine with each other and give rise to the formation of binary in nature since all the valence electrons present as bonding
covalent compounds, which are called interhalogen or non-bonding electrons are paired.
compounds.These are of four types. (iv) The boiling points increases with the increase in the
AB AB3 AB5 AB7 electronegativity difference between A and B atoms.
ClF ClF3 ClF5 lF7 (v) Thermal stability of AB type interhalogen compounds
BrF BrF3 BrF5 decreases with the decrease in electronegativity difference
between A and B atoms. IF > BrF > ClF > ICl > IBr > BrCl.
ICl ICl3 IF5
More polar is the A – B bond more is the stability of interhalogen.
IF IF3
(vi) Interhalogen compounds are more reactive than the parent
Preparation:
halogens but less reactive than F2.
(i) By the direct combination of halogens :
ICl + 2Na  NaI + NaCl
473 K
Cl2 + F2 (equal volumes)   2ClF The order of reactivity of some interhalogens is as follows :
573K ClF3 > BrF3 > IF7 > BrF5 > BrF.
Cl2 + 3F2 (excess)   2ClF3
(vii) Hydrolysis : All these undergo hydrolysis giving halide ion
I2 + Cl2  2ICl derived from the smaller halogen and a hypohalite (when
(equimolar) AB), halite (when AB3), halate (when AB5), and perhalate
(when AB7) anion derived from the larger halogen.
(ii) Diluted with water.
AB + H2O  HB + HOA
Br2 (g) + 3F2  2BrF3
(iii) F2 is diluted with N2 BrCl + H2O  HCl + HOBr
78ºC 2IF
I2 + 3F2  ICl + H2O  HCl + HIO
3
(iv) F2 is taken in excess. ICl3 + 2H2O  3HCl + HIO2

Br2 + 5F2 (excess)  2BrF5
IF5 + 3H2O  5HF + HIO3
IF7 can not be prepared by direct combination of I2 & F2 .
(ii) From lower Interhalogens: IF7 + 6H2O  7HF + H5IO6
ClF + F2  ClF3 BrF5 + 3H2O  5HF + HBrO3

350ºC ClF  Hydrolysis products are halogen acid and oxy-halogen acid.
ClF3 + F2 (excess)  5
Oxy-halogen acid is of larger central halogen atom.
200ºC BrF
BrF3 + F2 (excess)   Oxidation state of A atom does not change during hydrolysis.
5
(viii) Reaction with non-metallic and metallic oxides :

270ºC IF
IF5 + F2  7 4BrF3 + 3SiO2  3SiF4 + 2Br2 + 3O2
This method is generally applied for the preparation of halogen
fluorides. 4BrF3 + 3WO3  2WF6 + 2Br2 + 3O2
Properties: (ix) Addition reaction (of AB type compounds):
(i) These compounds may be gases, liquids or solids. – CH = CH – + ICI  – CHI – CHCl –
Gases : ClF, BrF, ClF3 , IF7
Liquids : BrF3, BrF5 CH2 = CH2 + BrCI  CH2Br – CH2Cl
Solids : ICl, IBr, IF3, ICl3. (x) Reaction with alkali metal halides :
(ii) Interhalogens containing fluorine are colourless but inter IBr + NaBr  NaIBr2 ICl3 + KCl  KICl4
halogens consisting of heavier halogens are coloured. The
SCAN CODE
Uses
noble gases.
These compounds can be used as non aqueous solvents.
Occurrence: All the noble gases except radon occur in the atmo-
Interhalogen compounds are very useful fluorinating agents. ClF3
sphere. Their atmospheric abundabce in dry air is ~ 1% by
and BrF3 are used for the production of UF6 in the enrichment of
volume of which argon is the major constituent. Helium and some-
235
U.
times neon are found in minerals of radioactive origin e.g., pitch-
U(s) + 3 ClF3 (l)  UF6 (g) + 3 ClF (g) blende, monazite, cleveite. The main commercial source of helium
is natural gas. Xenon and radon are the rarest elements of the
18. PSEUDO HALOGENS & PSEUDO HALIDES
group. Radon is obtained as a decay product of 226Ra.
Some inorganic compounds like (CN) 2 cyanogen, (SCN) 2
226 Ra  222 Rn  4 He
thiocyanogen, (SeCN) 2 selenocyanogen, (SCSN 3 ) 2 88 86 2
azidocarbondisulphide have been found to behave like halogens
& they are known as pseudo halogen solids. Similarly few ions Most abundant element in air is Ar. Order of abundance in the air
are known, consisting of two or more atoms of which at least one is Ar > Ne > Kr > He > Xe.
is N, that have properties similar to those of the halide ions. They 20.1 Electronic Configuration
are therefore called pseudohalide ions, e.g. (CN–) cyanide ion, All noble gases have general electronic configuration ns2np6 ex-
(SCN–) thiocyanate ion, (SeCN–) selenocyanate ion, (OCN–) cept helium which has 1s2 . Many of the properties of noble gases
cyanate ion, (NCN2–) cyanamide ion, (N3–) azide ion etc. including their inactive nature are ascribed to their closed shell
structures.
19. USES OF GROUP 17 ELEMENTS 20.2 Ionisation Enthalpy
It is used (i) for bleaching woodpulp (required) for the manufacture Due to stable electronic configuration these gases exhibit very
of paper and rayon), bleaching cotton and textiles, (ii) in the high ionisation enthalpy . However, it decreases down the group
extraction of gold and platinum (iii) in the manufacture of dyes, with increases in atomic size.
drugs and organic compounds such as CCl4, CHCl3, DDT, 20.3 Atomic Radii
refrigerants, etc. (iv) in sterlising drinking water and (v) preparation Atomic radii increase down the group with increase in atomic
of poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2), number.
mustard gas (ClCH2CH2SCH2CH2Cl). 20.4 Electron Gain Enthalpy
Since noble gases have stable electronic configurations, they
20. INTRODUCTION OF GROUP 18 ELEMENTS: have no tendency to accept the electron and therefore, have larger
(THE ZERO GROUP FAMILY) positive values of electron gain enthalpy.
Group 18 Consists of six elements: helium, neon, argon, krypton,
xenon and radon . All these are gases and chemically unreactive.
They form very few compounds . Because of this they are termed
Physical Properties of Group 18
Element He Ne Ar Kr Xe
Atomic Number 2 10 18 36 54
Atomic Mass 4 20.18 39.10 83.80 131.30
Electronic configuration 1s2 [He]2s22p6 [Ne]3s23p6 [Ar]3d104s24p6 [Kr]4d105s25p6
Covalent Radius/pm 120 160 190 200 220
Ionization enthalpy /(kJ mol ) –1
2372 2080 1520 1351 1170
Density (at STP)/g cm–3 1.8 ×10–4 9.0×10–4 1.8×10–3 3.7×10–3 5.9×10–3
Melting point/K – 24.6 83.8 115.9 161.3
Boiling point/K 4.2 27.1 87.2 119.7 165.0
SCAN CODE
Clatherate compounds : Inert gas molecules get trapped in
21. PHYSICAL PROPERTIES OF GROUP 18 the cages formed by the crystal structure of water.
ELEMENTS During the formation of ice Xe atoms will be trapped in the
All the noble gases are monoatomic. They are colourless, and cavities (or cages) formed by the water molecules in the
tasteless. They are sparingly soluble in water. They have very crystal structure of ice. Compounds thus obtained are called
low melting and boiling points because the only type of inter- clatherate compounds.
atomic interaction in these elements is weak dispersion forces,. There are no chemical bonds. They do not possess an exact
Helium has the lowest boiling point (4.2K) of any known sub- chemical formula but approx it is 6 water molecules : 1 inert
stance. It has a unusual property of diffusing through most com- gas molecule. The cavity size is just smaller than the atom of
monly used laboratory materials such as rubber, glass or plastics. the noble gas. Such compounds are also formed by the other
22. CHEMICAL PROPERTIES OF GROUP 18 organic liquids like dihydroxybenzene (for example quinol).
ELEMENTS
In general, noble gases are least reactive. Their inertness to chemi-
cal reactivity is attributed to the following reasons:
(i) The noble gases expect helium (1s2) have completely filled
ns2 np6 electronic configuration in their valence shell.
(ii) They have high ionisation enthalpy and more positive elec-
tron gain enthalpy. Fig 11.6: Clatherate compound
The reactivity of noble gases has been investigated occa- (ii) True chemical compounds (posses proper bonding).
sionally ever since their discovery, but all attempt to force
them to react to form the compounds were unsuccessful for
23. COMPOUNDS OF XENON
quite a few years. In March 1962, Neil Bartlett, then at the
23.1 Xenon Difluoride (XeF2)
University of British Columbia, observed the reaction of a
noble gas. First , he prepared a red compound which is Preparation:
formulated as O2+ PtF6–. He , then realised that the first
873K ,1bar
ionisation enthalpy of molecular oxygen (1175 kj mol –1) was (i) Xe + F2 Ni 
Tube or monel metal (alloy of Ni) XeF2
almost identical with that xenon (1170 kJ mol –1). He made
efforts to prepare same type of compound with Xe+ PtF6 – by Volume ratio should be 2:1 otherwise other higher fluorides
mixing Pt F6 and Xenon. After this discovery, a number of tend to form.
xenon compounds mainly with most electronegative ele- 118C XeF + O
(ii) Xe + O2 F2  2 2
ments like fluorine and oxygen, have been synthesised.
The compounds of krypton are fewer. Only the difluoride Hg (arc)
(iii) Xe + F2   XeF2
(KrF2) has been studied in detail. Compounds of radon have
not been isolated but only identified (e.g., RnF2) by radiotracer (iv) Recently discovered method :
technique. No true compounds of Ar, Ne or He are yet known. K+ [AgF4]– [potassium tetrafluoroargentate ()] is first
 If Helium is compressed and liquified it forms He() liquid at prepared and this is reacted with BF3 .
4.2 K. This liquid is a normal liquid like any other liquid. But
if it is further cooled then He() is obtained at 2.2 K, which is BF3 AgF (red solid) + KBF
K+ [AgF4]–   3 4
known as super fluid, because it is a liquid with properties of
gases. It climbs through the walls of the container & comes 2 AgF3 + Xe  2 AgF2 (Brown solid) + XeF2
out. It has very high thermal conductivity & very low Properties:
viscosity. (i) Colorless crystalline solid and sublimes at 298 K.
Compounds of inert gases are of following two types. (ii) Dissolves in water to give a solution with a pungent odour.
(i) Physical compounds (possess no proper bonding) Much soluble in HF liquid.
Physical compounds may be (A) compounds whose (iii) This is stored in a vessel made up of monel metal which is a
existence is on the basis of spectroscopic studies (temporary alloy of nickel.
phase not isolated) and (B) clatherate compounds.
SCAN CODE
(iv) Reaction with H2: It reacts with hydrogen gas at 400°C (viii) Reactions of XeF2 + HF (anhydrous):
HF
XeF2 + H2  Xe + 2HF Pt + 3XeF2  PtF6 + 3Xe
(v) Hydrolysis: S8 + 24 XeF2  8SF6 + 24 Xe
(a) 2XeF2 + 2H2O  2Xe + 4HF + O2 (slow) 2CrF2 + XeF2  2CrF3 + Xe
The above is neither a cationic hydrolysis nor an anionic 2MoO3 + 6XeF2  2MoF6 + 6Xe + 3O2
hydrolysis as seen in ionic equilibrium. It is a covalent
compound and hydrolysis is like that of PCl5 . Mo (CO)6 + 3 XeF2  Mo F6 + 3 Xe + 6CO
(b) Hydrolysis is more rapid with alkali. HF
2 C6H6 + XeF2  2 C6H5F + Xe
1
XeF2 + 2 NaOH  Xe + O + 2NaF + H2O (fast) 8 NH3 + 3 XeF2  N2 + 6 NH4 F + 3 Xe
2 2
The reaction (a) is slower probably due to dissolution of 2NO2 + XeF2  2 NO2 F + Xe
XeF2 in HF.
(nitronium fluoride)
(vi) Oxidising Properties: Higher the value of SRP better is the
oxidising property of the species. (ix) Formation of Addition Compounds: XeF2 reacts with fluoride
ion acceptors to form cataionic species and fluoride ion
The standard reduction potential for XeF2 is measured to be
donors to form fluoroanions.
+ 2.64 V. Therefore it acts as a strong oxidising agent.
2e– + 2H+ + XeF2  Xe + 2HF SRP = + 2.64 V XeF2 + PF5  [XeF]+ [PF6]–
This oxidises halides to their respective halogens. F5 (lewis acid) + XeF2  [XeF]+ [F6]–
XeF2 + 2 HCl  Xe + 2 HF + Cl2 2SbF5 (lewis acid) + XeF2  [XeF]+ [SbF6]–
Similar behaviour is shown by PF5 and AsF5
It oxidises 2Br –  Br2 + 2e– & 2–  2 + 2e–
Structure: Shape linear and geometry trigonal bipyramidal.
In this manner XeF2 will oxidise halide ions (except F–) into
free halogens.
Similarly it can oxidise BrO3– (bromate) which are themselves
good oxidising agents to BrO4– (perbromate ions) and Ce+3
to Ce+4 ion.
(vii) Oxidising as well as Fluorinating Properties: It can act as Hybridisation = sp3d
strong oxidising agent as well as fluorinating agent.
C6 H5  + XeF2  C6 H5 F2 + Xe Structure of XeF2
CH3+XeF2  CH3 F2 + Xe 23.2 Xenon Tetrafluoride (XeF4)
Preparation:
 CH3 F2 exists as CH3+F2– ,F2– is analogous to 3–
873K,  XeF
Xe  2F 
2 7bar 4
1 : 5 Ni tube
Properties:
Hybridisation = sp3d (i) It is a colorless crystalline solid and sublimes at 298 K.
(ii) It undergoes sublimation, soluble in CF3 COOH.
It undergoes hydrolysis violently hence no moisture
Structure of IF2- must be present during it’s preparation.
 F3– cannot be formed as it has no d-orbitals to attain sp3d (iii) Reaction with H2O :
hybridisation.
6 XeF4 + 12 H2O  4 Xe + 2XeO3 + 24 HF + 3O2
XeO3 is white solid and explosive compound (dry), soluble in
water (well behaved in water)
SCAN CODE
XeO3 reacts with NaOH forming sodium xenate Properties:
XeO3 + NaOH  Na+ [HXeO4]– (sodium xenate) (i) Colourless crystalline solid and sublimes at 298 K.
(ii) It gives yellow liquid on melting where as other form white
 It disproportionates into perxenate ion in basic medium.
liquids on melting (a point of difference)
2 [HXeO4]– + 2OH– [XeO6]4– + Xe + O2 + 2H2O
(iii) HF is a good solvent for all three fluorides.
Xenic acid (H2XeO4) is a very weak acid.
(iv) Hydrolysis:
H (a) Complete hydrolysis:
 XeO6 
4–
water  XeO3  O 2
(i) XeF6  3H 2 O  XeO3  2HF
 slow decomposition  
 whitesolid 

 XeO 6 
4–
(ii)  Mn 2  MnO 4–  XeO3 XeF6  H 2 O  XeOF4  2HF
(b) Partial hydrolysis: 
 colourless 
[XeO6]4– is obtainable as Na4 XeO6.8H2O 
(sodium perxenate) (v) Reaction with Silica (SiO2):

(iv) Oxidising properties of XeF4
2XeF6 + SiO2  2XeOF4 + SiF4
XeF4 + 2 H2  Xe + 4HF
(vi) Thermal Decomposition (effect of heat):
XeF4 + 2 Hg  Xe + 2HgF2 
2XeF6  XeF2 + XeF4 + 3 F2
(v) Addition Reactions: XeF4 reacts with fluoride ion acceptors XeF2 & XeF4 do not undergo decomposition
to form cataionic species and fluoride ion donors to form
(vii) Formation of Addition Compounds:
fluoroanions.
XeF6 + SbF5  [XeF5]+ [SbF6]
XeF4 + SbF5  [XeF3]+ [SbF6]–
XeF6 + BF3  [XeF5]+ [BF4]–
(vi) Fluorinating Agents:
(viii) Reaction with H2 :
XeF4 + Pt  PtF4 + Xe
XeF6 + 3H2  6HF + Xe
XeF4 + 4NO  Xe + 4NOF (nitrosyl Fluoride)
(ix) Reaction of XeF6 with XeO3 :
XeF4 + 4 NO2  Xe + 4 NO2 F (nitronium fluoride) XeO3 + 2 XeF6  3 XeOF4
XeF4 + 2C6 H6  C6H5F + 2HF + Xe (x) F– donating/F accepting properties: XeF6 reacts with fluoride
Structure : Shape square planar & geometry octahedral ion acceptors to form cataionic species and fluoride ion
donors to form fluoroanions.
XeF6 + MF  M+ [XeF7]– (M = Na, K, Rb or Cs)
donation { XeF6 + PtF5  (XeF5+) (PtF6–)
 CsF  XeF6  CsXeF7

  alkali metal   caesium heptafluoroxenate 
 

acceptance   fluride
  

Structure of XeF4 2CsXeF7 XeF6  Cs 2XeF8
  caesium octafluoraxenate 
 
23.3 Xenon Hexafluoride (XeF6)   
Preparation: Order of Oxidising Power:

Xe  3F2 573K,60–70 bar XeF2 > XeF4 > XeF6
(i)   XeF Structure: Shape caped octahedral (distorted oactahedral)
1 : 20 Ni  tube 6
(ii) XeF4 + O2 F2  XeF6 + O2
SCAN CODE
23.4 Xenon–Oxygen Compounds as cryogenic agent for carrying out various experiments at low
Hydrolysis of XeF4 and XeF6 with water gives XeO3. temperatures. It is used to produce and sustain powerful
superconducting magnets which form an essential part of modern
6 XeF4 + 12 H2O  4 Xe + 2 XeO3 + 24 HF + 3 O2 NMR spectrometers and Magnetic Resonance Imaging (MRI)
XeF6 + 3 H2O  XeO3 + 6 HF systems for clinical diagnosis. It is used as a diluent for oxygen in
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2 modern diving apparatus because of its very low solubility in
blood.
XeF6 + H2O  XeOF4 + 2 HF Neon is used in discharge tubes and fluorescent bulbs for
XeF6 + 2 H2O  XeO2F2 + 4 HF advertisement display purposes. Neon bulbs are used in botanical
XeO3 is a colourless explosive solid and has a pyramidal molecu- gardens and in green houses.
lar structure. XeOF4 is a colourless volatile liquid and has a square Argon is used mainly to provide an inert atmosphere in high
pyramidal molecular structure. temperature metallurgical process (arc welding of metals or alloys)
and for filling electric bulbs. It is also used in the laboratory for
24. USES OF GROUP 18 ELEMENTS
handing substances that are air–sensitive.
Helium is a non–inflammable and light gas. Hence, it is used in
Xenon and Krypton are used in light bulbs designed for special
filling balloons for meterological observations. It is also used in
purposes.
gas–cooled nuclear reactors. Liquid helium (b.p.4.2 K) finds use
SCAN CODE
SUMMARY
Group-15 Elements Group-17 Elements
 General Electron Configuration : ns2np3, extra stable  General Electron Configuration : ns2np5
electronic configuration due to half filled p-orbital.  Atomic & Ionic Radii : F < Cl < Br < I due to increasing
 Atomic and Ionic Radii : Increase down the group due to number of shells down the group.
increase in the number of inner shells.  Ionisation Enthalpy(IE) : F > Cl > Br > I due to increase in
 Ionisation Enthalpy(IE) : Decreases down the group due to size down the group.
increase in atomic size.  Electron Gain Enthalpy (EGE) : I > Br > F > Cl as size increases
 Electronegativity : Decreases down the group. down the group. F is an exception because the incoming
 Melting & Boiling Point : Boiling points increase from top electron faces greater interelectronic repulsions in the small-
to bottom and Melting points increase upto Arsenic & then sized 2p orbital of fluorine(F).
decrease upto Bismuth.  Electronegativity: Fluorine is the most electronegative
 Oxidation State : The tendency to exhibit -3 oxidation state element.
decreases down the group due to increase in size and metallic  Melting & Boiling Point : Their melting and boiling points
character (i.e electronegativity). +3 and +5 are generally the increase down the group with atomic number. Because the
covalency and the tendency to show (+3) O.S. in comparison strength of van der Waal force increases with increase in
to (+5) O.S. increases down the group due to the inert pair mass.
effect.  Order of Bond Dissociation Energy is Cl2 > Br2 > F2 > I2.
Group-16 Elements Group-18 Elements

 General Electron Configuration: ns2np4  General Electron Configuration : ns2np6 except helium which
 Atomic and Ionic Radii : Increase down the group due to has 1s2.
increase in the number of shells.  Ionisation Enthalpy : Decreases down the group, Due to
 Ionisation Enthalpy(IE) : Decreases down the group due to stable electronic configuration these gases exhibit very
increase in size. high ionisation enthalpy.
 Electron Gain Enthalpy (EGE) : Becomes less negative down  Atomic Radius : Increases down the group.
the group (S < Se < Te < Po < O) due to increase in size. O is  Electron Gain Enthalpy (EGE) : They have no tendency to
an exception due to interionic repulsion in its small size accept the electron & therefore, have large +ve values of
 Electronegativity : Decreases down the group. EGE.
 Melting & Boiling Point : Increase down the group as the  Melting & Boiling Point : They have low melting point and
strength of van der waals force increases with increase in boiling point. Boiling point increases down the group with
molar mass & size. increase in strength of dispersion forces.
 Oxidation State : The stability of -2 oxidation state decreases  All noble gases are monatomic, colourless, they are
down the group because of decrease in electronegativity. sparingly soluble in water.
The tendency or stability of +4 oxidation state in comparison
to +6 oxidation state increases down the group due to inert
pair effect.
SCAN CODE
p -BLOCK ELEMENTS (GROUP 15-18) 174

Introduction of Group 15 Elements 10. Which of the following statements is correct regarding the
1. Which of the following properties is not compatible with behaviour of white phosphorus?
nitrogen? (a) It is soft, waxy and reactive
(a) Hydrogen bonding (b) Catenation (b) It reacts with moist air to emit a light called
(c) Supporter of life (d) Low boiling point chemiluminescence.
2. N2 is commercially prepared by (c) It exists as tetrahedral P4 molecules both in the liquid

and gaseous states.
(a) fractional distillation of liquefied air
(d) All the above
(b) heating sodium nitrite
Chemical Properties of Group 15 Elements
(c) heating sodium azide
11. Which of the following halides is the most acidic?
(d) heating a mixture of ammonium chloride sodium nitrite
(a) PCl3 (b) SbCl3
3. Which of the following forms strong p - p bonding
(c) BiCl3 (d) CCl4
(a) P4 (b) As4
12. Which of the following halides of nitrogen is stable?
(c) N2 (d) Sb4
(a) NF3 (b) NCl3
4. Nitrogen is an essential constituent of
(c) NBr3 (d) NI3
(a) fats and carbohydrates
(b) carbohydrates and enzymes 13. PCl3 and PCl5 both exist; NCl3 exists but NCl5 does not exist.
It is due to
(c) Proteins and amino acids
(a) lower electronegativity of P than N
(d) vitamin A and vitamin B
(b) lower tendency of N to form covalent bond
5. White phosphorus is kept under
(c) availability of vacant d-orbital in P but not in N
(a) kerosene oil (b) water
(d) statement is itself incorrect
(c) concentrated HNO3 (d) ethanol
14. In which of the following arrangements, the sequence is not
6. Number of electrons shared in the formation of nitrogen
strictly according to the property written against it ?
molecule is
(a) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power
(a) 6 (b) 10
(b) HF < HCl < HBr < HI : increasing acid strength
(c) 2 (d) 8
(c) NH3 > PH3 < AsH3 < SbH3 : increasing basic strength
Physical Properties of Group 15 Elements
(d) B < C < O < N : increasing first ionisation enthalpy
7. Among the following, the element that does not show
allotropy is 15. Which of the following gases is the least reactive?
(a) N (b) P (a) O2 (b) N2
(c) As (d) Bi (c) H2 (d) O3
8. Which of the following, exhibits a layered structure? 16. White phosphorus reacts with NaOH to give PH 3 and
NaH2PO2. This reaction involves
(a) BN (b) N2
(a) oxidation (b) reduction
(c) P4 (d) AsH3
(c) disproportionation (d) neutralization
9. The struture of boron nitride resembles that of
17. Which of the following oxides will be the least acidic?
(a) nickel arsenide (b) graphite
(a) As4O6 (b) As4O10
(c) rock salt (d) diamond
(c) P4O10 (d) P4O6
18. White phosphorus is more reactive than N2 because 26. N2O3 is

(a) electronegativity of phosphorus is low (a) an acidic oxide and the anhydride of HNO2
(b) ionization energy of phosphorus is low (b) an acidic oxide and the anhydride of H2N2O2
(c) P—P bond is weaker than N  N bond (c) a neutral oxide and the anhydride of HNO3
(d) P—P bond is polymeric (d) a basic oxide and the anhydride of HNO2
General Properties and Compounds of Nitrogen 27. Which of the following oxides of nitrogen is a mixed
anhydride of two acids?
19. The bond order in the NO molecule is
(a) N2O3 (b) N2O4
(a) 3 (b) 1.5
(c) N2O5 (d) N2O
(c) 2.5 (d) 2.0
28. Which of the following oxides of nitrogen is paramagnetic?
20. Which of the following statements is true ?
(a) NO2 (b) N2O3
(a) H3PO3 is a stronger acid than H2SO3
(c) N2O (d) N2O5
(b) In aqueous medium HF is a stronger acid than HCl
29. Which of the following is a nitric acid anhydride?
(c) HClO4 is weaker acid than HClO3
(a) NO (b) NO2
(d) HNO3 is a stronger acid than HNO2 (c) N2O5 (d) N2O3
21. Which of the following statements is wrong ? 30. Ammonia gas can be dried by
(a) The stability of hydries increases from NH3 to BiH3 in (a) conc. H2SO4 (b) P4O10
group 15 of the Periodic Table (c) anhydrous CaCl2 (d) CaO
(b) Nitrogen can’t form d-p bond. 31. At present, HNO3 is industrially prepared by the
(c) Single N—N bond is weaker than the single P—P bond. (a) contact process
(d) N2O4 has two resonance structure (b) Birkeland-Eyde process
22. Which one of the following properties is not shown by (c) Ostwald process
NO ?
(d) Haber process
(a) It is a neutral oxide
32. Gold reacts with aqua regia forming
(b) It combines with oxygen to form nitrogen dioxide
(a) auric chloride (AuCl3)
(c) It’s bond order is 2.5
(b) chloroauric acid (HAuCl4)
(d) It is diamagnetic in gaseous state
(c) chloroaurous acid (HAuCl3)
23. Which one of the following molecules is paramagnetic ?
(d) purple of Cassius
(a) O3 (b) N2 33. Platinum reacts with aqua regia to produce chloroplatinic
(c) NO (d) CO acid represented by the formula
24. Aqueous solution of ammonia consists of (a) H4 [PtCl6] (b) H [PtCl4]
–
(a) H (b) OH (c) H2 [PtCl6] (d) H2 [PtCl4]
34. A solution of sodium in liquid ammonia is blue due to the
(d) NH4 and OH
–
(c) N 4
presence of
25. Iodine reacts with concentrated HNO3 to produce (a) solvated electrons (b) ammonium ions
(a) H5IO6 (b) HIO4 (c) solvated sodium ions (d) sodium atoms
(c) HIO3 (d) HIO
35. Among the following compounds of nitrogen and hydrogen, 42. The number of hydrogen atom(s) attached to phosphorus
the most acidic compound is atom in hypophosphorous acid is
(a) NH3 (b) N2H4 (a) three (b) one
(c) N2H2 (d) HN3 (c) two (d) zero
36. Which one of the following compounds is most explosive? 43. Syrupy H3PO4 is viscous due to
(a) NCl3 (b) PCl3 (a) intermolecular hydrogen bonding
(c) AsCl3 (d) NF3 (b) van der Waals forces among the H3PO4 molecules
37. The most stable oxidation states of nitrogen are (c) covalent bonding in P—O linkage
(a) -3, +3 and +5 (b) -3, 0 and -1 (d) low activation energy in H3PO4
(c) -3, +3 and 0 (d) -3, +3 and -5 44. Which of the following statements is true for the H3PO3
molecule?
General Properties and Compounds of Phosphorus
(a) It contains two acidic H atoms
38. Phosphorus reacts with concentrated HNO3 to produce
(b) It contains one reducing H atom
(a) hypophosphoric acid (b) orthophosphorus acid
(c) It can form two series of salts
(c) pyrophosphoric acid (d) orthophosphoric acid
(d) All of these
39. Which of the following structures represents
hypophosphoric acid? 45. PCl5 on hydrolysis gives
(a) H3PO2 (b) H3PO3
(c) H3PO4 (d) H5P3O10
(a) (b) 46. Solid PCl5 exists as
(a) [PCl4]+ and [PCl6]- ions
(b) [PCl4]- and [PCl6]+ ions
(c) covalent PCl5 molecules only
(c) (d) (d) [PCl4]2+ and [PCl6]2- ions
47. Identify the incorrect statement related to PCl5 from the
following:
40. Which of the following oxoacids of phosphorus is a reducing (a) PCl5 molecule is non-reactive.
agent and a monobasic acid as well?
(b) Three equatorial P – Cl bonds make an angle of 120° with
(a) Orthophosphorus acid (H3PO3) each other.
(b) Hypophosphorus acid (H3PO2) (c) Two axial P – Cl bond make an angle of 180° with each
(c) Pyrophosphorus acid (H4P2O5) other.
(d) Metaphosphorus acid (HPO3) (d) Axial P – Cl bonds are longer than equatorial P – Cl
41. The number of P—O—P bonds in cyclic metaphosphoric bonds.
acid is 48. Which one of the following substance is used in the
(a) zero (b) two laboratory for fast drying of neutral gases?
(c) three (d) four (a) Phosphorus pentoxide

(b) Active charcoal
(c) Anhydrous calcium chloride
(d) Na3PO4
49. The structural formula of hypophosphorus acid is 54. Which of the following statements regarding sulphur is
incorrect ?
(a) (b) (a) S2 molecule is paramagnetic.
(b) The vapour at 200ºC consists mostly of S8 rings.
(c) At 600ºC the gas mainly consists of S2 molecules.
(c) (d) None of these (d) The oxidation state of sulphur is never less than +4 in its
compounds.
Chemical Properties of Group 16 Elements
50. Which of the following statements is correct? 55. H2S is less stable than H2O because
(a) Phosphorus does not form p-p multiple bonds in its (a) the bonding orbitals of sulphur are larger and more
compounds. diffuse than those of oxygen, and hence they overlap
(b) Phosphorus forms weak to moderate d- p multiple less effectively with the 1s orbital of the hydrogen atom
bonds in some of its compounds. (b) the bonding orbitals of sulphur are smaller and more
(c) Phosphorus can expand its valence shell by utilizing diffuse than those of oxygen, and hence they overlap
inner 3d orbitals. less effectively with the 1s orbital of the hydrogen atom
(d) All of these (c) the bonding orbitals of sulphur are smaller and less
diffuse than those of oxygen, and hence they overlap
Uses of Group 15 Elements less effectively with the is orbital of the hydrogen atom
51. Regular use of which of the following fertilizers increase the
(d) H2O molecules form H bonds but H2S molecules do not
acidity of soil ?
56. The stability of the hydrides of oxygen, sulphur, selenium
(a) Potassium nitrate and tellurium decreases in the order
(b) Urea
(a) H2Te > H2Se >H2S > H2O
(c) Superphosphate of lime
(b) H2O > H2S >H2Se > H2Te
(d) Ammonium sulphate (c) H2O > H2S < H2Se > H2Te
Introduction and Physical Properties of Group 16 (d) H2O  H2S > H2Tee > H2Se
Elements 57. Which of the following compounds is thermodynamically
52. Group 16 elements (except polonium) are called unstable?
chalcogens because (a) H2O (b) H2Se
(a) these elements, particularly sulphur and oxygen, are (c) H2S (d) NH3
present in many metallic ores mainly as oxides and 58. Which would quickly absorb oxygen?
sulphides
(a) Alkaline solution of pyrogallol
(b) a large number of acids contain these elements,
(b) Conc. H2SO4
particularly sulphur and oxygen
(c) Lime Water
(c) these elements mainly form anions
(d) Alkaline solution of CuSO4
(d) these elements exist in different allotropic forms
59. PtF6 converts O2 to
53. In the cyclo-S8 molecule of rhombic sulphur, all the S—S
bond lengths and all the S—S—S bond angles are (a) O 2 PtF 6 (b) O 2 PtF 6
respectively (approximate values)
(c) F2+PtO2 (d) F2O + Pt
(a) 204 pm and 1070 (b) 102 pm and 1200
(c) 204 pm and 1800 (d) 102 pm and 600
General Properties and Compounds of Oxygen General Properties and Compounds of Sulphur
60. In ozone, the central oxygen atom uses 68. Which of the following statements is not correct for sulphur?
(a) roughly sp2 orbitals for  bonding (a) In sulphur, stronger p-d overlap takes place because
(b) sp orbitals for  bonding only the size of the d orbitals is similar to that of the p orbitals.
(c) sp3 orbitals for  bonding (b) The size of the atom and the size of the 3d orbitals
decrease from S to Cl because on crossing a period in
(d) pd 2z bonding for both  and  bonding the periodic table, the nuclear charge is increased and s
and p electrons shield the nuclear charge incompletely
61. Which of the following statements is correct?
(c) Due to stronger p-d overlap, only a few sulphur
(a) Ozone decomposes to give oxygen
compounds polymerize.
(b) Ozone is thermodynamically unstable.
(d) Sulphur belongs to 18th group.
(c) The decomposition of ozone is exothermic.
69. H2S turns an acidified K2Cr2O7 solution
(d) All of these
(a) violet (b) orange
62. Ozone is an extermely powerful oxidizing agent. It is
(c) green (d) colourless
(a) second only to F2 in oxidizing power
70. H2S turns an acidified KMnO4 solution
(b) second only to O2 in oxidizing power
(a) green (b) pink
(c) second only to Cl2 in oxidizing power
(c) blue-black (d) colourless

(d) second only to MnO in oxidizing power
4
71. Which of the following ions does not have an S—S linkage?
63. At room temperature, O3 is absorbed by (a) S2O 82  (b) S2O 26 

(a) water (b) palladium
(c) S2O 52  (d) S2O 32 
(c) acetic acid (d) turpentine oil
64. The gases absorbed by alkaline pyrogallol and oil of 72. Sulphur dioxide reacts with chlorine in the presence of
cinnamon are respectively charcoal (which acts as a catalyst) to give
(a) O3 and CH4 (b) O2 and O3 (a) sulphuryl chloride
(c) SO2 and CH4 (d) N2O and O3 (b) thionyl chloride
65. O3 is (c) sulphur dichloride and oxygen
(a) an allotrope of oxygen (b) an isomer of oxygen (d) chlorine monoxide and sulphur
(c) an isotone of oxygen (d) isostructural with O2 73. Which of the following gases may act both as an oxidizing
and a reducing agent?
66. Ozone is prepared by the action of silent electric discharge
upon oxygen in an apparatus called ozonizer. The reaction (a) H2S (b) SO3
(a) is exothermic (c) SO2 (d) O2
(b) is endothermic 74. When SO2 gas is passed into an acidified solution of K2Cr2O7,
the oxidation state of chromium changes
(c) leads to the dissociation of the O2 molecule
(a) from +12 to +6 (b) from +3 to +6
(d) leads to the formationi of O 2
(c) from +6 to +3 (d) from +6 to +4
67. Ozonized oxygen is a mixture of 75. A gas that cannot be collected over water is
(a) O3 and N2 (b) O3 and O 2 (a) N2 (b) O2

(c) SO2 (d) PH3
(c) O3 and O2 (d) O3 and Cl2
76. Dehydration of concentrated H2SO4 in the presence of P4O10 84. All the halogens are coloured. The colours arise due to
produces (a) weak van der Waals forces between the halogen
(a) SO2 (b) H2S molecules
(c) O2 (d) SO3 (b) strong oxidizing power of the halogens
77. H2SO4 is manufactured from SO2(g) by the (c) absorption of light which causes an electron to jump
(a) Hall process (b) contact process form the ground state to a higher state
(c) Raschig process (d) Haber process (d) absorption of light due to transfer of an electron from a
higher state to the ground state
78. In the presence of water, sulphur is oxidized by ozone to
give Chemical Properties of Group 17 Elements
(a) H2SO3 (b) SO2 85. Standard sodium thiosulphate solution is used in the
(c) H2SO4 (d) SO3 estimation of iodine present in a solution. The equivalent
weight of sodium thiosulphate which is required to make
Introduction of Group 17 Elements the standard solution is
79. Which of the following are not correctly matched? (a) (molecular weight)/2
(a) A halogen which is a liquid at room temperature  (b) (molecular weight)/3
bromine
(c) the same as the molecular weight
(b) The most electronegative element  fluorine
(d) (molecular weight)/4
(c) The strongest oxidizing halogen  iodine
86. Sodium thiosulphate reacts with iodine to give
(d) The most reactive halogen  fluorine
(a) SO 24  (b) SO 32 
80. Which of the following elements can have both positive
and negative oxidation states?
(c) S4O 26  (d) S2-
(a) Fluorine (b) Iodine
(c) Lithium (d) Helium 87. Bromine can be liberated from KBr by the action of
81. Which of the following halogens has only one oxidation (a) iodine solution (b) chlorine water
state of –1 in an aqeous solution? (c) sodium chloride (d) potassium iodide
(a) Iodine (b) Chlorine 88. Identify the incorrect statement among the following.
(c) Bromine (d) Fluorine (a) Ozone reacts with SO2 to give SO3
82. Which of the following reactions may be used for the (b) Silicon reacts with NaOH (aq) in the presence of air to
preparation of chlorine? give Na2SiO3 and H2O
(a) KMnO4+HCl (conc.)  (c) Cl2 reacts with excess of NH3 to give N2 and HCl
(b) NaCl + MnO2 + H2SO4 (conc.) 
(d) Br2 reacts with hot and strong NaOH solution to give
(c) Ca(OCl)Cl + H2O  NaBr, NaBrO4 and H2O
(d) All of these 89. Which of the following halide ions the most basic?
Physical Properties of Group 17 Elements
(a) F– (b) Cl–
83. Which of the following statements is correct for the iodine
(c) Br– (d) I–
molecule?
90. Which one among the following is the most powerful
(a) In liquid state it conducts electricity, though very slightly,
oxidizing agent?
due to self-ionization: 3I2  I 3 + I 3 (a) Cl2 (b) Br2
(b) Its conductivity increases with the rise in temperature. (c) F2 (d) I2
(c) It behaves like an intrinsic semiconductor
(d) All the above
91. Which of the following is arranged in order of increasing General Properties and Compounds of Halogens
bond energy?
98. SiO2 reacts with HF to produce
(a) I2 < Br2 < Cl2 < F2 (b) I2 < F2 < Br2 < Cl2
(a) Si and H2O (b) Si and HFO2
(c) I2 < Br2 < F2 < Cl2 (d) Cl2 < Br2 < F2 < I2
(c) SiF6 and H2O (d) H2[SiF6] and H2O
92. One of the reasons why the F—F bond is weak is that
99. Concentrated hydrochloric acid when kept in open air
(a) the repulsion between the nonbonding pairs of electrons sometimes produces a cloud of white fumes. The explanation
of the two fluorine atoms is high for it is that
(b) the ionization energy of the fluorine atom is very high (a) concentrated hydrochloric acid emits strongly smelling
(c) the F—F bond distance is large HCl gas all the time
(d) the F—F bond distance is small and hence internuclear (b) oxygen in air reacts with the emitted HCl gas to form a
repulsion is small cloud of chlorine gas
93. In spite of having lower dissociation energies, bromine and (c) strong affinity of HCl gas for moisture in air results in
iodine are weaker oxidizing agents than chlorine due to their forming of droplets of liquid solution which appears like
(a) smaller electron affinities and greater hydration energies a cloudy smoke
(b) smaller electron affinities and smaller hydration energies (d) due to strong affinity for water, concentrated hydrochloric
acid pulls moisture of air towards itself. This moisture
(c) greater electron affinities and greater hydration energies forms droplets of water and hence, the cloud
(d) greater electron affinities and smaller hydration energies
Interhalogen Compounds and Uses of Group 17
94. Fluorine react with water to produce
Elements
(a) HF, O2 and O3 (b) HF and O2
100. Which of the following statements is not appropriate
(c) HF and OF2 (d) HF and O3 regarding the characteristics of interhalogen compounds?
95. When Cl2 gas reacts with hot and concentrated sodium (a) They are usually less reactive than halogens (except
hydroxide solution, the oxidation number of chlorine fluorine).
changes from
(b) They are not so stable, but none of them is explosive
(a) zero to +1 and zero to –5
(c) They are covalent in nature
(b) zero to –1 and zero to +5
(d) They have low boiling points and are highly volatile
(c) zero to –1 and zero to +3
101. The bleaching action of chlorine is due to
(d) zero to +1 and zero to –3
(a) reduction (b) hydrogenation
96. Which of the following is used in the preparation of chlorine?
(c) chlorination (d) oxidation
(a) Both MnO2 and KMnO4
Introduction and Physical Properties of Group 18
(b) Only KMnO4
Elements
(c) Only MnO2
102. Which of the following forms the least number of
(d) Either MnO2 or KMnO4 compounds?
97. When SO2 gas is passed into chlorine water, the products (a) Helium (b) Argon
formed are
(c) Krypton (d) Xenon
(a) SCl2 and S2Cl2 (b) H2SO4 and HCl
103. Which of the following noble gases is the least polarizable?
(c) SO2Cl2 (d) SOCl2 and HCl
(a) He (b) Ar
(c) Ne (d) Xe
104. The element which has the highest first ionization energy is
(a) hydrogen (b) xenon
(c) fluorine (d) helium
105. Noble gases are difficult to liquefy because their 110. Which of the following xenon-OXO compounds may not
(a) dispersion forces are large be obtained by hydrolysis of xenon fluorides?
(b) dispersion forces are small (a) Xe O3 (b) Xe O4

(c) ionization energies are low (c) Xe O2F2 (d) Xe O F4
(d) electron affinities are high 111. XeF4 reacts violently with water to give
Compounds of Xenon (a) Xe and O2 (b) XeOF4
106. Indentify the incorrect statement, regarding the molecule (c) Xe, O3 and HF (d) XeO3, O2 and HF
XeO4. Uses of Group 18 Elements
(a) XeO4 molecule is square planar.
112. Which of the following noble gases is used for cryogenic
(b) There are four p-d bonds. works?
(c) There are four sp 3  p ,bonds. (a) Neon (b) Krypton

(c) Helium (d) Argon
(d) XeO4 molecule is tetrahedral.
113. For breathing, deep-sea divers use a mixture of
107. Which one of the following reaction of xenon compounds
is not feasible ? (a) O2 and H2 (b) O2 and N2
(a) XeO3 + 6HF  XeF6 + 3H2O (c) O2 and He (d) O2 and Ar

114. Which one of the following statements regarding helium is
(b) 3XeF4 + 6H2O  2Xe + XeO3 + 12HF + 1.5O2
incorrect ?
(c) 2XeF2 + 2H2O  2Xe + 4HF + O2
(a) It is used to fill gas balloons instead of hydrogen because
(d) XeF6 + RbF  Rb [XeF7] it is lighter and non-inflammable
108. Xenon trioxide (XeO3) has a shape of a (b) It is used as a cryogenic agent for carrying out
(a) trigonal bipyramid (b) octahedron experiments at low temperatures
(c) pyramid (d) tetrahedron (c) It is used to produce and sustain powerful
superconducting magnet
109. The structure of XeO3F2 is
(d) It is used in gas-cooled nuclear reactors
(a) square pyramidal (b) pentagonal bipyramidal
(c) trigonal bipyramidal (d) octahedral
EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

Questions marked with asterisk (*) are
deleted from JEE Main 9 *. Which one of the following is used to remove most of
1 *. Chemical nature of the nitrogen oxide compound obtained plutonium from spent nuclear fuel? (2021)
from a reaction of concentrated nitric acid and P4 O10 (a) ClF3 (b) O2F2
(c) I2O5 (d) BrO3
(in 4 : 1 ratio) is: (2021)
10. Which one of the following is formed (mainly) when red
(a) acidic (b) basic
phosphorus is heated in a sealed tube at 803 K?
(c) amphoteric (d) neutral
(2021)
2 *. Which one of the following gases is reported to retard
(a) White phosphorus (b) Yellow phosphorus
photosynthesis (2021)
(a) CO (b) CFCs (c)  -Black phosphorus (d)  -Black phosphorus
(c) CO2 (d) NO2 11. Which one of the following correctly represents the order
3. Which one of the following group-15 hydrides is least of stability of oxides, X2O; (X = halogen)? (2021)
stable? (2021) (a) Br > Cl > I (b) Br > I > Cl
(a) AsH3 (b) BiH3 (c) Cl > I > Br (d) I > Cl > Br
(c) PH3 (d) SbH3 12. The number of S=O bonds present in sulphurous acid,
4. Number of Cl = O bonds in chlorous acid, chloric acid and peroxodisulphuric acid and pyrosulphuric acid,
perchloric acid respectively are: (2021) respectively are: (2021)
(a) 3, 1 and 1 (b) 4, 1 and 0 (a) 2, 3 and 4 (b) 1, 4 and 3
(c) 4, 1 and 0 (d) 1, 2 and 3 (c) 2, 4 and 3 (d) 1, 4 and 4
5 *. The incorrect statement is: (2021) 13. The oxide without nitrogen-nitrogen bond is : (2021)
(a) Cl2 is more reactive than ClF (a) N2O (b) N2O4
(b) F2 is more reactive than ClF (c) N2O3 (d) N2O5
(c) On hydrolysis CIF froms HOCl and HF. 14. The set that represents the pair of neutral oxides of
nitrogen is : (2021)
(d) F2, is a stronger oxidizing agent than Cl2 in aqueous
solution (a) N 2 O and NO2 (b) NO and N 2 O
6 *. The number of non-ionisable hydrogen atoms present in
(c) N 2 O and N 2 O3 (d) NO and N 2 O3
the final product obtained from the hydrolysis of PCl5 is
(2021) 15*. The number of ionisable hydrogens present in the product
obtained from a reaction of phosphorus trichloride and
(a) 0 (b) 2
phosphonic acid is : (2021)
(c) 1 (d) 3
(a) 2 (b) 3
7. Chalcogen group elements are: (2021)
(c) 1 (d) 0
(a) Se, Tb and Pu (b) Se, Te and Po
16. Among the following allotropic forms of sulphur, the
(c) S, Te and Pm (d) O, Ti and Po number of allotropic forms, which will show
8. In polythionic acid, H2SxO6 (x = 3 to 5) the oxidation state(s) paramagnetism is (2021)
of sulphur is/are: (2021)
(A)  -sulphur
(a) + 5 only (b) + 6 only
(B)  -sulphur
(c) + 3 and + 5 only (d) 0 and + 5 only
(C) S2-form
Questions marked with asterisk (*) are 21*. Match List –I with List – II
deleted from JEE Main List I List II
17*. Among the following, the number of halide(s) which is/ Industrial process Application
are inert to hydrolysis is_____. (2021) A Haber’s process (i) HNO synthesis
B Ostwald’s process (ii) Aluminium extraction
(a) BF3 (b) SiCl4 C Contact process (iii) NH3 synthesis
(c) PCl5 (d) SF6 D Hall-Heroult (iv) H2SO4 synthesis
process
18*. A xenon compound ‘A’ upon partial hydrolysis give
XeO 2 F2 . The number of lone pair of electrons present in AChoose the correct answer from the options given below
compound A is .................... . (Round off to the Nearest (2021)
Integer) (2021) (a) A – (iii), B – (iv), C – (i), D – (ii)
19. These are physical properties of an element (2021) (b) A – (ii), B – (iii), C – (iv), D – (i)
(a) Sublimation enthalpy (b) Ionisation enthalpy (c) A – (iii), B – (i), C – (iv), D – (ii)
(c) Hydration enthalpy (d) Electron gain enthalpy (d) A – (iv), B – (i), C – (ii), D – (iii)
The total number of above properties that affect the 22. Match List-I with List-II
reduction potential is...... .
20. The number of halogen(s) forming halic (V) acid is List I List II
__________. (2021) Name of oxo acid Oxidation
state of ‘P’
A Hypophosphorous acid (i) +5
Match the Following B Orthophosphoric acid (ii) +4
C Hypophosphoric acid (iii) +3
Each question has two columns. Four options D Orthophosphorous acid (iv) +2
are given representing matching of elements (v) +1
from Column-I and Column-II. Only one of Choose the correct answer from the options given below:
these four options corresponds to a correct (2021)
matching. For each question, choose the (a) A – (iv), b – (i), C – (ii), D – (iii)
option corresponding to the correct matching (b) A – (iv), b – (v), C – (ii), D – (iii)
(c) A – (v), b – (iv), C – (ii), D – (iii)
(d) A – (v), b – (i), C – (ii), D – (iii)
Questions marked with asterisk (*) are 31. Given below are two statements: one is labelled
as Assertion A and the other is labelled as Reason R.
deleted from JEE Main Assertion A: Flourine forms one oxoacid.
23. PCl5 is well known, but NCl5 is not. Because, Reason R: Flourine has smallest size amongst all
(JEE Main 2022) halogens and is highly electronegative.
In the light of the above statements, choose the most
(a) Nitrogen is less reactive than phosphorous.
appropriate answer from the options given below.
(b) Nitrogen doesn't have d-orbitals in its valence shell. (JEE Main 2022)
(c) Catenation tendency is weaker in nitrogen than (a) Both A and R are correct and R is the correct
phosphorous. explanation of A.
(d) Size of phosphorous is larger than nitrogen. (b) Both A and R are correct but R is NOT the correct
24. The most stable trihalide of nitrogen is : explanation of A.
(JEE Main 2022) (c) A is correct but R is not correct.
(d) A is not correct but R is correct.
(a) NF3 (b) NCl3
32*. Heating white phosphorus with conc. NaOH solution
(c) NBr3 (d) NI3
gives mainly: (JEE Main 2022)
25*. The number of bridged oxygen atoms present in
(a) Na3P and H2O
compound B formed from the following reactions is
(b) H3PO and NaH
Pb  NO3 2 
673K
 A  PbO  O2 (c) P(OH)3 and NaH2PO4
A 
Dimerise
B (JEE Main 2022) (d) PH3 and NaH2PO2
(a) 0 (b) 1 33*. Nitrogen gas is obtained by thermal decomposition of
(c) 2 (d) 3 (JEE Main 2022)
26. The correct order of melting points of hydrides of (a) Ba(NO3)2 (b) Ba(N3)2
group 16 elements is: (JEE Main 2022) (c) NaNO2 (d) NaNO3
(a) H2S < H2Se < H2Te < H2O 34. Given below are two statements:
(b) H2O < H2S < H2Se < H2Te Statement I: The pentavalent oxide of group-15
(c) H2S < H2Te < H2Se < H2O element, E2O5, is less acidic than trivalent oxide, E2O3,
(d) H2Se < H2S < H2Te < H2O of the same element.
27*. Consider the following reaction: Statement II: The acidic character of trivalent oxide
A + alkali → B (Major Product) of group 15 elements, E2O3, decreases down the group.
If B is an oxoacid of phosphorus with no P–H bond, In light of the above statements, choose most
then A is: (JEE Main 2022) appropriate answer from the options given below:
(a) White P4 (b) Red P4 (JEE Main 2022)
(c) P2O3 (d) H3PO3 (a) Both Statement I and Statement II are true
28. The oxide which contains an odd electron at the (b) Both Statement I and Statement II are false
nitrogen atom is (JEE Main 2022) (c) Statement I true, but statement II is false
(a) N2O (b) NO2 (d) Statement I is false but statement II is true
(c) N2O3 (d) N2O5 35. Among the given oxides of nitrogen; N2O, N2O3,
29. Identify the incorrect statement for PCl5 from the N2O4 and N2O5, the number of compound/ (s) having
following. (JEE Main 2022) N – N bond is: (JEE Main 2022)
(a) In this molecule, orbitals of phosphorous are (a) 1 (b) 2
assumed to undergo sp3d hybridization. (c) 3 (d) 4
(b) The geometry of PCl5 is trigonal bipyramidal. 36. Which of the following oxoacids of sulphur contains
(c) PCl5 has two axial bonds stronger than three “S” in two different oxidation states?
(JEE Main 2022)
equatorial bonds.
(a) H2S2O3 (b) H2S2O6
(d) The three equatorial bonds of PCl5 lie in a plane. (c) H2S2O7 (d) H2S2O8
30*. The gas produced by treating an aqueous solution of 37. The oxoacid of phosphorus that is easily obtained from
ammonium chloride with sodium nitrite is a reaction of alkali and white phosphorus and has two
(JEE Main 2022) P-H bonds, is: (JEE Main 2022)
(a) Phosphonic acid
(a) NH3 (b) N2
(b) Phosphinic acid
(c) N2O (d) Cl2 (c) Pyrophosphorus acid
(d) Hypophosphoric acid
Questions marked with asterisk (*) are (c) HIO3, NO2 and H2O
(d) HIO4, N2O and H2O
deleted from JEE Main 45*. Consider the following reactions:
38*. The interhalogen compound formed from the reaction PCl3 + H2O → A + HCl
of bromine with excess of fluorine is a: A + H2O → B + HCl
(JEE Main 2022) The number of ionisable protons present in the product
(a) Hypohalite (b) Halate B is _____ (JEE Main 2022)
46. Consider the following sulphur based oxoacids.
(c) Perhalate (d) Halite
H2SO3, H2SO4, H2S2O8 and H2S2O7.
39. Which oxoacid of phosphorous has the highest number Amongst these oxoacids, the number of those with
of oxygen atoms present in its chemical formula? peroxo(O-O) bond is______. (JEE Main 2022)
(JEE Main 2022) 47*. Which of the Phosphorus oxoacid can create silver
(a) Pyrophosphorous acid mirror from AgNO3 solution? (JEE Main 2023)
(b) Hypophosphoric acid (a) ( HPO3 ) n (b) H 4 P2 O5
(c) Phosphoric acid
(c) H 4 P2 O6 (d) H 4 P2 O7
(d) Pyrophosphoric acid
48*. Reaction of thionyl chloride with white phosphorus
40*. White phosphorus reacts with thionyl chloride to give
forms a compound [A], which on hydrolysis gives [B],
(JEE Main 2022) a dibasic acid. [A] and [B] are respectively
(a) PCl5, SO2 and S2Cl2 (JEE Main 2023)
(b) PCl3. SO2 and S2Cl2 (a) P4 O6 and H 3 PO3
(c) PCl3, SO2 and Cl2 (b) PCl3 and H 3 PO3
(d) PCl5, SO2 and Cl2 (c) PCl5 and H 3 PO4
41. Dinitrogen and dioxygen are the main constituents of
(d) POCl3 and H 3 PO4
air and do not react with each other in atmosphere to
form oxides of nitrogen because (JEE Main 2022) 49. Inert gases have positive electron gain enthalpy. Its
(a) N2 is unreactive in the condition of atmosphere. correct order is (JEE Main 2023)
(b) Oxides of nitrogen are unstable. (a) Xe < Kr < Ne < He
(c) Reaction between them can occur in the presence (b) He < Ne < Kr < Xe
of a catalyst. (c) He < Xe < Kr < Ne
(d)The reaction is endothermic and require very high
(d) He < Kr < Xe < Ne
temperature.
50. The bond dissociation energy is highest for
42*. Dinitrogen is a robust compound, but reacts at high
altitude to form oxides. The oxide of nitrogen that can (JEE Main 2023)
damage plant leaves and retard photosynthesis is : (a) Cl2 (b) I 2
(JEE Main 2022) (c) Br2 (d) F2
(a) NO (b) NO3–
(c) NO2 (d) NO2– 51*. “A” obtained by Ostwald’s method involving air
43*. Match List-I with List-II, match the gas evolved oxidation of NH 3 , upon further air oxidation produces
during each reaction. “B”. “B” on hydration forms an oxoacid of Nitrogen
List-I List-II along with evolution of “A”. The oxoacid also
(A) (NH4)2 Cr2O7  
 (I) H2 produces “A” and gives positive brown ring test
(B) KMnO4 + HCl → (II) N2 (JEE Main 2023)
(C) Al + NaOH + H2O → (III) O2
 (a) NO2 , N 2 O5 (b) NO2 , N 2 O4
(D) NaNO3   (IV) Cl2
Choose the correct answer from the options given (c) NO, NO (d) N 2 O3 , NO2
below: (JEE Main 2022) 52. For OF2 molecule consider the following:
(a) (A) – (II), (B) – (III), (C) – (I), (D) – (IV)
(A) Number of lone pairs on oxygen is 2.
(b) (A) – (III), (B) – (I), (C) – (IV), (D) – (II)
(B) FOF angle is less than 104.5 .
(c) (A) – (II), (B) – (IV), (C) – (I), (D) – (III)
(C) Oxidation state of O is –2.
(d) (A) – (III), (B) – (IV), (C) – (I), (D) – (II)
(D) Molecule is bent ‘V’ shaped.
44*. Concentrated HNO3 reacts with Iodine to give (E) Molecular geometry is linear.
(JEE Main 2022) Correct options are: (JEE Main 2023)
(a) HI, NO2 and H2O (a) C, D, E only (b) B, E, A only
(b) HIO2, N2O and H2O (c) A, C, D only (d) A, B, D only
Questions marked with asterisk (*) are In the light of the above statements, choose the most
appropriate answer from the options below.
deleted from JEE Main (JEE Main 2023)
53. Bond dissociation energy of E–H bond of the “ H 2 E ” (a) Both Statement I and Statement II are incorrect
(b) Statement I is correct but Statement II is incorrect
hydrides of group 16 elements (given below), follows
(c) Statement I is incorrect but Statement II is correct
order.
(d) Both Statement I and Statement II are correct
(A) O (B) S
(C) Se (D) Te 59. The number of P – O – P bonds in H 4 P2 O7 , ( HPO3 )3 ,
(JEE Main 2023) and P4 O10 are respectively (JEE Main 2023)
(a) A > B > C > D (b) A > B > D > C (a) 1, 3, 6 (b) 1, 2, 4
(c) B > A > C > D (d) D > C > B > A (c) 0, 3, 4 (d) 0, 3, 6
54. Given below are two statements: 60. ClF5 at room temperature is a: (JEE Main 2023)
Statement I: Chlorine can easily combine with
(a) Colourless liquid with trigonal bipyramidal
oxygen to from oxides: and the product has a tendency
geometry
to explode.
(b) Colourless liquid with square pyramidal geometry
Statement II: Chemical reactivity of an element can
(c) Colourless gas with trigonal bipyramidal
be determined by its reaction with oxygen and
geometry
halogens.
(d) Colourless gas with square pyramidal geometry
answer from the options given below. 61*. The connect group of halide ions which can be
(JEE Main 2023) oxidised by oxygen in acidic medium is
(a) Both the statements I and II are true (JEE Main 2023)
(b) Statement I is true but Statement II is false (a) Br – only
(c) Statement I is false but Statement II is true (b) I – only
(d) Both the Statements I and II are false (c) Cl – , Br – and I – only
55. Match List I with List II. (d) Br – and I – only
List Oxide List II Type of bond 62. Sum of  -bonds present in peroxodisulphuric acid
A. N 2 O4 I. 1 N = O bond and pyrosulphuric acid (JEE Main 2023)
B. NO2 II. 1 N – O – N bond 63. Total number of acidic oxides among
C. N 2 O5 III. 1 N – N bond N 2 O3 , NO2 , N 2 O, Cl2 O7 , SO2 , CO, CaO, Na2O and
IV. 1 N = N/N = N bond NO is _______. (JEE Main 2023)
D. N 2 O
64. The oxidation sate of phosphorus in hypophosphoric
Choose the correct answer from the options given acid is + ________ . (JEE Main 2023)
below: (JEE Main 2023) 65. Sum of oxidation states of bromine in bromic acid and
(a) A - III, B - I, C - IV, D - II perbromic acid is ________ . (JEE Main 2023)
(b) A - III, B - I, C - II, D - IV
66*. XeF4 reacts with SbF5 to form
(c) A - II, B - IV, C - III, D - I
 XeFm 
n
(d) A - II, B - I, C - III, D - IV [ SbFy ]x –
56*. Which halogen is known to cause the reaction given m + n + y + z = ___________ (JEE Main 2023)
below: 67. The ratio of sigma and  bonds present in
2Cu 2  4 X –  Cu2 X 2  s   X 2 (JEE Main 2023) pyrophosphoric acid is ________ (JEE Main 2023)
(a) Only Chlorine (b) All halogens 68. The number of species from the following carrying a
(c) Only Iodine (d) Only Bromine single lone pair on central atom Xenon is _______
57*. One mole of P4 reacts with 8 moles of SOCl2 to give XeF5  , XeO3 , XeO2 F2 , XeF5 – , XeO3 F2 , XeOF4 , XeF4
4 moles of A, x mole of SO2 and 2 moles of B. A, B (JEE Main 2023)
69*. In the following reactions, the total number of oxygen
and x respectively are (JEE Main 2023)
atoms in X and Y is _______
(a) POCl3 , S2 Cl2 and 4
Na2 O  H 2 O  2 X
(b) PCl3 , S 2 Cl2 and 2
Cl2 O7  H 2 O  2Y (JEE Main 2023)
(c) POCl3 , S2 Cl2 and 2 70. The sum of lone pairs present on the central atom of
(d) PCl3 , S 2 Cl2 and 4 the interhalogen IF5 and IF7 are _____
58. Given below are two statements: (JEE Main 2023)
Statement I: SbCl5 is more covalent than SbCl3 71*. The difference in the oxidation state of Xe between the
Statement II: The higher oxides of halogens also tend oxidised product of Xe formed on complete hydrolysis
to be more stable than the lower ones. of XeF4 and XeF4 is _____ (JEE Main 2023)
Objective Questions I [Only one correct option] (d) decomposition of nitrogenous compounds to yield
free nitrogen.
1. Which one of the following elements is most metallic ?
10. Which one of the following is the strongest base ?
(a) P (b) As
(c) Sb (d) Bi (a) AsH3 (b) NH3
2. A white precipitate is obtained on hydrolysis of (c) PH3 (d) SbH3
(a) PCl5 (b) NCl3 11. Which of the following phosphorus is most reactive ?
(c) BiCl3 (d) AsCl3 (a) Red phosphorus (b) White phosphorus
3. In the cationic parts of solid N2O5 and solid N2O4, the (c) Scarlet phosphorus (d) Violet phosphorus
bond order of N–O are, respectively, 12. The reaction of white phosphorus with aqueous NaOH
(a) 3.0 and 2 (b) 2 and 3 gives phosphine and another phosphorus containing
(c) 2.5 and 3.0 (d) 3 in both compound. The reaction type, the oxidation states of
phosphorus in phosphine and other product are
4. Which of the following oxides of nitrogen is a coloured
respectively:
gas ?
(a) redox reaction, -3 and -5
(a) N2O (b) NO (b) redox reaction, +3 and +5
(c) N2O4 (d) NO2 (c) disproportionation reaction, -3 and +1
5. Which of the following compounds consists of a P–P (d) disproportionation reaction, -3 and +3
linkage? 13. There is no S—S bond in
(a) hypophosphoric acid
(b) pyrophosphorous acid (a) S2 O 24 (b) S2 O52
(c) dipolyphosphoric acid (c) S2 O32 (d) S2 O 72
(d) metaphosphoric acid
6. Sulphuric acid reacts with PCl5 to give 14. Which of the following has the highest boiling point?
(a) thionyl chloride H 2 O, H 2S, H 2Se and H 2 Te
(b) sulphur monochloride
(a) H 2 O because of hydrogen bonding
(c) sulphuryl chloride
(d) sulphur tetrachloride (b) H 2 Te because of higher molecular weight
7. Liquid ammonia bottles are opened after cooling them (c) H 2S because of hydrogen bonding
in ice for sometime. It is because liquid NH3
(a) Brings tears to the eyes (d) H2Se because of lower molecular weight
(b) Has a high vapour pressure 15. The products of the chemical reaction between Na2S2O3,
Cl2 and H2O are:
(c) Is a corrosive liquid
(d) Is a mild explosive (a) S, HCl, Na2SO4 (b) S, HCl, Na2S
8. What causes nitrogen to be chemically inert ? (c) S, HCl, Na2SO3 (d) S, NaClO3
(a) Multiple bond formation in the molecule 16. Sodium thiosulphate is prepared by
(b) Absence of bond polarity (a) reducing Na2SO4 solution with H2S
(c) Short internuclear distance (b) boiling Na2SO3 solution with S in alkaline medium
(d) High bond energy (c) neutralising H2S2O3 solution with NaOH
9. Fixation of nitrogen means :
(d) boiling Na2SO3 solution with S in acidic medium
(a) reaction of nitrogen with oxygen.
17. The formation of which of the substance is known as
(b) conversion of free atmospheric nitrogen into tailing of mercury?
nitrogen compounds.
(a) Hg2O (b) HgO
(c) the action of denitrifying bacteria on nitrogen
compounds. (c) Hg(NO3)2 (d) HgS
18. Tailing of mercury test can be used for which of the 28. N 2 H 4 reacts with conc. H 2 SO 4 to produce a salt
following gas?
[NH3 – NH3]2+ SO24  in which
(a) Dioxygen (b) Dihydrogen
(c) Dinitrogen (d) Ozone (a) dN–N (salt) > dN–N (N2H4)
19. O3 cannot oxidise: (b) dN–N (salt) < dN–N (N2H4)
(a) KI (b) FeSO4 (c) dN–N (salt) = dN–N (N2H4)
(c) KMnO4 (d) K2MnO4 (d) Cannot be predicted
20. Which of the following does not have S—S linkage?
29. Sulphur on reaction with concentrated HNO3 gives (A)
(a) S2O 82  (b) S2O 26  which reacts with NaOH gives (B). (A) and (B) are:
(a) H2SO3, Na2S2O3 (b) NO2, Na2S
(c) S2O 52  (d) S2O 32 
(c) H2SO4, Na2SO4 (d) H2S2O3, Na2S2O3
21. Which has maximum pH in aqueous solution?
30. White phosphorus on reaction with limewater gives
(a) NaClO (b) NaClO2 calcium salt of an acid (A) along with a gas (X). Which of
(c) NaClO3 (d) NaClO4 the following is correct?
22. What products are expected from disproportionation (a) (A) on heating gives (X) and O2
reaction of hypochlorus acid? (b) The bond angle in (X) is less than that in case of
(a) HClO3 and Cl2O (b) HClO2 and HClO4 ammonia
(c) HCl and Cl2O (d) HCl and HClO3 (c) (A) is a dibasic acid
(d) (X) is more basic than ammonia
23. HClO4 + P2O5 (A) + (B)
31. Among the oxides given below which are acidic?
(A) and (B) are:
CrO3, Mn2O7, CuO, CO, SO2
(a) HClO3, H3PO4 (b) Cl2O6, HPO3
(a) Only SO2 (b) CrO3, Mn2O7 and SO2
(c) ClO2, H3PO4 (d) Cl2O7 , HPO3
(c) Mn2O7 and SO2 (d) CO and SO2
24. Which of the following is the life saving mixture for an
asthma patient ? 32. In which of the following reactions O2 is not formed as
(a) Mixture of helium and oxygen one of the product?
(b) Mixture of neon and oxygen MnO2
(a) KClO3  
(c) Mixture of xenon and nitrogen Heat
(d) Mixture of argon and oxygen (b) SnCl2 + HCl + O3 


25. The oxidation state of xenon atom in XeF4, HXeO and4 (c) FeSO4 + H2SO4 + O3 

Na4XeO6 are respectively:
(d) PbS + O3 

(a) + 4, + 6, + 6 (b) + 4, + 6, + 7
33. In the following statements which combination of true
(c) + 4, + 6, + 8 (d) + 4, + 5, + 8
(T) and false (F)options is correct?
26. Which of the following compounds is explosive?
(I) Ionic mobility is the highest for I– in water as
(a) XeF2 (b) XeF4
compared to other halides.
(c) XeO3 (d) XeF3
(II) Stability order is : Cl3 > Br3 > I3
27. In the reaction
(III) Reactivity order is F < Cl < Br < I
3Br2  6CO32   3H 2 O  5Br  BrO3  6HCO3
(IV) Oxidizing power order is : F2 < Cl2 < Br2 < I2
(a) bromine is oxidised and carbonate is reduced
(a) TFTF (b) TFFF
(b) bromine is both oxidised and reduced
(c) TFFT (d) FTFT
(c) bromine is reduced and water is oxidised
34. The number of S—S bonds in sulphur trioxide trimer S3O9
(d) bromine is neither oxidised nor reduced
is:
(a) three (b) two
(c) one (d) zero
35. When an inorganic compound reacts with SO2 in aqueous Match the Following
medium produces (A). (A) on reaction with Na2CO3 gives Each question has two columns. Four options are
the compound (B) which with sulphur gives a substance given representing matching of elements from
(C) used in photography. The compound (C) is: Column-I and Column-II. Only one of these four
(a) Na2S2O3 (b) Na2SO4 options corresponds to a correct matching, for
(c) Na2S (d) Na2S2O7 each question.
36. When sulphur is boiled with Na2SO3, a compound (A) is
41. Match the Oxides with solutions in which they are
produced. (A) with excess of AgNO3 solution gives a absorbed
compound (B) which is water soluble and produces a
Column I Column II
black coloured sulphide (C). Compounds (A), (B) and (C)
will be respectively: (A) CO (p) Absorbed by ethanol amine.
(a) Na2S2O3, Ag2S2O3, Ag2S (B) CO2 (q) Absorbed by FeSO4 solution
(b) Na2SO4, Ag2SO4, Ag2S (C) NO (r) Absorbed by aqueous
(c) Na2S2O7, Ag2SO4, Ag2S suspension of Cu2Cl2.
(d) Na2SO5,Ag2SO5,Ag2SO4 (s) Absorbed by KOH solution
37. Which of the following is/are correct? 42. Match the compounds with their properties
(a) O3 + moist iodine  HIO3 Column I Column II
(A) N2O (p) Neutral towards water
(b) FeCl3 + H2S  colloidal sulphur
(B) NO (q) Acidic towards water
(c) O3 + Ag  black silver
(C) N2O3(unsymmetrical) (r) N–N linkage is present
(d) All
38. The following acids have been arranged in the order of (D) N2O4 (s) Molecule having the highest
bond order of N–O bond
decreasing acid strength. Identify the correct order.
(E) N2O5
ClOH (I), BrOH (II), IOH (III)
43. Match the xenon compounds with their properties.
(a) I > II > III (b) II > I > III
Column I Column II
(c) III > II > I (d) I > III > II
(A) XeO64– (p) Central atom is sp3d2
39. Which of the following reactions of xenon compounds is
not feasible? hybridized
(a) XeO3 + 6HF  XeF6 + 3H2O (B) XeF4 (q) On treatment with conc.
H2SO4 produces XeO4
(b) 3XeF4 + 6H2O  2Xe + XeO3+12HF + 1.5 O2
(C) XeO3 (r) Only one lone pair is present
(c) 2XeF3 + 2H2O  2Xe + 4HF + O2
on the central atom
(d) XeF6 + RbF  Rb [XeF7]
(D) XeO2F2 (s) Central atom of the molecule
40. White phosphorus (P4) does not have has four surrounding atoms.
(a) six P—P single bonds
(b) four P–—P single bonds
Fill in the Blanks
(c) four lone pairs of electrons
44. ................ phosphorus is reactive because of its highly
(d) PPP angle of 60º
strained tetrahedral structure.
45. The oxidation state of S atom in H2S2O7 is ....... .
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

Objective Questions [Only one correct option] 11. Which of the following is not oxidised by O3 ? (2005)
1. The number of P—O—P bonds in cyclic metaphosphoric (a) KI (b) FeSO4
acid is (2000) (c) KMnO4 (d) K2MnO4
(a) zero (b) two 12. The percentage of p-character in the orbitals forming
(c) three (d) four P—P bonds in P4 is (2007)
2. The correct order of acidic strength is (2000) (a) 25 (b) 33
(a) Cl2O7 > SO2 > P4O10 (b) CO2 > N2O5 > SO3 (c) 50 (d) 75
(c) Na2O > MgO > Al2O3 (d) K2O > CaO > MgO 13. Aqueous solution of Na2S2O3 on reaction with Cl2 gives
3. Amongst H2O, H2S, H2Se and H2Te, the one with the (2008)
highest boiling point is (2000) (a) Na2S4O6 (b) NaHSO4
(a) H2O because of hydrogen bonding (c) NaCl (d) NaOH
(b) H2Te because of higher molecular weight 14. The reaction of P4 with X leads selectively to P4O6. The X,
(c) H2S because of hydrogen bonding is (2009)
(d) H2Se because of lower molecular weight (a) dry O2
4. The number of S—S bonds in sulphur trioxide trimer, (S3O9) (b) a mixture of O2 and N2
is (2001) (c) moist O2
(a) three (b) two (d) O2 in the presence of aqueous NaOH
(c) one (d) zero 15. Extra pure N2 can be obtained by heating (2010)
5. Polyphosphates are used as water softening agents (a) NH3 with CuO (b) NH4NO3
because they (2002) (c) (NH4)2Cr2O7 (d) Ba (N3)2
(a) form soluble complexes with anionic species 16. The product formed in the reaction of SOCl 2 with
(b) precipitate anionic species phosphorous is (2014)
(c) form soluble complexes with cationic species (a) PCl3 (b) SO2Cl2
(d) precipitate cationic species (c) SCl2 (d) POCl3
6. For H3PO3 and H3PO4 the correct choice is (2003) 17. The order of the oxidation state of the phosphorus atom
(a) H3PO3 is dibasic and reducing in H3PO2, H3PO4, H3PO3 and H4P2O6 is (2018)
(b) H3PO3 is dibasic and non-reducing (a) H3PO4 > H3PO2 > H3PO3 > H4P2O6
(c) H3PO4 is tribasic and reducing
(b) H3PO4 > H4P2O6 > H3PO3 > H3PO2
(d) H3PO3 is tribasic and non-reducing
7. Which of the following has —O—O— linkage ? (2004) (c) H3PO2 > H3PO3 > H4P2O6 > H3PO4
(a) H2S2O6 (b) H2S2O8 (d) H3PO3 > H3PO2 > H3PO4 > H4P2O6
(c) H2S2O3 (d) H2S4O6
8. Which of the following isomers of phosphorus is Objective Questions II
thermodynamically most stable ? (2005)
(a) Red (b) White
(c) Black (d) Yellow
9. A pale blue liquid which obtained by equimolar mixture of 18. The nitrogen oxide (s) that contain (s) N—N bonds (s) is
two gases at – 30ºC is (2005) (are) (2009)
(a) N2O (b) N2O3 (a) N2O (b) N2O3
(c) N2O4 (d) N2O5 (c) N2O4 (d) N2O5
10. Which gas is evolved when PbO2 is treated with conc.
HNO3 ? (2005)
(a) NO2 (b) O2
(c) N2 (d) N2O
19. The correct statement(s) regarding. (i) HClO, (ii) HClO2, Numerical Value Type Questions
(iii) HClO3 and (iv) HClO4, is (are) (2015)
(a) The number of Cl = O bonds in (ii) and (iii) together is 26. Reaction of Br2 with Na2CO3 in aqueous solution gives
two sodium bromide and sodium bromate with evolution of
(b) The number of lone pairs of electrons on Cl in (ii) and CO2 gas. The number of sodium bromide molecules
(iii) together is three involved in the balanced chemical equation is (2008)
(c) The hybridization of Cl in (iv) is sp3 27. Among the following, the number of compounds that
(d) Amongst (i) to (iv), the strongest acid is (i) can react with PCl5 to give POCl3 is O2, CO2, SO2, H2O,
20. The nitrogen containing compound produced in the H2SO4, P4O10. (2009)
reaction of HNO3 with P4O10 (2016) 28. The total number of compounds having at least one
(a) can also be prepared by reaction of P4 and HNO3 bridging oxo group among the molecules given below is
(b) is diamagnetic ......... . (2018)
(c) contains one N–N bond N2O3, N2O5, P4O6, P4O7, H4P2O5, H5P3O10, H2S2O3, H2S2O5
(d) reacts with Na metal producing as brown gas 29. Ozonolysis of ClO produces an oxide of chlorine. The
average oxidation state of chlorine in this oxide is ____.
21. The correct statement(s) about the oxoacids, HClO4 and
(2021)
HClO, is (are) (2017)
(a) The central atom in both HClO 4 and HClO is Paragraph Type Questions
sp3-hybridised Use the following passage, to solve Q. 30 to Q. 32
(b) HClO4 is formed in the reaction between Cl2 and H2O Passage
(c) The conjugate base of HClO4 is weaker base than H2O The noble gases have closed-shell electronic configuration and
(d) HClO4 is more acidic than HClO because of the are monoatomic gases under normal conditions. The low boiling
resonance stabilisation of its anion points of the lighter noble gases are due to weak dispersion forces
22. The colour of the X2 molecules of group 17 elements between the atoms and the absence of other interatomic
changes gradually from yellow to violet down the group. interactions.
This is due to (2017) The direct reaction of xenon with fluorine leads to a series of
(a) decrease in * – * gap down the group compounds with oxidation numbers +2, +4 and +6. XeF4 reacts
(b) decrease in ionisation energy down the group violently with water to give XeO3. The compounds of xenon exhibit
rich stereochemistry and their geometries can be deduced
(c) the physical state of X2 at room temperature changes
considering the total number of electron pairs in the valence shell.
from gas to solid down the group
(2007)
(d) decreases in HOMO-LUMO gap down the group
30. Argon is used in arc welding because of its
23. The compound(s) which generates N2 gas upon thermal
(a) low reactivity with metal
decomposition below 300ºC is (are) (2018)
(b) ability to lower the melting point of metal
(a) NH4NO3 (b) (NH4)2Cr2O7
(c) flammability
(c) Ba(N3)2 (d) Mg3N2
(d) high calorific value
24. Based on the compounds of group 15 elements, the correct
statement(s) is (are) (2018) 31. The structure of XeO3 is
(a) Bi2O5 is more basic than N2O5 (a) linear (b) planar
(b) NF3 is more covalent than BiF3 (c) pyramidal (d) T-shaped
(c) PH3 boils at lower temperature than NH3 32. XeF4 and XeF6 are expected to be
(d) The N-N single bond is stronger than the P-P single (a) oxidising (b) reducing
bond (c) unreactive (d) strongly basic
25. The correct statement(s) related to oxoacids of
phosphorous is(are) (2021)
(a) Upon heating, H3PO3 undergoes disproportionation
reaction to produce H3PO4 and PH3.
(b) While H3PO3 can act as reducing agent, H3PO4 cannot.
(c) H3PO3 is a monobasic acid.
(d) The H atom of P-H bond in H3PO3 is not ionizable in
water.
Use the following passage, to solve Q. 33 to Q. 35 36. Dissolving 1.24 g of white phosphorous in boiling NaOH
Passage solution in an inert atmosphere gives a gas Q. The amount
of CuSO4 (in g) required to completely consume the gas Q
There are some deposits of nitrates and phosphates in earth’s
is _______.
crust. Nitrates are more soluble in water. Nitrates are difficult to
reduce under the laboratory conditions but microbes do it easily. [Given: Atomic mass of H = 1, O = 16, Na = 23, P = 31, S =
Ammonia forms large number of complexes with transition metal 32, Cu = 63] (2022)
ions. Hybridisation easily explains the ease of sigma donation 37. The treatment of galena with HNO3 produces a gas that is
capability of NH3 and PH3. Phosphine is a flammable gas and is (2022)
prepared from white phosphorus. (2008) (a) paramagnetic (b) bent in geometry
33. Among the following, the correct statement is (c) an acidic oxide (d) colorless
(a) Phosphates have no biological significance in humans 38. The reaction of Xe and O2F2 gives a Xe compound P. The
(b) Between nitrates and phosphates, phosphates are number of moles of HF produced by the complete
less abundant in earth’s crust hydrolysis of 1 mol of P is _______. (2022)
(c) Between nitrates and phosphates, nitrates are less 39. The reaction of Pb(NO3)2 and NaCl in water produces a
abundant in earth’s crust precipitate that dissolves upon the addition of HCl of
(d) Oxidation of nitrates is possible in soil appropriate concentration. The dissolution of the
34. Among the following, the correct statement is precipitate is due to the formation of (2022)
(a) Between NH3 and PH3, NH3 is a better electron donor (a) PbCl2 (b) PbCl4
because the lone pair of electrons occupies spherical (c) [PbCl4]2– (d) [PbCl6]2–
‘s’ orbital and is less directional 40. Match the reactions (in the given stoichiometry of the
(b) Between NH3 and PH3, PH3 is a better electron donor reactants) in List-I with one of their productsgiven in
because the lone pair of electrons occupies sp3 orbital List-II and choose the correct option. (2023)
and is more directional List-I List-II
(c) Between NH3 and PH3, NH3 is a better electron donor (P) P2O3 + 3H2O  (1) P(O)(OCH3)Cl2
because the lone pair of electrons occupies sp3 orbital (Q) P4 + 3NaOH + 3H2O  (2) H3PO3
and is more directional (R) PCl5 + CH3COOH  (3) PH3
(d) Between NH3 and PH3, PH3 is a better electron donor (S) H3PO2 + 2H2O + 4AgNO3  (4) POCl3
because the lone pair of electrons occupies spherical
(5) H3PO4
‘s’ orbital and is less directional
(a) P  2; Q  3; R  1; S  5
35. White phosphorus on reaction with NaOH gives PH3 as
one of the products. This is a (b) P  3; Q  5; R  4; S  2
(a) dimerisation reaction (c) P  5; Q  2; R  1; S  3
(b) disproportionation reaction (d) P  2; Q  3; R  4; S  5
(c) condensation reaction 41. Consider the following molecules : Br3O8, F2O, H2S4O6,
H2S5O6, and C3O2.
(d) precipitation reaction
Count the number of atoms existing in their zero oxidation
state in each molecule. Their sum is____. (2023)
p -BLOCK ELEMENTS (GROUP 15-18)

d & f BLOCK ELEMENTS
Chapter 10 194
d & f BLOCK ELEMENTS
1. d BLOCK ELEMENTS - INTRODUCTION

1.1 Definition 1.2 Position of d-Block Elements in Periodic Table
“The elements in which the last differentiating electron enters into In modern periodic table, d-block elements are placed in between
the d-orbitals of the penultimate shell are called d-block elements”. s-block and p-block elements. There are total 10 groups of d-
The properties of these elements are intermediate between the block elements placed in the middle of periodic table. These are
properties of s-block and p-block elements. from group-3 to group-12. d-block elements are further classified
into four series.
These elements represent a change or transition in properties
from more electropositive elements (s-block) to less electropositive 4th period (21Sc to 30Zn, 10 elements) 1st Transition series.
elements (p-block). Therefore these elements are called transition 5th period (39Y to 48Cd, 10 elements) 2nd Transition series.
elements.
6th period (51La, 72Hf to 80Hg, 10 elements) 3rd Transition series.
A transition element may also be defined as the element which
7th period (89Ac, 104
Rf to 112
Cn, 10 elements)  4th Transition
has partially filled d-orbital in their ground state or most stable
series.
oxidation state.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9 (Cupric ion)
SCAN CODE
d & f Block Elements
d & f BLOCK ELEMENTS 195
1.3 Electronic Configuration Thus, the electronic configuration of chromium (Z = 24) and copper
In d-block elements with increase in atomic number, the d-orbitals (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 2p6 3s6 3p6 3d10 4s1
of penultimate shell i.e. (n-1) d are gradually filled by electrons. respectively.
The general electronic configuration of d-block element is, (n-1) 1.4 General Properties of Transition Elements
d1-10, ns0-2.
1.4.1 Physical Properties
Depending upon the d-orbitals of which penultimate shell (i.e. n =
All the transition elements show typical metallic properties like
4, 5, 6, 7) are filled, four rows (called series) of ten elements each
high tensile strength, ductility, malleability, high thermal and
obtained. They correspond to 3d, 4d, 5d and 6d subshells.
electrical conductivity and metallic lustre. With the exceptions of
Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’ subshell, Zn, Cd, Hg and Mn, they have one or more typical metallic
hence ns orbital is filled first then (n – 1) d orbitals. structures at normal temperatures.
The electronic configuration of d-block elements of four series is Lattice Structures of d-Block Elements
shown as follows : Sc Ti V Cr Mn Fe Co Ni Cu Zn
First (3d) Transition Series (Sc–Zn) hcp hcp bcc bcc X bcc ccp ccp ccp X
(bcc) (bcc) (bcc, (hcp) (hcp) (hcp)
At. No. 21 22 23 24 25 26 27 28 29 30 ccp)
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4s 2 2 2 1 2 2 2 2 1 2 hcp hcp bcc bcc hcp hcp ccp ccp ccp X
3d 1 2 3 5 5 6 7 8 10 10 (bcc) (bcc) (hcp)
La Hf Ta W Re Os Ir Pt Au Hg
Second (4d) Transition Series (Y-Cd) hcp hcp bcc bcc hcp hcp ccp ccp ccp X
At. No. 39 40 41 42 43 44 45 46 47 48 (ccp, (bcc)
bcc)
Element Y Zr Nb Mo Tc Ru Rh Pd Au Cd
5s 2 2 1 1 1 1 1 0 1 2 The melting and boiling points of transition metals are very high.
4d 1 2 4 5 6 7 8 10 10 10 The high melting points of these metals are attributed to the
Third (5d) Transition Series (La–Hg) involvement of greater number of electrons from (n-1)d in addition
At. No. 57 72 73 74 75 76 77 78 79 80 to the ns electrons.
Element La Hf Ta W Re Os Ir Pt Au Hg
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
Fourth (6d) Transition Series
At. No. 89 104 105 106 107 108 109 110 111 112
Element Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
7s 2 2 2 2 2 2 2 2 1 2
6d 1 2 3 4 5 6 7 8 10 10
Exceptional Configuration of Cr and Cu:

The exceptions observed in the first series are in case of electronic
configurations of chromium (Z = 24) and copper (Z = 29). It may be
noted that unlike other elements, chromium and copper have a
single electron in the 4s-orbital. This is due to the gain of additional
stability by the atom by either having half-filled configuration
(i.e., containing 5 electrons in the d-sublevel) or completely filled
configuration, (i.e., containing 10 electrons in the d-sublevel).
The 3d-level in case of chromium gets exactly half-filled with
configuration 3d5 4s1 and that in case of copper, it gets completely Melting points of transition elements
filled with configuration 3d10 4s1. This can be explained on the In any series of transition elements the melting points rise to a
basis of exchange energy. maximum at d5 except for anomalous values of Mn and Tc and fall
regularly as the atomic number increases. Mn has stable electronic
configuration (3d5 half filled, 4s2 fully filled). As a result 3d electrons
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are more tightly held by the nucleus and this reduces the Explanation
delocalisation of electrons resulting in weaker metallic bonding. Near the end of series, the increased electron-electron
Transition elements have high enthalpies of atomisation. The repulsions between added electrons in the same orbitals are
maxima at about the middle of each series indicate that one greater than the attractive forces due to the increased nuclear
unpaired electron per d orbital is particularly favourable for strong charge. This results in the expansion of the electron cloud
interatomic interaction. In general, greater the number of valence and thus the atomic radius increases.
electrons, stronger is the resultant bonding. Metals with very (iv) The atomic radii increase down the group. This means that
high enthalpy of atomisation tend to be noble in their reactions. the atomic radii of second series are larger than those of first
The transition metals of the second and third series have greater transition series. But the atomic radii of the second and third
enthalpies of atomisation than the corresponding elements of the transition series are almost the same.
first series. The atomic radii of the elements of the second and third
transition metals are nearly same due to lanthanide contraction
(or also called lanthanoid contraction) discussed later.)
Enthalpies of atomisation of transition elements

1.4.2 Atomic Radii
(i) The atomic radii of the transition metals lie in-between those
of s- and p-block elements.
(ii) Generally the atomic radii of d-block elements in a series Atomic radii of transition elements
decrease with increase in atomic number but the decrease in 1.4.3 Ionic Radii
atomic size is small after midway. (i) The trend followed by the ionic radii is the same as that
Explanation followed by atomic radii.
The atomic radius decreases with the increase in atomic (ii) Ionic radii of transition metals are different in different
number as the nuclear charge increases whereas the shielding oxidation states.
effect of d-electron is small. After midway, as the electrons (iii) The ionic radii of the transition metals are smaller than those
enter the last but one (penultimate) shell, the added d-electron of the representative elements belonging to the same period.
shields (screens) the outermost electron. Hence, with the
1.4.4 Ionisation Enthalpies
increase in the d-electrons, screening effect increases. This
counterbalances the increased nuclear charge due to increase (i) The first ionisation enthalpies of d-block elements lie between
in atomic number. As a result, the atomic radii remain practically s-block and p-block elements. They are higher than those of s-
same after chromium. For example in Fe, the two opposing block elements and are lesser than those of p-block elements.
tendencies almost counterbalance and there is no change in The ionisation enthalpy gradually increases with increase in
the size from Mn to Fe. atomic number along a given transition series though some
(iii) At the end of the period, there is a slight increase in the irregularities are observed.
atomic radii.
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Ionisation Enthalpies of 3d Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Ionisation enthalpy/ i Ho /kJ mol-1
lHo I 631 656 650 653 717 762 758 736 745 906
lH o
II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
lH o
III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3837
Standard
electrode M2+/M  -1.63 -1.18 -0.90 -1.18 -0.44 0.28 -0.25 +0.34 -0.76
potential Eo/V M 3+/M 2+  -0.37 -0.26 -0.41 +1.57 +0.77 +1.97   
Explanation
The increasing ionization enthalpies are due to increased nuclear removed from ‘(n-1)d’ orbitals as easily as ‘ns’ orbitals
charge with increase in atomic number which reduces the size of electrons.
the atom making the removal of outer electron difficult. (ii) After removing ‘s’ electrons, the remainder is called Kernel
(ii) In a given series, the difference in the ionisation enthalpies of the metal cations. In d-block elements, the Kernel is
between any two successive d-block elements is very much unstable and therefore it loses one or more electrons from (n
less than the difference in case of successive s-block or p- – 1)d electrons. This results in formation of cations with
block elements. different oxidation states.
Explanation (2) All transition elements show variable oxidation state except
last element in each series.
The addition of d electrons in penultimate shell with increase
in atomic number provides a screening effect and thus shields (3) Minimum oxidation state = Total number of 4s electrons lost.
the outer s electrons from inward nuclear pull. Thus, the Maximum oxidation state = (Total number of 4s electrons
effects of increased nuclear charge and addition of d electrons lost + 3d electrons lost).
tend to oppose each other. In ‘3d’ series all elements contain 2 electrons in ‘4s’ and hence
(iii) The first ionization enthalpy of Zn, Cd and Hg are, however, they all give a common minimum oxidation state of +2. (Except
very high because of the fully filled (n-1) d10 ns2 configuration. ‘Cr’ and ‘Cu’ where minimum oxidation state is +1.] The
maximum oxidation state is given by Mn i.e. Mn+7 in which
(iv) Although second and third ionization enthalpies also, in
two electrons are removed from 4s and five unpaired electrons
general, increase along a period, but the magnitude of increase
are removed from 3d orbitals.
for the successive elements is much higher.
(4) The highest oxidation state is shown by Ruthenium (Ru) and
(v) The high values of 3rd ionization enthalpies for Cu, Ni and
Osmium (Os) i.e. +8.
Zn explain why they show a maximum oxidation state of +2.
(5) Across the period oxidation state increases and it is maximum
(vi) The first ionisation enthalpies of 5d elements are higher as
at the centre and than decreases even if atomic number
compared to those of 3d and 4d elements. This is because
increases. The element which shows highest oxidation state
the weak shielding of nucleus by 4f electrons in 5d elements
occur in the middle or near the middle of the series and than
results in greater effective nuclear charge acting on the outer
decreases.
valence electrons.
(6) Transition metals also show zero oxidation states in metal
1.4.5 Oxidation State
carbonyl complex.
(1) With the exception of few elements, most of the d-block
Example : Ni in [Ni(CO)4] (Nickel tetracarbonyl) has zero
elements show more than one oxidation state i.e. they show
oxidation state.
variable oxidation states. The elements show variable
oxidation state because of following reasons: (7) The bonding in the compounds of lower oxidation state (+2,
+3) is mostly ionic and the bonding in the compounds of
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block elements
higher oxidation state is mostly covalent.
have almost same energies and therefore electron can be
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(8) The relative stabilities of some oxidation states can be (9) Cu+2 is more stable than Cu+ even when Cu+ is 3d10 while
explained on the basis of rule extra stability, according to Cu+2 is 3d due to high heat of hydration.
which d0, d5 and d10 are stable configurations. Variable oxidation states shown by 3d-series of d-block
For example, the stability order of some ions is as follows: elements.
Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)
Oxidation States in 3d Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
Oxidation states
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
1.4.6 Standard Electrode Potentials (Eo)

In solution, the stability of the compounds of transition metals
depends upon electrode potentials. Electrode potential values
depend upon factors such as enthalpy of sublimation (or
atomisation) of the metal, the ionisation enthalpy and the hydration
enthalpy, i.e.,
M  s  
 sub H
 M  g  , (  sub H is enthalpy of sublimation)
Trends in the M2+/M Standard Electrode Potentials:
M  g  
 iH
 M   g   e , (  i H is ionisation enthalpy) (i) There is no regular trend in the Eo (M2+/M) values. This is
because their ionization enthalpies (IE1 + IE2) and sublimation
enthalpies do not show any regular trend.
M   g   aq   M   aq  , (  hyd H is enthalpy of hydration)
hyd  H
(ii) The general trend towards less negative Eo values along the
The total energy, T H , for the process involving sublimation, series is due to the general increase in the sum of first and
ionisation and hydration simultaneously, i.e., for the process, second ionization enthalpies.
(iii) Copper shows a unique behaviour in the series as it is the
M  s  
 M   aq   e  , will be the sum of the three types of
only metal having positive value for Eo. This explains why is
enthalpies, i.e., does not liberate H2 gas from acids. It reacts only with the
 T H   sub H   i H   hyd H. oxidizing acids (HNO3 and H2SO4) which are reduced. The
reason for positive Eo value for copper is that the sum of
Thus, T H , is the total enthalpy change when solid metal, M is enthalpies of sublimation and ionization is not balanced by
brought in the aqueous medium in the form of monovalent ion, hydration enthalpy.
M+ (aq).
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Eo ( M 2+  M o ) Values for Ti to Zn Chemical Reactivity and Eo Values:

The transition metals vary widely in their chemical reactivity. Some
M a Ho 1H1o 1H o2  Hyd H o  M 2   Eo/V
of them are highly electropositive and dissolve in mineral acids
Ti 469 656 1309 –1866 –1.63 whereas a few of them are ‘noble’, i.e., they do not react with simple
V 515 650 1414 –1895 –1.18 acids. Some results of chemical reactivity of transition metals as
Cr 398 653 1592 –1925 –0.90 related to their Eo values are given below :
Mn 279 717 1509 –1862 –1.18 (i) The metals of the first transition series (except copper) are
Fe 418 762 1561 –1998 –0.44 relatively more reactive than the other series. Thus, they are
Co 427 758 1644 –2079 –0.28 oxidized by H+ ions though the actual rate is slow, e.g., Ti and
Cu 339 745 1958 –2121 0.34 V are passive to dilute non-oxidizing acids at room
Zn 130 906 1734 –2059 –0.76 temperature.
(ii) As already explained, less negative Eo values for M2+/M along
(iv) The values of Eo for Mn, Ni and Zn are more negative than
the series indicate a decreasing tendency to form divalent
expected from the general trend. This is due to greater stability
cations.
of half-filled d-subshell (d5) in Mn2+, and completely filled d-
subshell (d10) in Zn2+. The exceptional behaviour of Ni towards (iii) More negative Eo values than expected for Mn, Ni and Zn
Eo value from the regular trend is due to its high negative show greater stability for Mn2+, Ni2+ and Zn2+.
enthalpy of hydration. (iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+
and Co3+ ions ar the strongest oxidizing agents in aqueous
solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
agents and can liberate hydrogen from a dilute acid, e.g.,
2 Cr2+ (aq) + 2 H+ (aq) 
 2 Cr3+ (aq) + H2 (g)
1.4.7 Catalytic Properties
Most transition elements and their compounds have good catalytic
properties because
(a) They possess variable oxidation state.
(b) They provide a large surface area for the reactant to be
absorbed.
Some Common Catalysts
Catalysts Uses
TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in
Eo ( M 2  Mo ) values for Ti to Zn polymerisation of ethylene
Trends in the M3+/M2+ Standard Electrode Potentials: V2O5 Contact process SO2  SO3
Fe Haber Bosch process
(i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
PdCl2 Wacker’s process for CH3CHO
Sc3+ ion which has a noble gas configuration.
manufacturing
(ii) The highest value for Zn is on account of very high stability
Pd Hydrogenation of alkene,
of Zn2+ ion with d10 configuration. It is difficult to remove an
alkyne
electron from it to change it into +3 state.
Pt/PtO Adam’s catalyst for selective
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows that
reduction
Mn 2+ is very stable which is on account of stable d 5
Pt Catalytic convertor, for
configuration of Mn2+.
cleaning car exhaust fumes
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
Pt/Rh Ostwald’s process :
of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy
NH3  NO
of Fe.
Cu Oxidation of alcohols
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1.4.8 Magnetic Behaviour [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH3)4]2+, [Ni(CN)4]2–
When a magnetic field is applied to substances, mainly two types and [PtCl4]2–
of magnetic behaviour are observed: diamagnetism and Such complex compounds are not formed by s - and p - block
paramagnetism. elements.
Diamagnetic substances are repelled by the applied field while Explanation. The transition elements form complexes because of
the paramagnetic substances are attracted. Most of the transition the following reasons :
metal ions are paramagnetic due to the presence of unpaired (i) Comparatively smaller size of their metal ions.
electrons. Each such electron having a magnetic moment
(ii) Their high ionic charges and high charge/size ratio.
associated with its spin angular momentum and orbital angular
momentum. (iii) Availability of vacant d-orbitals so that these orbitals can
accept lone pairs of electrons donated by the ligands.
In first transition elements series the orbital angular magnetic
moment is insignificant the orbital contribution is quenched by 1.4.10 Formation of Coloured Compounds
the electric fields of the surrounding atoms so magnetic moment Transition elements form coloured ions due to presence of
is equal to the spin magnetic moment only. incompletely filled d-orbitals and unpaired electrons. They can
It can be calculated by using the formula: undergo d-d transition by absorbing colour from visible region
and radiating complementary colour, e.g. Cu2+ (blue), V2+(violet),
 eff  n (n  2) BM Cr3+(green). Cu+(3d10), Zn2+(3d10), Cd2+(4d10), Sc3+(3d0 ) are white
due to presence of no unpaired electrons and cannot undergo d-
n  no. of unpaired electron.
d transition.
The magnetic moment increases with the increasing number of
Colour of Ions of 3d Series
unpaired electrons. Thus, the observed magnetic moment is
directly related to the number of unpaired electrons present in the Configuration Example Colour
atom, molecule or ion. 3d0 Sc3+ colourless
Magnetic Moments of 3d Series Ions 3d0 Ti4+ colourless
1 3+
3d Ti purple
Ion Unpaired Magnetic moment 3d 1
V 4+
blue
electron(s) Calculated Observed 2 3+
3d V green
Sc3+ 3d0 0 0 0 3d3 V2+ violet
Ti3+ 3d1 1 1.73 1.75 3d3 Cr3+ violet
2+ 2
Tl 3d 2 2.84 2.76 3d 4
Mn 3+
violet
V2+ 3d3 3 3.87 3.86 3d 4
Cr 2+
blue
Cr2+ 3d4 4 4.90 4.80
3d5 Mn2+ pink
Mn2+ 3d5 5 5.92 5.96
3d5 Fe3+ yellow
Fe2+ 3d6 4 4.90 5.3 – 5.5 6 2+
3d Fe green
Co2+ 3d7 3 3.87 4.4 – 5.2 6 7 3+ 2+
3d 3d Co Co bluepink
Ni2+ 3d8 2 2.84 2.9 – 3, 4
3d8 Ni2+ green
Cu2+ 3d9 1 1.73 1.8 – 2.2 9 2+
3d Cu blue
Zn2+ 3d10 0 0
10 2+
3d Zn colourless
1.4.9 Complex Formation
1.4.11 Interstitial Compounds
Transition metal ions form a large number of complex compounds.
The transition metals form a large number of interstitial compounds
Complex compounds are those which have a metal ion linked to a
in which small atoms such as hydrogen, carbon, boron and
number of negative ions (anions) or neutral molecules having
nitrogen occupy the empty spaces (interstitial sites) in their lattices
lone pairs of electrons. These ions or molecules are called ligands.
(Fig.).
They donate lone pairs of electrons to the central transition metal
ion forming coordinate bonds. They are represented by formulae like TiC, TiH2, Mn4N, Fe3H,
Fe3C etc. However, actually they are non-stoichiometric materials,
A few examples are given below :
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e.g., TiH1.7, VH0.56 etc. and the bonds present in them are neither metal is equal to its group number, e.g., 7 in Mn2O7. Beyond
typically ionic nor covalent. Some of their important characteristics group 7, no higher oxides of iron above Fe2O are known.
are as follows: Some metals in higher oxidation state stabilize by forming
(i) They are very hard and rigid, e.g., steel which is an interstitial oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+.
compound of Fe and C is quite hard. Similarly, some borides
are as hard as diamond. (iv) All the metals except scandium form the oxides with the
formula MO which are ionic in nature. As the oxidation number
(ii) They have high melting points which are higher than those
of the metal increases, ionic character decreases, e.g., Mn2O7
of the pure metals.
is a covalent green oil. Even CrO3 and V2O5 have low melting
(iii) They show conductivity like that of the pure metal. points.
(iv) They acquire chemical inertness. 2 8 / 3 3 4 7
1.4.12 Alloy Formation MnO Mn 3O 4 Mn 2O 3 MnO 2 Mn 2O 7
Alloys are homogeneous solid solutions of two or more metals (v) In general, the oxides in the lower oxidation states of the
obtained by melting the components and then cooling the melt. metals are basic and in their higher oxidation states, they are
These are formed by metals whose atomic radii differ by not more acidic whereas in the intermediate oxidation state, the oxides
than 15% so that the atoms of one metal can easily take up the are amphoteric.
positions in the crystal lattice of the other. For example, the behaviour of the oxides of manganese may
As transition metals have similar atomic radii and other be represented as follows :
characteristics, hence they form alloys very readily.
2 8/ 3 3 4 7
Alloys are generally harder, have higher melting points and more MnO Mn 3O 4 Mn 2 O3 MnO 2 Mn 2 O 7
Basic Amphoteric Amphoteric Amphoteric Acidic
resistant to corrosion than the individual metals.
The most commonly used are the ferrous alloys the metals Thus, Mn2O7 dissolves in water to give the acid HMnO4.
chromium, vanadium, molybdenum, tungsten and manganese are 2.2 Potassium Dichromate, K2Cr2O7
used in the formation of alloy steels and stainless steels. Some 2.2.1 Preparation Process
alloys of transition metals with non-transition metals are also very
It is prepared from the ore called chromite or ferrochrome or chrome
common. e.g., brass (Cu + Zn) and bronze (Cu + Sn)
iron, FeO.Cr2O3. The various steps involved are as follows :
(i) Preparation of Sodium Chromate:
The ore is finely powdered, mixed with sodium carbonate
and quick lime and then roasted, i.e., heated to redness in a
reverberatory furnace with free exposure to air when sodium
chromate (yellow in colour) is formed and carbon dioxide is
evolved. Quick lime keeps the mass porous and thus facilitates
oxidation.
4FeCr2O4 + 8Na2CO3+ 7O2 

 8Na2CrO4 + 2Fe2O3 + 8CO2
Alloy Formation Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with water
when sodium chromate is completely dissolved while ferric
2. IMPORTANT COMPOUNDS OF TRANSITION oxide is left behind. Ferric oxide is separated out by filtration.
ELEMENTS (ii) Conversion of Sodium Chromate into Sodium Dichromate:
2.1 Oxides and Oxocations The filtrate containing sodium chromate solution is treated
with concentrated sulphuric acid when sodium chromate is
(i) The metals of the first transition series form oxides with
converted into sodium dichromate.
oxygen at high temperature.
2Na 2 CrO 4  H 2SO 4   Na 2 Cr2 O 7  Na 2SO 4  H 2 O
(ii) The oxides are formed in the oxidation, states +1 to +7. Sod.chromate  Conc. Sod. dichromate
(iii) The highest oxidation state in the oxides of any transition Sodium sulphate being less soluble crystallizes out as
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decahydrate, Na2SO4. 10H2O and is removed. The clear equilibrium with CrO24  ions at pH = 4, i.e.,
solution is then evaporated in iron pans to a specific gravity
of 1.7 when a further crop of sodium sulphate is formed. It is 
pH  4
Cr2 O72   H 2 O  2
 2CrO 4  2H

Yellow
removed and the solution is cooled when orange crystals of Orange red
 dichromate   chromate 
sodium dichromate, Na2Cr2O7. 2H2O separate on standing.
(e) Action of Concentrated Sulphuric Acid :
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 : (i) In cold, red crystals of chromic anhydride (chromium trioxide)
Hot concentrated solution of sodium dichromate is treated are formed.
with calculated amount of potassium chloride when potassium K 2 Cr2 O7  2H 2SO 4 
 2CrO3  2KHSO4  H 2 O
dichromate, being much less soluble than sodium salt,
(ii) On heating the mixture, oxygen is evolved.
crystallizes out on cooling as orange crystals.
 2K 2SO 4  2Cr2 SO 4 3 + 8H2O + 3O2
2K 2 Cr2 O7  8H 2SO 4 
Na 2 Cr2 O7  2KCl 
 K 2 Cr2 O7  2NaCl
Sodium dichromate Potassium dichromate (f) Oxidising Properties: It is a powerful oxidising agent. In the
2.2.2 Structures of Chromate and Dichromate Ions presence of dilute sulphuric acid, one molecule of potassium
dichromate furnishes 3 atoms of available oxygen as indicated
The chromate ion, CrO42– is tetrahedral and the dichromate ion, by the equation :
Cr2O72– is made up of two tetrahedra sharing one corner with Cr–
 K 2SO 4  Cr2  SO 4 3 + 4H2O + 3O
K 2 Cr2 O7  4H 2SO 4 
O–Cr bond angle of 126°.
or Cr2 O72   14H   6e 
 2Cr 3  7H 2 O
Mol. wt. 294

 Eq. wt. of K 2 Cr2 O 7    49
6 6
(i) It liberates I2 from KI
 4K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2SO 4  6KI 
Structure of chromate and dichromate ions 3I2  7H 2 O

2.2.3 Properties of Potassium Dichromate (ii) It oxidises ferrous salts to ferric salts
(a) Colour and Melting Point: It forms orange crystals which  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2 SO 4  6FeSO 4 
melt at 669 K.
(b) Solubility: It is moderately soluble in cold water but freely 3Fe2  SO4 3  2H 2 O
soluble in hot water. (iii) It oxidises H2S to sulphur
(c) Action of Heat: When heated to a white heat, it decomposes
with the evolution of oxygen.  K 2 SO 4  Cr2 SO 4 3
K 2 Cr2 O7  4H 2SO 4  3H 2S 
4K 2 Cr2 O7 
 4K 2 CrO4  2Cr2 O3  3O2 + 7H2O + 3S
(iv) It oxidises sulphites to sulphates and thiosulphates to
(d) Action of Alkalies: When an alkali is added to an orange red sulphates and sulphur
solution of dichromate, a yellow solution results due to the
formation of chromate.  K 2SO4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3Na 2SO3 
K Cr O  KOH 
2 2 7  2K 2 CrO 4  H 2 O + 4H2O + 3Na2SO4
Pot. dichromate Pot.chromate (v) It oxidises nitrites to nitrates
or Cr2 O72   2 OH  
 2 CrO42   H 2 O  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4 H 2SO 4  3NaNO 2 
On acidifying, the colour again changes to orange red due to + 3 NaNO3 + 4 H2O
the reformation of dichromate.
(vi) It oxidises halogen acids to halogen
2 K 2 CrO 4  H 2SO4 
 K 2 Cr2 O7  K 2SO4  H 2 O
K 2 Cr2 O7  14 HCl 
 2KCl  2CrCl3  7H 2 O  3Cl2
2  2
or 2 CrO 4  2 H 
 Cr2 O  H 2 O
7 (vii) It oxidises SO2 to sulphuric acid
This interconversion is explained by the fact that in  K 2 SO 4  Cr2  SO 4 3  3H 2 O
K 2 Cr2 O 7  H 2 SO 4  3SO 2 
2
dichromate solution, the Cr2 O 7
ions are invariably in
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(viii) It oxidises stannous salts to stannic salts NOTE
C r2 O 72   14 H   3Sn 2   
 2 C r 3   3 Sn 4   7 H 2 O
Unlike K2Cr2O7, Na2Cr2O7 is not used in volumetric analysis
(ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.
because it is deliquescent.
 K 2SO 4  Cr2  SO 4 3  4H 2 O  3O
K 2 Cr2 O7  4H 2SO 4  2.3 Potassium Permanganate (KMnO4)
CH 2 CH 2 OH  O 
 CH3CHO  H 2 O 2.3.1 Preparation Methods
Ethyl alcohol
On a large scale, it is prepared from the mineral, pyrolusite, MnO2.
CH 3 CHO O 
 CH 3 COOH The preparation involves the following two steps:
Acetaldehyde Acetic acid
(i) Conversion of MnO2 into Potassium Manganate:
Test for a drunken driver : The above reaction helps to test The finely powdered pyrolusite mineral is fused with
whether a driver has consumed alcohol or not. He is asked to potassium hydroxide or potassium carbonate in the presence
breathe into the acidified K2Cr2O7 solution taken in a test tube. If of air or oxidising agent such as potassium nitrate or
the orange colour of the solution changes into green colour (due potassium chlorate when green coloured potassium
to Cr2(SO4)3 formed in the reaction), the driver is drunk, otherwise manganate is formed.
not.
(g) Chromyl Chloride test : (Reaction with a chloride and conc. 2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2 O
sulphuric acid). When heated with concentrated hydrochloric acid Potassium manganate
or with a chloride and strong sulphuric acid, reddish brown
vapours of chromyl chloride are obtained. 2MnO2 + 2K2CO3 + O2 
 2K2MnO4 + 2 CO2
K 2 Cr2 O 7  4KCl  6H 2SO 4 

 2CrO 2 Cl2  6KHSO 4  3H 2 O MnO2 + 2KOH + KNO3 
 K2MnO4 + KNO2 + H2O
Chromyl chloride
 Re d vapour 
(h) Reaction with Hydrogen Peroxide : Acidified K2Cr2O7 solution 3MnO2 +6KOH+KClO3 
 3K2MnO4 +KCl+2H2O
reacts with H2O2 to give a deep blue solution due to the formation (ii) Oxidation of Potassium Manganate to Potassium
of peroxo compound, CrO (O2)2. Permanganate:
Potassium manganate thus formed undergoes
Cr2 O72   2 H   4 H 2 O2 
 2 CrO5  5 H 2 O
disproportionation in the neutral or acidic solution as follows,
The blue colour fades away gradually due to the decomposition if allowed to stand for some time :
VI VII IV
of CrO5 into Cr3+ ions and oxygen. 3 MnO 24   4 H  
2 MnO 4  MnO 2  2 H 2 O
Manganate ion Permanganate ion
The structure of CrO5 is in which Cr is in +6 oxidation The fused mass is extracted with water and the solution after
filtration is converted into potassium permanganate by
state. bubbling carbon dioxide, chlorine or ozonised oxygen through
2.2.4 Uses of Potassium Dichromate the green solution.
(i) In volumetric analysis, it is used as a primary standard for the 3K 2 MnO4  2CO2 
 2KMnO 4  MnO 2  2K 2 CO3
estimation of Fe2+ (ferrous ions) and I– (iodides) in redox
2K 2 MnO4  Cl2 
 2KMnO4  2KCl
titrations.
(ii) In industry, it is used 2K 2 MnO4  H 2 O  O3 
 2KMnO4  2KOH  O2
(a) In chrome tanning in leather industry. The carbon dioxide process is uneconomical as one third of the
original manganate is reconverted to manganese dioxide. However,
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. 24H2O
this process has the advantage that the potassium carbonate
and other industrially important compounds such as Cr2O3,
formed as a by-product can be used for the oxidative fusion of
CrO3, CrO2Cl2, K2CrO4, CrCl3 etc.
manganese dioxide. In the chlorine process, potassium chloride
(c) In calico printing and dyeing. obtained as a by-product is lost.
(d) In photography and in hardening gelatine film.
(iii) In organic chemistry, it is used as an oxidising agent.
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2.3.2 Structure of Manganate and Permanganate ions or MnO4  8H   5 e  
 Mn 2   4H 2 O.
Both manganate  MnO 4  and permanganate  MnO 4  ions are
2 
Since in the above reaction, MnO4 ion gains 5 electrons of
tetrahedral. Here the  -bonding takes place by overlap of p five atoms of oxygen are available from two molecules of
KMnO4. Hence.
orbitals of oxygen with d orbitals of manganese. The green
manganate ion is paramagnetic because of one unpaired electron Mol. wt. 158
Eq. wt. of KMnO 4    31.6
but the permanganate ion is diamagnetic due to the absence of 5 5
any unpaired electron. Some oxidizing properties of KMnO4 in the acidic medium:
Its intense colour and diamagnetism along with temperature- These are given below :
dependent weak paramagnetism can be explained by molecular (i) It oxidises H2S to S.
orbital theory. 2KMnO4  3H 2SO4  5H 2S 
 K 2SO 4  2MnSO 4  2H 2 O  5O
(ii) It oxidises sulphur dioxide to sulphuric acid.
2KMnO 4  5 SO 2  2H 2 O 
 K 2SO4  2MnSO4  2H 2SO4
(iii) It oxidises nitrites  NO 


2 to nitrates  NO  , arsenites

3
 AsO 
3
3
3
to arsentates AsO 4   and sulphites and
thiosulphates to sulphates.
2KMnO 4  3H 2SO4  5KNO 2 
 K 2SO4  2MnSO4 
Structure of manganate and permanganate ions 3H 2 O  5KNO3
2.3.3 Properties of Potassium Permanganate (iv) It oxidises oxalates or oxalic acid to CO2
(a) Colour : Potassium permanganate exists as deep purple black 2KMnO4  3H 2SO4  5C2 H 2 O4 
 K 2SO4  2MnSO4 
prisms with a greenish lustre which become dull in air due to
8H 2 O  10 CO2
superficial reduction.
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous
(b) Solubility : It is moderately soluble in water at room salt to ferric salt).
temperature and it is more soluble in hot water.
2KMnO4  8H 2SO4  10FeSO4 
 K 2SO 4  2MnSO 4 
(c) Action of Heat : When heated to 513 K, it readily decomposes
giving oxygen. 5Fe2  SO4 3  8H 2 O
2KMnO 4 
 K 2 MnO 4  MnO 2  O 2 (vi) It oxidises H2O2 to H2O and O2. This is because acidified
Pot. manganate KMnO4 is a stronger oxidising agent than H2O2.
At red heat, potassium manganate formed decomposes into 2KMnO4  3H 2SO4  5H 2 O 2 
 K 2SO4  2MnSO4 
potassium manganite (K2MnO3) and oxygen.
8H 2 O  5O 2
2K 2 MnO4 
 2K 2 MnO3  O 2
(vii) It oxidises potassium iodide to iodine
(d) Action of heat in current of hydrogen : When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water 2KMnO 4  3H 2SO 4  10KI 
 K 2SO 4  2MnSO 4 
vapours. 8H 2 O  5I 2

2KMnO4  5H 2 
 2KOH  2MnO  4H 2 O (viii) It oxidises HX (where X = Cl, Br, I) to X2
(e) Oxidising Property. Potassium permanganate is powerful 2KMnO4  3H 2SO 4  10 HX 
 K 2SO 4  2MnSO 4 
oxidising agent. The actual course of reaction depends on
the use of the permanganate in (a) acidic medium (b) neutral 8H 2 O  5X 2
medium or (c) alkaline medium. (ix) It oxidises ethyl alcohol to acetaldehyde
(i) In acidic medium : Potassium permanganate in the presence 2KMnO 4  3H 2SO4  5CH3 CH 2 OH 
 K 2SO4  2MnSO4 
of dil. sulphuric acid, i.e., in acidic medium, acts as a strong 5CH 3 CHO  8H 2 O.
oxidising agent because of the reaction
(ii) In neutral solution :
2KMnO4  3H 2SO 4 
 K 2SO 4  2MnSO 4  3H 2 O  5O Potassium permanganate acts as a moderate oxidising agent
in neutral aqueous solution because of the reaction :
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2KMnO4  H 2 O   2KOH  2MnO2  3O (i) It oxidises potassium iodide to potassium iodate.

or 2KMnO 4  H 2 O  KI 
 2MnO 2  2KOH  KIO3
MnO 4  2H 2 O  3 e  
 MnO2  4OH  Pot. iodate
or
Thus, MnO4 ion gains 3 electrons. Also, according to the I   6OH  
 IO3  3H 2 O  6 e
above equation, in neutral medium, from two moles of
permanganate, three oxygen atoms are available. In fact, In this case, iodine is not liberated unlike the case of acidic
during the course of reaction, the alkali generated renders medium.
the medium alkaline even when we start with neutral solutions.
Similar reaction takes place with KBr.
Hence, Eq. wt. of KMnO4 in neutral or weakly alkaline medium
(ii) It oxidises olefinic compounds to glycols, i.e., when an olefinic
Mol. wt. 158 compound is shaken with alkaline KMnO4, pink colour of
   52.67
3 3 KMnO4 is discharged.
Some oxidizing properties of KMnO4 in the neutral medium.
These are given below :
(i) It oxidises hot manganous sulphate to manganese dioxide.
2KMnO4  3MnSO4  2H 2 O 
 K 2SO 4  2H 2SO 4  5MnO2
Presence of ZnSO4 or ZnO catalyses the oxidation.
(ii) It oxidises sodium thiosulphate to sodium sulphate. Alkaline KMnO4 used for this test is known as Baeyer’s
reagent. It is used for oxidation of a number of organic
8KMnO 4  3Na 2S2 O3  H 2 O 
 3K 2SO4  8MnO 2  compounds.
2.3.4 Uses of Potassium Permanganate
3Na 2SO 4  2KOH (i) It is often used in volumetric analysis for the estimation of
(iii) It oxidises hydrogen sulphide to sulphur. ferrous salts, oxalates, iodides and hydrogen peroxide.
2KMnO4  4H 2S 
 2MnS  S  K 2SO4  4H 2 O However, it is not a primary standard because it is difficult to
obtain it in the pure state and free from traces of MnO2. It is,
(iii) In alkaline solution : In strongly alkaline solution, MnO 24  therefore, always first standardised with a standard solution
(manganate) ion is produced. of oxalic acid.
2KMnO4  2KOH 
 2K 2 MnO4  H 2 O  O or (ii) Volumetric titrations inolving KMnO4 are carried out only in

MnO  e  
 MnO 2 presence of dilute H2SO4 but not in the presence of HCl or
4 4
HNO3. This is because oxygen produced from KMnO4 + dil.
Mol. wt. 158
 Eq. wt. of KMnO 4    158 H2SO4 is used only for oxidizing the reducing agent. Moreover,
1 1 H2SO4 does not give any oxygen of its own to oxidize the
Potassium manganate is also further reduced to MnO2 when
reducing agent. In case HCl is used, the oxygen produced
a reducing agent is present. from KMnO4 + HCl is partly used up to oxidize HCl to chlorine
K 2 MnO4  H 2 O 
 MnO2  2KOH  O and in case HNO3 is used, it itself acts as oxidizing agent and
partly oxidizes the reducing agent.
or MnO24   2H 2 O  2 e   MnO2  4OH  (iii) It is used as a strong oxidising agent in the laboratory as well
So the complete reaction is : as in industry. Alkaline potassium permanganate is used for
testing unsaturation in organic chemistry and is known as
2KMnO4  H 2 O   2MnO2  2 KOH  3O
Baeyer’s reagent.
or
MnO 4  2H 2 O  3 e  
 MnO2  4OH  (iv) Potassium permanganate is also widely used as a disinfectant
and germicide. A very dilute solution of permanganate is used
which is the same as that for neutral medium. Hence, for washing wounds and gargling for mouth sore. It is also
equivalent weight of KMnO4 in weakly alkaline medium is used for purifying water of stinking wells.
same as that in the neutral medium, viz., 52.67
(v) Because of its strong oxidizing power, it is also used for
Some oxidizing properties of KMnO4 in the alkaline medium: bleaching of wool, cotton, silk and other textile fibres and
These are given below : also for decolourisation of oils.
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1. f BLOCK ELEMENTS - INTRODUCTION 2.2 Oxidation State
The innter transition elements are also known as f-block elements. The sum of the first three ionization energies for each element are
There are two f-block series, lanthanoids (the fourteen elements low. Thus the oxidation state (+III) is ionic and Ln3+ dominates
following lanthanum) and actinoids (the fourteen elements the chemistry of these elements. The Ln2+ and Ln4+ ions that do
following actinium). The lanthanoids resemble each other closely. occur are always less stable than Ln3+.
They have only one stable oxidation state and their chemistry Oxidation numbers (+II) and (+IV) do occur, particularly when
resembles largely with each other. On the other hand, the chemistry they lead to :
of the actinoids is much more complicated due to the occurrence
of a wide range of oxidation states and radioactive nature. 1. a noble gas configuration e.g. Ce4+ (f 0)
2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
2. THE LANTHANIDE SERIES
3. a completely filled f level, e.g. Yb2+ (f14).
The 14 elements after La-57 are collectively called lanthanoides or
lanthanide series or 4f series. Some times, lanthanoides are NOTE
collectively represented by symbol Ln.
The 4f electrons in the antipenultimate shell are very effectively
2.1 Electronic Confignration
shielded from their chemical environment outside the atom by
These elements have electronic configration [Xe]4f1-14 5d0-1 6s2. the 5s and 5p electrons. Consequently the 4f electrons do not
They have 6s2 common but with variable occupancy of 4f and 5d take part in bonding. Whether the f orbitals are filled or empty
level. The electronic configurations of all tripositive ions are of has little effect on the normal chemical properties. However, it
the form 4f1-14. does affect their spectra and their magnetic properties.
Electronic Configuration and Oxidation States of Lanthanoides

Element Electronic Electronic Oxidation States
Configuration Configuration of M 3+
Lanthanum La [Xe] 5d1 6s2 [Xe] +3

Cerium Ce [Xe] 4f 5d 6s
1 1 2
[Xe] 4f 1
+3 (+ 4)
Praseodymium Pr [Xe] 4f 3
6s 2
[Xe] 4f 2
+3 (+ 4)
Neodymium Nd [Xe] 4f 4
6s 2
[Xe] 4f 3
(+2) +3
Promethium Pm [Xe] 4f 5 6s2 [Xe] 4f 4 (+2) +3
Samarium Sm [Xe] 4f 6
6s 2
[Xe] 4f 5
(+2) +3
Europium Eu [Xe] 4f 7
6s 2
[Xe] 4f 6
(+ 2) +3
Gadolinium Gd [Xe] 4f 5d7 1
6s 2
[Xe] 4f 7
+3
Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)
Dysprosium Dy [Xe] 4f 10
6s 2
[Xe] 4f 9
+3 (+ 4)
Holmium Ho [Xe] 4f 11
6s 2
[Xe] 4f 10
+3
Erbium Er [Xe] 4f 12
6s 2
[Xe] 4f 11
+3
Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 12 (+ 2) +3
Ytterbium Yb [Xe] 4f 14
6s 2
[Xe] 4f 13
(+ 2) +3
Lutetium Lu [Xe] 4f 5d14 1
6s 2
[Xe] 4f 14
+3
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2.3 Atomic and Ionic Radii (Lanthanide Contraction) radii of Zr (160 pm) and Hf (159 pm), a consequence of the
In lanthanide series, with increasing atomic number, there is a lanthanoid contraction, account for their occurrence together in
progressive decrease in the atomic as well as ionic radii of trivalent nature and for the difficulty faced in their separation.
ions from La3+ to Lu3+. This regular decrease in the atomic and
ionic radii with increasing atomic number is known as lanthanide
contraction.
As we move along the lanthanide series, the nuclear charge
increases by one unit at each successive element. The new
electron is added into the same subshell (4f subshell). As a result,
the attraction on the electrons by the nucleus increases and this
tends to decrease the size. Further, as the new electron is added
into the f-subshell, there is imperfect shielding of one electron by
another in this subshell due to the shapes of these f-orbitals. This
imperfect shielding is unable to counterbalance the effect of the
increased nuclear charge. Hence, the net result is a contraction in
the size though the decrease is very small.
It is interesting to note that in lanthanides, the decrease in the
atomic radius for 14 elements [Ce (58) to Lu (71)] is only 11pm
(from 183 to 172 pm). Similarly, decrease in ionic radii from Ce3+ to
Lu3+ is only 17 pm (103 to 86 pm).
The cumulative effect of the contraction of the lanthanoid series,
known as lanthanoid contraction, causes the radii of the members
Trends in ionic radii of lanthanoids
of the third transition series to be very similar to those of the
corresponding members of the second series. The almost identical
Atomic and Ionic Radii of Lanthanoides
Atomic Electronic configurations Radii/pm

Number Name Symbol Ln Ln2+ Ln3+ Ln 4+
Ln Ln3+
1 2 1
57 Lanthanum La 5d 6s 5d 4f0 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103
3 2 3
59 Praseodymium Pr 4f 6s 4f 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
5 2 5
61 Promethium Pm 4f 6s 4f 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
7 2 7
63 Europium Eu 4f 6s 4f 4f6 199 95
7 1 2 7 1
64 Gadolinium Gd 4f 5d 6s 4f 5d 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
10 2 10
66 Dysprosium Dy 4f 6s 4f 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 176 89
12 2 12
68 Erbium Er 4f 6s 4f 4f11 175 88
69 Thulium Tm 4f136s2 4f13 4f12 174 87
14 2 14
70 Ytterbium Yb 4f 6s 4f 4f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 – –
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2.4 Magnetic Behaviour They form oxides M2O3 and hydroxides M(OH)3. The oxides and
Paramagnetism is shown by the positive ions of lanthanides hydroxides are basic like alkaline earth metal oxides and
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). This hydroxides.
property of the lanthanides is due to presence of unpaired
electrons in the incomplete 4f subshell.
Lanthanides differ from transition elements in the fact that their
magnetic moments do not obey ‘spin only’ formula, viz.,
 eff  n ( n  2) B.M. where n is the number of unpaired

electrons. This because in case of transition elements, the orbital
contribution is quenched by the electric field of the environment
but in case of lanthanides, 4f orbitals lie to deep to be quenched.
Hence, their magnetic moment is calculated by considering spin
as well as orbital contribution, i.e,
 eff  4 S (S  1)  L ( L  1) B.M.
where S is spin quantum number and L is orbital quantum number. Chemical reactions of the lanthanoids
The hydroxides Ln(OH) 3 are precipitated as gelationous
NOTE precipitates by the addition of NH4OH to aqueous solutions. These
Separation of the Lanthanide Elements hydroxides are ionic and basic. They are less basic than Ca(OH)2
but more basic than Al(OH)3 which is amphoteric. The metals,
Since the change in ionic radius is very small, the chemical oxides and hydroxides all dissolve in dilute acids, forming salts.
properties are similar. This makes the separation of the element Ln(OH)3 are sufficiently basic to absorb CO2 from the air and form
in pure state difficult. Separation is done by Ion Exchange carbonates. The basicity decreases as the ionic radius decreases
methods which is based on the ionic size. from Ce to Lu. Thus Ce(OH)3 is the most basic, and Lu(OH3),
2.5 Colour which is the least basic, is intermediate between Scandium and
The lanthanides are silvery white metals. However, most of the Yttrium in basic strength. The decrease in basic properties is
trivalent metal ions are coloured, both in the solid state and in illustrated by the hydroxides of the later elements dissolving in
aqueous solution. This is due to the partly filled-f-orbitals which hot concentrated NaOH, forming complexes.
permit f-f transition. Yb(OH)3 + 3NaOH  3Na+ + [Yb(OH)6]3–
NOTE Lu(OH)3 + 3NaOH  3Na+ + [Lu(OH)6]3–

2.7 Uses of Lanthanides
Lanthanides ions with x f electrons have a similar colour to those
The lanthanoids are mainly used for :
with (14–x) f electrons e.g., La3+ and Lu3+ are colourless, Sm3+
and Dy3+ are yellow and Eu3+ and Tb3+ are pink. (i) Production of alloy steels for plates and pipes
2.6 Chemical Reactivity (ii) Production of Mischmetall, it is an alloy containing (95%)
lanthanoid metals + (5%) iron + traces of S, C, Ca and Al.
Chemically the earlier members of the lanthanide series are quite
similar to calcium but, with increasing atomic number, they behave (iii) Mischmetall is used as Mg based alloy to produce bullets
more like aluminium. shell and lighter flints.
These metals combine with hydrogen when gently heated in (iv) Mixed oxides of lanthanoids are used as catalyst in petroleum
hydrogen gas to from hydrides (LnH3). cracking.
When these metals are heated with carbon, they give carbides, (v) Some lanthanide oxides are used as phosphors in television
Ln3C, Ln2C3 and LnC2. screens and similar fluorescing surfaces.
They liberate hydrogen from dilute acids and burn in halogens to
form halides (LnX3).
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3. THE ACTINIDES SERIES 3.2 Oxidation State

Unlike lanthanides, actinides show a large number of oxidation
The actinoids include the fourteen elements from Th to Lr.
states. This is because of very small energy gap between 5f, 6d
The actinoids are radioactive elements and the earlier members and 7s subshells. Hence, all their electrons can take part in bond
have relatively long half-lives, the latter ones have half-life values formation. The dominant oxidation state of these element is +3
ranging from a day to 3 minutes for lawrencium (Z =103). The (similar to Lanthanides). Besides +3 state, Actinides also exhibit
latter members could be prepared only in nanogram quantities. an oxidation state of +4. Some Actinides show still higher oxidation
3.1. Electronic Configuration states. The maximum oxidation state first increases upto the middle
of the series and then decreases, e.g., it increases from + 4 from
All the actinoids have the electronic configuration of 7s2 and
Th to +5, +6, and +7 for Pa, U and Np but decreases in the
variable occupancy of the 5f and 6d subshells. The fourteen
succeeding elements.
electrons are formally added to 5f, though not in thorium (Z = 90)
but from Pa onwards the 5f orbitals are complete at element 103. The actinides resemble lanthanides in having more compounds
The irregularities in the electronic configurations of the actinoids, in +3 state than in the +4 state. However, the compounds in the +3
like those in the lanthanoids are related to the stabilities of the f0, and +4 state tend to undergo hydrolysis.
f7 and f14 occupancies of the 5f orbitals. Thus, the configurations 3.3 Atomic and Ionic Radii
of Am and Cm are [Rn] 5f7 7s2 and [Rn] 5f76d17s2. Although the 5f
The actinides show actinide contraction (very much like lanthanide
orbitals resemble the 4f orbitals in their angular part of the wave-
contraction) due to poor shielding effect of the 5f-electrons. As a
function, they are not as buried as 4f orbitals and hence 5f electrons
result, the radii of the atoms or ions of these metals decrease
can participate in bonding to a far greater extent than 4f orbitals in
regularly across the series. The contraction is greater from element
case of lanthanoides.
to element in this series due to poorer shielding by 5f electrons
compared to 4f electrons in lanthanoides. This is because 5f
orbitals extend in space beyond 6s and 6p orbitals whereas 4f
orbitals are buried deep inside the atom.
Atomic and Ionic Radii of Actinoids

Atomic Electronic configurations* Radii/pm
Number Name Symbol M M3+ M4+ M 3+
M4+
1 2 0
89 Actinium Ac 6d 7s 5f 111
90 Thorium Th 6d27s2 5f1 5f0 99
2 1 2 2
91 Protactinium Pa 5f 6d 7s 5f 5f1 96
3 1 2 3
92 Uranium U 5f 6d 7s 5f 5f2 103 93
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92
6 2 5
94 Plutonium Pu 5f 7s 5f 5f4 100 90
95 Americium Am 5f77s2 5f6 5f5 99 89
7 1 2 7
96 Curium Cm 5f 6d 7s 5f 5f6 99 88
97 Berkelium Bk 5f97s2 5f8 5f7 98 87
10 2 9
98 Callifornium Cf 5f 7s 5f 5f8 98 86
11 2 10
99 Einstenium Es 5f 7s 5f 5f9 – –
100 Fermium Fm 5f127s2 5f11 5f10 – –
13 2 12
101 Mendelevium Md 5f 7s 5f 5f11 – –
102 Nobelium No 5f147s2 5f13 5f12 – –
14 1 2 14
103 Lawrencium Lr 5f 6d 7s 5f 5f13 – –
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3.4 Magnetic Behaviour 4. COMPARISON OF LANTHANIDES AND
Like lanthanides, the actinides are strongly paramagnetic. The ACTINIDES
variation in magnetic susceptibility of actinides with the
increasing number of unpaired electrons is similar to that of Similarities :
lanthanides but the values are higher for the actinides than the As both lanthanides and actinides involve filling of f-orbitals,
lanthanides. they show similarities in many respects as follows :
3.5 Colour (i) Both show mainly oxidation state of +3.
These metals are silvery white. However, actinide cations are (ii) Both are electropositive and very reactive.
generally coloured. The colour of the cation depends upon the
(iii) Both exhibit magnetic and spectral properties.
number of 5f-electrons. The cations containing no 5f-electron or
having seven 5f-electrons (i.e., exactly half-filled f-subshell) are (iv) Actinides exhibit actinide contraction like lanthanide
colourless. The cations containing 2 to 6 electrons in the 5f- contraction shown by lanthanides.
subshell are coloured both in the crystalline state as well as in Differences :
aqueous solution. The colour arises due to f–f transition e.g. The show differences in some of their characteristics as follows :
Ac3+ (5f 0) = colourless, U3+ (5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+
Difference between Lanthanides and Actinides
(5f 5) = Violet, Am3+ (5f 6) = Pink, Cm3+ (5f 7) = Colourless,
Lanthanides Actinides
Th3+ (5f 0) = Colourless as so on.
(i) Besides + 3 oxidation (i) Besides +3 oxidation
3.6 Chemical Reactivity
state they show + 2 and +4 state, they show higher
Actinides show almost similar chemical behaviour to lanthanides. oxidation states only in few oxidation states of +4, +5,
cases. +6, + 7.
(ii) Most of their ions are (ii) Most of their ions are
colourless. coloured.
(iii)They have less tendency (iii) They have greater
towards complex formation. tendency towards complex
formation.
(iv) Lanthanides compounds (iv) Actinides compounds
are less basic. are more basic.
(v) They do not form (v) They from oxocations.
oxocation. e.g. UO 22  , PuO 22  and UO  .
(vi) Except promethium, (vi) They are radioactive.
they are non-radioactive.
Chemical reactions of the actinides (vii) Their magnetic (vii) Their magnetic
properties can be explained properties cannot be
easily. explained easily.
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SUMMARY
d-Block Elements f-Block Elements
 d-block elements are those in which the last electron goes  The elements in which the last electron enters f-orbital of
to (n-1) d-orbitals.
(n-2)th shell are called f-block elements. f-block elements
 General electronic configurations of d-block elements is :
are of two types lanthanides and actinides.
ns1-2, (n-1)d1-10
 Transition metals have high values of melting and boiling  General electronic configuration of f-block elements is ns2,
points which are due to the presence of strong metallic (n-1)d0-1, (n-2)f1-14
bonding in these metals.  + 3 oxidation state (O.S.) is the most stable O.S. of
lanthanides.
 Due to lanthanide contraction, atomic radii for the
elements of 3rd transition series are almost equal to those  There is a steady decrease in atomic and ionic (M³+ ions)
for the elements of 2nd transition series. radii of lanthanides. This steady decrease in atomic and
ionic radii is called lanthanide contraction.
 The values of ionisation energies increase as we move
from left to right in each series.  Magnetic moment value of lanthanides and actinides is
calculated by considering both orbital spin contribution.
 Except for Cu, E°red values for other metals of Ist transition
series are negative. µeff value is given by µeff = 4S (S+1)+L(L+1) B.M, here S
spin quantum number and L= orbital quantum number
 Excepting a few metals, most of the metals show several
oxidation states. This is due to the fact that (n-1)d and ns  Mischmetal is an important alloy of lanthanides. It
orbitals have almost the same energy. contains 90% lanthanides (La= 40%, Ce and other
lanthanides= 50% ) , Fe = 5% and traces of other elements
 Transition metal ions which contain partially filled d-
like C, S, Al, Ca.
orbitals are usually coloured. The colour arises because of
d-d transition. Transition metal ions with d0 or d10  The actinide elements lying beyond U (Np-93 to Lw-103)
configuration are colourless because d-d transition is not are called trans-uranic or trans-uranium elements.
possible in such ions.  Unlike lanthanides, actinides show a large number of
oxidation states.
 Transition metals form interstitial compounds.
 Many transition metals and their alloys and compounds  Actinides have lower values of ionisation energies.
act as catalysts in many chemical reactions.  Most of actinide halides form complex compounds with
alkali metal halides. The degree of complex formation for
the ions decreases as : M4+ > MO22+ > M3+ > MO2+.
 Thorium is used in atomic reactors and in the treatment of
cancer. Uranium is used as a nuclear fuel. Plutonium is
used as a fuel for atomic reactors as well as for making
atomic bombs.
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d AND f BLOCK ELEMENTS 213

General Introduction of d Block Elements
1. Transition elements have 11. The electronic configuration of chromium is actually
(a) completely filled ‘d’ levels [Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
is because
(b) completely filled ‘s’ levels and d levels
(a) an exactly half-filled d level gives additional stability,
(c) incompletely filled ‘s’ levels and completely filled ‘d’
according to the Hund rule of maximum multiplicity
levels
(b) the 4s orbital has higher energy than the 3d orbitals
(d) incompletely filled ‘d’ levels
(c) the 4s orbitals has lower energy than the 3d orbitals
2. The general electronic configuration of the transition
elements is (d) the 3d and 4s orbitals have equal energies and hence
electron migration occurs readily
(a) (n – 1)d10 (n + 1)s2 (b) (n – 1)d1–10 (n + 1)s1–2
(c) (n – 1)d np ns
1–10 6 2
(d) (n – 1)d1–10 ns1–2 12. Which of the following ions has the maximum number of
unpaired d electrons ?
3. Which of the following transition elements has completely
filled d orbitals (the d10 configuration) (a) Fe3+ (b) V3+
(a) Co (b) Cr (c) Ti3+
(d) Mg2+
(c) Hg (d) Ni
13. Which of the following ions possesses the maximum
4. The last electron of a d-block element occupies the orbital
number of unpaired electrons ?
(a) (n – 1)d (b) nd
(a) Ni2+ (b) Fe2+
(c) np (d) (n – 1)s
(c) Cu +
(d) Zn2+
5. The general electronic configuration of group 12 elements
is 14. Which of the following does not possess unpaired
electrons ?
(a) ns2 (b) ns2np6
(a) Co3+ (b) Cu2+
(c)  n  1 d10 ns 2 (d)  n  1 d110 ns 2
(c) Ti2+ (d) Hg2+
6. The transition elements are 15. Which of the following electronic configurations
(a) more reactive than group 1 elements represents Fe3+ ?
(b) more reactive than group 2 elements (a) [Ar]3d64s2 (b) [Ar]3d54s1
(c) less reactive than group 1 elements but more reactive (c) [Ar]3d 4s
5 2
(d) [Ar]3d54s0
than group 2 elements 16. Which of the following is not true about the transition
(d) less reactive than group 1 and 2 elements elements ?
7. Transition elements (a) They show variable oxidation states
(a) exhibit inert-pair effect (b) Their ions have a strong tendency to form complexes
(b) show nonmetallic character (c) Their compounds usually do not absorb ultraviolet
(c) do not form complex compounds and visible lights
(d) exhibit variable oxidation states (d) Their ions and complex ions usually possess magnetic
moments.
8. The electronic configuration of silver is
17. Which of the following transition metals does not show
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1
variable oxidation states ?
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2
(a) Mercury (b) Zinc
9. The electronic configuration of palladium is
(c) Gold (d) Silver
(a) [Ar]3d84s2 (b) [Kr]4d85s2
(c) [Kr]5d86s2 (d) [Kr]4d105s0
10. The electronic configuration of platinum is
(a) [Xe] 4f145d96s1 (b) [Ar] 4f145d106s2
(c) [Ar] 4f 6d 7s
14 10 2
(d) [Ar] 4f146d97s1
18. Which of the following statements is incorrect ? 23. For a given ion, the magnetic moment is 2.83 BM. The
(a) The compounds formed by the 3d transition metals in total spin (s) of all the unpaired electrons is
lower valence states are ionic but those in higher (a) 2 (b) 1
valence states are covalent. (c) 3/2 (d) 1/2
(b) The 4d and 5d transition metals form less ionic 24. The oxidation states shown by transition elements is
compounds than do the 3d transition metals. related to their
(c) The compounds formed by the 3d transition metals (a) electropositive characters
are less ionic than the corresponding compounds
formed by the 4d and 5d transition metals. (b) electronic configurations
(d) The ionization energies of 3d, 4d and 5d transition (c) atomic weights
metals are greater than those of group 1 and 2 metals. (d) atomic sizes
19. The noble character of platinum and gold is favoured by 25. Identify the species having an atom in +6 oxidation state.
(a) high enthalpies of sublimation, high ionization (a) MnO4 (b)  

energies and low enthalpies of solvation

(b) high enthalpies of sublimation, low ionization energies (c) NiF63 (d) CrO2Cl2
and low enthalpies of solvation
26. Which one of the following exhibits the largest number of
(c) low enthalpies of sublimation, high ionization energies oxidation states?
and low enthalpies of solvation
(a) Mn (25) (b) Ti (22)
(d) high enthalpies of sublimation, high ionization
energies and high enthalpies of solvation (c) Cr (24) (d) V (23)
27. Formation of interstitial compound makes the transition
metal
Physical Properties of d Block Elements (a) more soft (b) more metallic
(c) more ductile (d) more hard
20. Which of the following arrangements does not represent 28. Which of the following ions is colourless in solution ?
the correct order of the property stated against it ? (a) V3+ (b) Cr3+
(c) Co2+ (d) Sc3+
(a) V 2  Cr 2  Mn 2  Fe2 : paramagnetic behaviour
29. Which one of the following ionic species will impart colour
(b) Ni 2  Co 2  Fe2  Mn 2 : ionic size to an aqueous solution ?
(a) Ti4+ (b) Cu+
(c) Co3  Fe3  Cr 3  Sc3 : stability in aqueous solution
(c) Zn2+ (d) Cr3+
(d) Sc  Ti  Cr  Mn : number of oxidation states 30. Which of the following ions is expected to be coloured in
21. The covalent radii of transition metals decrease from left solution ?
to right in a period because (a) Cu+ (b) Cu2+
(a) the densities of the metals decrease with increasing (c) Ti 4+
(d) Sc3+
atomic number due to poor shielding of electrons 31. Which of the following compounds is expected to be
(b) the screening of nuclear charge by d electrons is poor coloured ?
and hence the nuclear charge attracts all the electrons (a) Ag2SO4 (b) CuF2
strongly, causing a decrease in size (c) MgF2 (d) CuCl
(c) the ionization energies also decrease correspondingly
(d) the metallic character decreases as the atomic number
increases Chemical Properties of d Block Elements
22. Among the transition metals, the melting points of Zn,
Cd and Hg are relatively low because 32. Which of the following statements is incorrect for CrO3 ?
(a) their d shells are not completely filled (a) It is a bright orange solid.
(b) their d electrons do not participate in metallic bonding (b) It is commonly called chromic acid.
(c) It is prepared by adding concentrated H2SO4 to a
(c) their densities are higher
saturated solution of sodium dichromate.
(d) of all the above
(d) The colour arises due to d–d transition.
33. Which of the following oxides of chromium is amphoteric 41. Which one of the following oxides of chromium is
in nature ? amphoteric in nature ?
(a) CrO (b) CrO3 (a) CrO (b) Cr2O3
(c) Cr2O3 (d) CrO5 (c) CrO3 (d) CrO5
34. Transition metals 42. Which of the following oxides of manganese is
(a) form only ionic compounds amphoteric ?
(a) MnO2 (b) Mn2O3
(b) form exclusively covalent compounds
(c) Mn2O7 (d) MnO
(c) may form either ionic or covalent compounds 43. Four successive members of the first series of the
depending on the condition transition metals are listed below. For which one of
(d) exclusively form coordination compounds but no
simple compounds 
o
them the standard potential E M 2 / M  value has a
35. Which of the following is an incorrect statement? positive sign?
(a) The lowest oxidation state oxide of a transition metal (a) Co (Z = 27)
is acidic whereas the highest one is usually basic. (b) Ni (Z = 28)
(b) A transition metal usually exhibits higher oxidation (c) Cu (Z = 29)
states in its fluorides than in its iodides. (d) Fe (Z = 26)
(c) Transition metal halides become more covalent with 44. Deep red-yellow vapour of CrO2Cl2 is passed into an
the increasing oxidation state of the transition metal aqueous solution of NaOH. The solution turns
and are more susceptible to hydrolysis. (a) yellow due to the formation of Na2Cr2O7
(d) The highest oxide of a transition metal is acidic whereas (b) yellow due to the formation of Na2CrO4
the lowest one is usually basic. (c) green due to the formation of CrCl3
36. The highest possible oxidation state shown by osmium (d) red due to the formation of Na2CrO4
in its compounds is 45. Which of the following oxides of manganese is acidic ?
(a) +4 (b) +8 (a) MnO (b) Mn2O3
(c) +6 (d) +10 (c) Mn2O7 (d) MnO2
37. Iron exhibits +2 and +3 oxidation states. Which of the 46. Which of the following oxides of manganese is stable as
following statements about iron is incorrect ? well as basic ?
(a) Ferrous oxide is more basic in nature than the ferric (a) MnO2 (b) Mn2O7
oxide. (c) MnO (d) Mn2O3
(b) Ferrous compounds are relatively more ionic than the 47. Which of the following compounds is colourless?
corresponding ferric compounds. (a) K2MnO4 (b) HgI2
(c) Ferrous compounds are less volatile than the (c) ZnSO4 (d) FeSO4
corresponding ferric compounds. 48. Ammonia forms the complex ion [Cu(NH3)4]2+ with copper
ions in alkaline solutions but not in acidic solutions. What
(d) Ferrous compounds are more easily hydrolysed than
is the reason for it ?
the corresponding ferric compounds.
(a) In acidic solutions protons coordinate with ammonia
38. The transition metals sometimes form nonstoichiometric molecules forming NH4+ ions and NH3 molecules are
compounds. These compounds have not available
(a) definite structures and definite proportions (b) In alkaline solutions insoluble Cu(OH)2 is precipitated
(b) indefinite structures and definite proportions which is soluble in excess of any alkali
(c) definite structures and indefinite proportions (c) Copper hydroxide is an amphoteric substance
(d) indefinite structures and indefinite proportions (d) In acidic solutions hydration protects copper ions
39. Which of the following ions is paramagnetic ?
(a) Zn2+ (b) N3– Potassium Permanganate
(c) Mn 4+
(d) Cu+
40. Which of the following ions is diamagnetic ? 49. Which of the following compounds has colour but no
(a) Ni2+ (b) Ti4+ unpaired electrons?
(a) KMnO4 (b) MnSO4
(c) Cr3+
(d) Co3+
(c) K2MnO4 (d) MnC12
50. MnO 4 is prepared by treating a solution containing Mn2+ Potassium Dichromate

ions with a very strong oxidizing agent such as 57. When hydrogen peroxide is added to an acidic solution
of a dichromate, the most probable product is
(a) PbO2 (b) C2 O42 (a) K2CrO4 (b) CrO3
(c) I2 (d) Fe3+ (c) Cr2O3 (d) CrO(O2)2
51. Which of the following compounds is green in colour ? 58. Number of moles of K2Cr2O7 reduced by one mole of
(a) KMnO4 (b) (NH4)2Cr2O7 Sn2+ ions is
(c) MnO2 (d) K2MnO4 1
(a) (b) 3
52. KMnO4 is manufactured on a large scale by 3
(a) fusing MnO2 with KOH and then oxidizing the fused 1
mixture with KNO3 (c) (d) 6
6
(b) fusing MnO2 with Na2CO3 in the presence of O2
59. CrO3 dissolves in aqueous NaOH to give
(c) fusing MnO2 with KOH and KNO3 to form K2MnO4
which is then electrolytically oxidized in an alkaline (a) CrO 24  (b) Cr(OH)2
solution
(c) Cr2 O 72  (d) Cr(OH)3
(d) fusing MnO2 with KNO3 and then acidifying the fused
mixture 60. Cr2 O 72  reacts with OH– as
53. When KMnO4 acts as an oxidising agent and ultimately
forms [MnO4]2–, MnO2 Mn2O3, Mn+2 then the number of Cr2 O 27   2(OH  )  2CrO 42   H 2 O
electrons transferred in each case repectively is The change in oxidation number of Cr is
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (a) 6 (b) 3
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1 (c) zero (d) 4
54. Amount of oxalic acid present in a solution can be 61. CrO 24  reacts with H+ as
determined by its titration with KMnO4 solution in the
presence of H2SO4. The titration gives unsatisfactory 2CrO 24   2H   Cr2 O 72   H 2 O
result when carried out in the presence of HCl, because
The change in oxidation number of Cr is
HCl
(a) +5 (b) +7
(a) reduces permanganate to manganate
(c) +6 (d) zero
(b) furnishes H+ ions in addition to those from oxalic acd 62. Acidified K2Cr2O7 on treatment with KI produces
(c) reduces permanganate to Mn2+ (a) KIO3 (b) I2
(d) oxidises oxalic acid to carbon dioxide and water (c) KIO4 (d) 
55. KMnO4 in an acidic medium will not oxidize 63. What would happen when a solution of potassium
(a) NO 2 (b) SO24 chromate is treated with an excess of dilute nitric acid ?
(a) Cr2O72– and H2O are formed
(c) HN3 (d) H2O2
(b) CrO42– is reduced to +3 state of Cr
56. Which of the following is an incorrect statement ?
(a) In a redox reaction in acidic medium, KMnO4 produces (c) CrO42– is oxidized to +7 state of Cr
Mn2+ ions. (d) Cr3+ and Cr2O72– are formed
(b) In a redox reaction in strongly alkaline medium, KMnO4 64. Which of the following is not formed when H2S reacts
produces MnO24 ions. with acidic K2Cr2O7 solution?
(a) CrSO4 (b) Cr2(SO4)3
(c) In a redox reaction in neutral medium, KMnO4 produces (c) K2SO4 (d) S
MnO2.
65. K 2 Cr2 O7 on heating with aqueous NaOH gives
(d) In a redox reaction in alkaline medium, KMnO4
produces Mn2O7. (a) Cr2 O 72  (b) Cr  OH  2
(c) CrO 24  (d) Cr  OH 3

Other Compounds of d-Block Elements 74. Permanent magnets are generally made from the alloy of
(a) Co (b) Zn
66. The value of magnetic moment (m spin only) for Cu2+ in
CuSO4.5H2O is (c) Al (d) Pb
(a) 5.92 BM (b) 4.92 BM 75. Match the catalyst with the process :
Catalyst Process
(c) 2.83 BM (d) 1.73 BM
(i) V2 O 5 (p) The oxidation of ethyne to
67. Calomel (Hg2Cl2) on reaction with ammonium hydroxide
ethanal
gives
(ii) TiC14 (q) Polymerisation of alkynes
(a) HgO (b) Hg2O (iii) PdC12 (r) Oxidation of SO2 in the
manufacture of H2SO4
(c) NH2 – Hg – Hg – Cl (d) Hg NH2 Cl (iv) Nickel Complexes (s) Polymerisation of ethylene
68. A red solid is insoluble in water. However it becomes Which of the following is the correct option?
soluble if some KI is added to water. Heating the red solid (a) (i)-(r), (ii)-(s), (iii)-(p), (iv)-(q)
in a test tube results in liberation of some violet coloured (b) (i)-(p), (ii)-(q), (iii)-(r), (iv)-(s)
fumes and droplets of a metal appear on the cooler parts (c) (i)-(p), (ii)-(r), (iii)-(q), (iv)-(s)
of the test tube. The red solid is (d) (i)-(r), (ii)-(p), (iii)-(s), (iv)-(q)
(a) HgI2 (b) HgO
(c) Pb3O4 (d) (NH4)2Cr2O7
General Characteristics of f-block Elements
69. Na2CrO4 on treatment with lead acetate gives a precipitate.
This precipitate is dried and the solid is used as a pigment
for road signs and markings. The solid is known as 76. Lanthanides are characterized by the filling of the
(a) white lead (b) chrome green (a) penultimate 4f energy level
(c) chrome yellow (d) red lead (b) antipenultimate 4f energy level
70. The compound ZnSO4 is white because (c) penultimate 3f energy level
(a) charge is transferred from the metal to the oxygen (d) antipenultimate 3f energy level
atoms 77. The general electronic configuration f-block elements is
(b) electron transfer to d level does not occur as the level represented by
is already filled to capacity in zinc (a) (n – 2)f1–14 (n – 1)d0–1ns2
(c) Zn2+ has d10 configuration and d–d transition occurs (b) (n – 2)f1–14 (n – 1)d0–5ns0–2
easily (c) (n – 2)f1–14 (n – 1)d0–10ns1–2
(d) Zn2+ ions absorb light of the visible range (d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2
71. Consider the following equilibrium 78. The electronic configurations of the first four members of
 the actinide series cannot be written accurately in a regular
AgCl + 2NH3  [Ag (NH3)2]+ + Cl– manner because of
White precipitate of AgCl appears on adding which of the (a) small difference in energy between 5f and 6d orbitals
following? (b) large difference in energy between 5f and 6d orbitals
(a) aqueous HNO3 (b) aqueous NaCl (c) small difference in energy between 5f and 6s orbitals
(c) aqueous NH4Cl (d) NH3 (d) violation of the Pauli exclusion principle
72. Which of the following compounds gives red precipitate 79. The electronic configuration of cerium is
with AgNO 3 ? (a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1
(a) KI (b) NaBr (c) [Xe]4f15d26s2 (d) [Xe]4f25d06s2
(c) K2CrO4 (d) NaNO3 80. The outer electronic configuration of Gd (At. No. 64) is
(a) 4f3 5d5 6s2 (b) 4f8 d0 6s2
Uses of d Block Elements
(c) 4f4 5d4 6s2 (d) 4f7 5d1 6s2
73. Corrosion of iron can be prevented by coating the
surface with
(a) Zn (b) Sn
(c) Ni (d) Any of these
81. Which of the following statements concerning (a) 1.40 Å (b) 1.06 Å
lanthanide elements is false? (c) 0.85 Å (d) 1.60 Å
(a) All lanthanides are highly dense metals.
87. The atomic and ionic radii (M3+ ions) of lanthanide
(b) More characteristic oxidation state of lanthanide
elements decrease with increasing atomic number. This
elements is +3.
effect is called
(c) Lanthanides are separated from one another by ion
exchange method. (a) lanthanide contraction (b) lanthanide expansion
(d) Ionic radii of trivalent lanthanides steadily increases (c) actinide contraction (d) none of these
with increase in the atomic number. 88. Lanthanide contraction occurs because
82. Which of the following statements is correct for the (a) the 4f electrons, which are gradually added, create a
lanthanoids ? strong shielding effect
(a) The 4f electrons do not take part in bonding. (b) the 4f orbitals are greater in size than the 3d and 3f
(b) The 4f electrons can neither be removed to produce orbitals
ions nor be made to take part in crystal field (c) the 5f orbitals strongly penetrate into the 4f orbitals
stabilization of complexes.
(d) the poor shielding effect of 4f electrons is coupled
(c) The 4f electrons in the antipenultimate shell are very with increased attraction between the nucleus and the
effectively shielded by the 5s and 5p electrons. added electrons
(d) All of these 89. Which of the following statements is correct ?
83. Identify the incorrect statement among the following : (a) The second-row elements have smaller radii than the
(a) 4f and 5f orbitals are equally shielded. corresponding third-row ones.
(b) Because of lanthanide contraction, the radii of the third-
(b) d–Block elements show irregular and erratic chemical
row elements are almost the same as those of the first-
properties among themselves. row elements.
(c) La and Lu have partially filled d–orbitals and no other (c) Because of lanthanide contraction, the radii of the third-
partially filled orbitals. row elements are almost the same as those of the
second-row elements.
(d) The chemistry of various lanthanoids is very similar.
(d) Because of lanthanide contraction, the separation of
84. In context of the lanthanoids, which of the following second-row elements from one another is easier.
statements is not correct ?
90. The lanthanide contraction is responsible for the fact that
(a) There is a gradual decrease in the radii of the members
(a) Zr and Zn have the same oxidation state
with increasing atomic number in the series.
(b) All the member exhibit +3 oxidation state. (b) Zr and Hf have about the same radius
(c) Because of similar properties the separation of (c) Zr and Nb have similar oxidation state
lanthanoids is not easy.
(d) Zr and Y have about the same radius
(d) Availability of 4f electrons results in the formation of
compounds in +4 state for all the members of the 91. Which of the following factors may be regarded as the
series. main cause of lanthanide contraction ?
85. Arrange Ce+3, La+3, Pm+3 and Yb+3 in increasing order of (a) Greater shielding of 5d electrons by 4f electrons
their ionic radii.
(a) Yb+3 < Pm+3 < Ce+3 < La+3 (b) Poorer shielding of 5d electrons by 4f electrons
(b) Ce+3 < Yb+3 < Pm+3 < La+3 (c) Effective shielding of one of 4f electrons by another in
(c) Yb+3 < Pm+3 < La+3 < Ce+3 the subshell
(d) Pm+3 < La+3 < Ce+3 < Yb+3
(d) Poor shielding of one of 4f electron by another in the
86. The radius of La3+ (Atomic number of La = 57) is 1.06 Å. subshell
Which one of the following given values will be closest
to the radius of Lu3+ (Atomic number of Lu = 71) ? 92. Which of the following elements shows the maximum
number of different oxidation states in its compounds ?
(a) Eu (b) La
(c) Gd (d) Am
93. The most common and stable oxidation state of 97. Lanthanide elements have
lanthanides is (a) similar lattice energies but widely different solvation
(a) +II (b) +IV and ionization energies
(c) +VII (d) +III (b) similar lattice and solvation energies but widely
94. Knowing that the chemistry of lanthanoids (Ln) is different ionization energies
dominated by its +3 oxidation state, which of the (c) similar lattice and ionization energies but widely
following statements is incorrect ? different hydration energies
(a) The ionic size of Ln (III) decrease in general with (d) similar lattice energies, solvation energies and
increasing atomic number ionization energies
98. The hardness, melting point and boiling point of elements
(b) Ln (III) compounds are generally colourless.
increase from Ce to Lu because
(c) Ln (III) hydroxide are mainly basic in character. (a) the attraction between the atoms increases as the size
(d) Because of the large size of the Ln (III) ions the bonding increases
in its compounds is predominantly ionic in character. (b) the attraction between the atoms decreases as the size
95. The actinoids exhibit more number of oxidation states in increases
general than the lanthanoids. This is because (c) the attraction between the atoms increases as the size
decreases
(a) The 5f orbitals extend further from the nucleus than
the 4f orbitals (d) the attraction between the atoms remains the same as
the size increases
(b) The 5f orbitals are more buried than the 4f orbitals
99. Select the correct statement(s) for comparison of
(c) There is a similarity between 4f and 5f orbitals in their lanthanoids with actinoids.
angular part of the wave function (a) Actinide contraction is greater from element to
(d) The actinoids are more reactive than the lanthanoids. element due to poor shielding by 5f electrons
96. Larger number of oxidation states are exhibited by the (b) Magnetic properties of actinoids are more complex,
actinoids than those by the lanthanoids, the main reason with corresponding lanthanides having higher values
being (c) Lanthanoids have higher I.E.
(a) 4f orbitals more diffused than the 5f orbitals (d) All of the above
100. Colour of lanthanide ions are observed mainly due to :
(b) lesser energy difference between 5f and 6d than
between 4f and 5d orbitals (a) f-f transitions
(c) more energy difference between 5f and 6d than between (b) crystal field splitting
4f and 5d orbitals (c) full f-orbital
(d) more reactive nature of the actinoids than the (d) partially filled d-subshell
lanthanoids
EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

2+
1. The electrode potential of M /M of 3d-series elements 9. The nature of oxides V2O3 and CrO is indexed as 'X' and 'Y'
shows positive value for (2021) type respectively. The correct set of X and Y is
(a) Fe (b) Co (2021)
(c) Zn (d) Cu (a) X = basic, Y = amphoteric
2. Which is the correct order of the following elements with (b) X = amphoteric, Y = basic
respect to their density? (2021) (c) X = acidic, Y = acidic
(a) Cr < Zn < Co < Cu < Fe (b) Zn < Cu < Co < Fe < Cr (d) X = basic, Y = basic
(c) Zn < Cr < Fe < Co < Cu (d) Cr < Fe < Co < Cu < Zn 10. Potassium permanganate on heating at 573 K gives a
3. In which of the following pairs, the outer most electronic product which is (2021)
configuration will be the same? (2021) (a) paramagnetic and colourless
2+ + 2+ +
(a) Ni and Cu (b) Fe and Co (b) diamagnetic and green
+ 2+ 2+ +
(c) Cr and Mn (d) V and Cr (c) diamagnetic and colourless
4. Which one of the following lanthanoids does not form (d) paramagnetic and green
MO2? [M is lanthanoid metal] (2021)
11. In the structure of the dichromate ion, there is a:
(a) Dy (b) Nd
(2021)
(c) Yb (d) Pr
(a) linear symmetrical Cr–O–Cr bond.
5. On treating a compound with warm dil. H2SO4, gas X is
(b) non-linear symmetrical Cr–O–Cr bond.
evolved which turns K2Cr2O7 solution acidified with dil.
H2SO4 to a green compound Y. X and Y respectively are : (c) linear unsymmetrical Cr–O–Cr bond.
(2021) (d) non-linear unsymmetrical Cr–O–Cr bond
(a) X = SO2, Y = Cr2(SO4)3 (b) X = SO2, Y = Cr2O3 12. Which one of the following lanthanides exhibits +2
oxidation state with diamagnetic nature?
(c) X = SO3, Y = Cr2(SO4)3 (d) X = SO3, Y = Cr2O3
(Given Z for Nd = 60, Yb = 70, La = 57, Ce =58)
6. The oxide that shows magnetic property is : (2021)
(2021)
(a) SiO2 (b) Na 2 O (a) Nd (b) Yb
(c) Mn 3 O 4 (d) MgO (c) La (d) Ce
2+
13. The Eu ion is a strong reducing agent in spite of its
7. The set having ions which are coloured and paramagnetic
ground state electronic configuration (outermost): [Atomic
both, is - (2021)
number of Eu = 63] (2021)
(a) Cu 2  , Cr 3 ,Sc  (b) Cu 2  , Zn 2  , Mn 4  (a) 4f 6s
7 2
(b) 4f
6
7 6 2
(c) 4f (d) 4f 6s
(c) Sc 2  , Zn 2  , Mn 4  (d) Ni 2  , Mn  , Hg 2 
14. What is the spin-only magnetic moment value (BM) of a
3+ 2+
8. The spin only magnetic moments (in BM) for free Ti , V divalent metal ion with atomic number 25, in it’s aqueous
3+
and Sc ions respectively are (At. No. - Sc: 21, Ti: 22, V: 23) solution? (2021)
(2021) (a) 5.26 (b) 5.92
(a) 3.87, 1.73, 0 (b) 1.73, 3.87, 0 (c) zero (d) 5.0
(c) 1.73, 0, 3.87 (d) 0, 3.87, 1.73
15. The common positive oxidation states for an element with (a) Statement I is incorrect but statement II is correct
atomic number 24, are: (b) Statement I is correct but statement II is incorrect
(2021) (c) Both statement I and statement II are correct
(a) + 2 to + 6 (b) + 1 and + 3 (d) Both statement I and statement II are incorrect
(c) + 1 to + 6 (d) + 1 and + 3 and + 6 23. Given below are two statement: one is labelled as Assertion
16. The major components of German Silver are (2021) A and the other is labelled as Reason R:
3+ 3+
(a) Ge, Cu and Ag (b) Cu, Zn and Ni Assertion A: Size of Bk ion is less than Np ion.
(c) Zn, Ni and Ag (d) Cu, Zn and Ag Reason R: The above is a consequence of the lanthanoid
contraction.
17. In a mildly alkaline medium, thiosulphate ion is oxidized by
MnO 4 to “A”. The oxidation state of sulphur in “A” is
answer from the options given below:
_________. (2021) (2021)
18. In the ground state of atomic Fe (Z = 26), the spin-only (a) Both A and R are true but R is not the correct explanation
1
magnetic moment is _______ 10 BM . (Round off to of A.
the Nearest Integer). (b) A is true but R is false.
(c) A is false but R is true.
[Given: 3  1.73, 2  1.41 ] (2021)
(d) Both A and R are true and R is the correct explanation of
3+
19. Number of electrons present in 4f orbital of Ho ion is A.
_________.(Given Atomic No. of Ho = 67) (2021) 24. Given below are two statements:
20. The number of 4f electrons in the ground state electronic Statement I: Potassium permanganate on heating at 573 K
2+
configuration of Gd is ______. forms potassium manganate.
[Atomic number of Gd = 64] (2021) Statement II: Both potassium permanganate and potassium
21. The number of f electrons in the ground state electronic manganate are tetrahedral and paramagnetic in nature.
configuration of Np (Z = 93) is ________. (Nearest integer) In the light of the above statements, choose the most
(2021) appropriate answer from the options given below:
22. Given below are two statements: (2021)
o 4+ 3+
Statement I: The E value for Ce /Ce is + 1.74 V. (a) Both statement I and statement II are false
4+ 3+
Statement II: Ce is more stable in Ce state than Ce state. (b) Statement I is true but statement II is false
In the light of the above statements, choose the most (c) Statement I is false but statement II is true
appropriate answer from the options given below. (d) Both statement I and statement II are true
(2021)
25. Metals generally melt at very high temperature. (a) Mn2+ (b) Mn4+
3+
Amongst the following the metal with the highest (c) Mn (d) Mn6+
melting point will be (JEE Main 2022) 35. The dark purple colour of KMnO4 disappears in the
(a) Hg (b) Ag titration with oxalic acid in acidic medium. The
(c) Ga (d) Cs overall change in the oxidation number of manganese
26. Cerium (IV) has a noble gas configuration. Which of in the reaction is : (JEE Main 2022)
the following is correct statement about it? (a) 5 (b) 1
(JEE Main 2022) (c) 7 (d) 2
(a) It will not prefer to undergo redox reactions. 36. The products obtained from a reaction of hydrogen
(b) It will prefer to gain electron and act as an peroxide and acidified potassium permanganate are
oxidizing agent (JEE Main 2022)
(c) It will prefer to give away an electron and behave (a) Mn4+, H2O only
as reducing agent (b) Mn2+, H2O only
(d) It acts as both, oxidising and reducing agent. (c) Mn4+, H2O, O2 only
27. Among the following, which is the strongest (d) Mn2+, H2O, O2 only
oxidizing agent? (JEE Main 2022) 37. Given below are two statements:
3+
(a) Mn (b) Fe3+ Statement I: Iron (III) catalyst, acidified
3+
(c) Ti (d) Cr3+ K2Cr2O7 and neutral KMnO4 have the ability to
28. The metal ion(in gaseous state) with lowest spin-only oxidise I– to I2 independently.
magnetic moment value is (JEE Main 2022) Statement II: Manganate ion is paramagnetic in
(a) V2+ (b) Ni2+ nature and involves pπ–pπ bonding.
2+
(c) Cr (d) Fe2+ In the light of the above statements, choose the
29. The most common oxidation state of Lanthanoid correct answer from the options. (JEE Main 2022)
elements is +3. Which of the following is likely to (a) Both statement I and Statement II are true
deviate easily from +3 oxidation state? (b) Both statement I and Statement II are false
(JEE Main 2022) (c) Statement I is true but Statement II is false
(a) Ce (At. No. 58) (b) La (At. No. 57) (d) Statement I is false but Statement II is true
(c) Lu (At. No. 71) (d) Gd (At. No. 64) 38. The total number of Mn = O bonds in Mn2O7 is ____.
30. In 3d series, the metal having the highest M2+/M (JEE Main 2022)
standard electrode potential is (JEE Main 2022) (a) 4 (b) 5
(a) Cr (b) Fe (c) 6 (d) 3
(c) Cu (d) Zn 39. In neutral or alkaline solution, MnO4 oxidises
31. The 'f' orbitals are half and completely filled,
thiosulphate to: (JEE Main 2022)
respectively in lanthanide ions 2
(a) S2O (b) S2O82 
[Given: Atomic no. Eu, 63; Sm, 62; Tm, 69; Tb, 65; 7
Yb, 70; Dy, 66] (JEE Main 2022) (c) SO32  (d) SO42 
(a) Eu2+ and Tm2+ (b) Sm2+ and Tm3+ 40. The reaction of zinc with excess of aqueous alkali,
(c) Tb4+ and Yb2+ (d) Dy3+ and Yb3+ evolves hydrogen gas and gives : (JEE Main 2022)
32. Which one of the lanthanoids given below is the most (a) Zn(OH)2 (b) ZnO
stable in divalent form? (JEE Main 2022) (c) [Zn(OH)4]2– (d) [ZnO2]2–
(a) Ce (Atomic Number 58) 41. In following pairs, the one in which both transition
(b) Sm (Atomic Number 62) metal ions are colourless is: (JEE Main 2022)
(c) Eu (Atomic Number 63 (a) Sc3+, Zn2+ (b) Ti4+, Cu2+
(d) Yb (Atomic Number 70) (c) V2+, Ti3+ (d) Zn2+, Mn2+
33. The electronic configuration of Pt (atomic number 42. Which of the following 3d-metal ion will give the
78) is: (JEE Main 2022) lowest enthalpy of hydration ( hyd H ) when
(a) [Xe] 4f14 5d9 6s1 (b) [Kr] 4f14 5d10
dissolved in water ? (JEE Main 2022)
(c) [Xe] 4f14 5d10 (d) [Xe] 4f14 5d8 6s2
(a) Cr2+ (b) Mn2+
34. The reaction of H2O2 with potassium permanganate
(c) Fe2+ (d) Co2+
in acidic medium leads to the formation of mainly:
(JEE Main 2022)
43. Manganese (VI) has ability to disproportionate in 54. The disproportionation of MnO42– in acidic medium
acidic solution. The difference in oxidation states of resulted in the formation of two manganese
two ions it forms in acidic solution is ______ compounds A and B. If the oxidation state of Mn in
(JEE Main 2022) B is smaller than that of A, then the spin-only
44. The difference in oxidation state of chromium in magnetic moment (μ) value of B in BM is
chromate and dichromate salts is_____. ___________. (Nearest integer) (JEE Main 2022)
(JEE Main 2022) 55. The magnetic moment of a transition metal
45. The spin-only magnetic moment value of the most compound has been calculated to be 3.87 B.M. The
basic oxide of vanadium among V2O3, V2O4 and metal ion is (JEE Main 2023)
V2O5 is _____ B.M. (Nearest integer) (a) Cr 2  (b) Mn 2
(JEE Main 2022)
(c) V 2  (d) Ti 2
46. The number of statement(s) correct from the
56. An ammoniacal metal salt solution gives a brilliant
following for Copper (at. No. 29) is/are_____.
red precipitate on addition of dimethylglyoxime. The
(A) Cu(II) complexes are always paramagnetic
metal ion is: (JEE Main 2023)
(B) Cu(I) complexes are generally colourless
(C) Cu(I) is easily oxidized (a) Cu 2  (b) Co 2 
(D) In Fehling solution, the active reagent has Cu(I) (c) Fe2 (d) Ni 2 
(JEE Main 2022) 57. K 2 Cr2 O7 paper acidified with dilute H 2SO 4 turns
47. Acidified potassium permanganate solution oxidises green when exposed to (JEE Main 2023)
oxalic acid. The spin-only magnetic moment of the (a) Carbon dioxide
manganese product formed from the above reaction (b) Sulphur trioxide
is_____ B.M. (Nearest Integer). (JEE Main 2022) (c) Hydrogen sulphide
48. The number of terminal oxygen atoms present in the (d) Sulphur dioxide
product B obtained from the following reaction 58. Match List I with List II
is_____.
FeCr2O4 + Na2CO3 + O2 → A + Fe2O3 + CO2 List I List II
A + H+ → B + H2O + Na+ (JEE Main 2022)
A. Cobalt
49. An acidified manganate solution undergoes I.  H 2  Cl2  production
catalyst
disproportionation reaction. The spin-only magnetic
moment value of the product having manganese in B. Syngas II. Water gas production
higher oxididation state is_____ B.M. (Nearest
integer) (JEE Main 2022) C. Nickel
III. Coal gasification
50. Among Co3+, Ti2+, V2+ and Cr2+ ions, one if used as a catalyst
reagent cannot liberate H2 from dilute mineral acid
D. Brine
solution, its spin-only magnetic moment in gaseous IV. Methanol production
solution
state is ……B.M. (Nearest integer)
(JEE Main 2022) Choose the correct answer from the options given
51. The spin-only magnetic moment value of M3+ ion (in below:- (JEE Main 2023)
gaseous state) from the pairs Cr3+/Cr2+, Mn3+/Mn2,
(a) A-IV, B-I, C-II, D-III
Fe3+/Fe2+ and Co3+/Co2+ that has negative standard
electrode potential, is _____ B.M. [Nearest integer] (b) A-IV, B-III, C-I, D-II
(JEE Main 2022) (c) A-II, B-III, C-IV, D-I
52. The spin-only magnetic moment value of the (d) A-IV, B-III, C-II, D-I
compound with strongest oxidizing ability among
MnF4, MnF3 and MnF2 is ______ B.M. [nearest 59. Potassium dichromate acts as a strong oxidizing agent
integer] (JEE Main 2022) in acidic solution. During this process, the oxidation
53. The spin only magnetic moment of the complex state changes from (JEE Main 2023)
present in Fehling’s reagent is______ B.M. (Nearest
(a) +3 to +1 (b) +6 to +3
integer). (JEE Main 2022)
(c) +2 to +1 (d) +6 to +2
60. The set of correct statements is:
(i) Manganese exhibits +7 oxidation state in its (a) Both (A) and (R) are true and (R) is the correct
oxide. explanation of (A)
(ii) Ruthenium and osmium exhibit +8 oxidation in (b) Both (A) and (R) are true but (R) is not the correct
their oxides. explanation of (A)
(iii) Sc shows +4 oxidation state which is oxidizing (c) (A) is false but (R) is true
in nature. (d) (A) is true but (R) is false
(iv) Cr shows oxidising nature in +6 oxidation state. 67. Which of the following elements have half-filled f-
(JEE Main 2023) orbitals in their ground state?
(a) (ii) and (iii) (b) (i), (ii) and (iv) (Given: atomic number
(c) (i) and (iii) (d) (ii), (iii) and (iv) Sm  62; Eu  63;Tb  65;Gd  64, Pm  61 )
61. A solution of CrO5 in amyl alcohol has a colour A. Sm B. Eu
(JEE Main 2023) C. Tb D. Gd
(a) Green (b) Orange-Red E. Pm
(c) Yellow (d) Blue Choose the correct answer from the options given
62. To inhibit the growth of tumours, identify the below: (JEE Main 2023)
compounds used from the following: (a) B and D only (b) A and E only
(A) EDTA (c) A and B only (d) C and D only
(B) Coordination Compounds of Pt 68. Highest oxidation state of Mn is exhibited in
(C) D - Penicillamine Mn 2 O7 . The correct statements about Mn 2 O7 are
(D) Cis – Platin (A) Mn is tetrahedrally surrounded by oxygen
Choose the correct answer from the option given atoms
below: (JEE Main 2023) (B) Mn is octahedrally surrounded by oxygen atoms
(a) B and D Only (b) C and D Only (C) Contains Mn-O-Mn bridge
(c) A and B Only (d) A and C Only (D) Contains Mn-Mn bond
63. KMnO 4 oxidises I  in acidic and neutral/faintly Choose the correct answer from the options given
below (JEE Main 2023)
alkaline solution, respectively to (JEE Main 2023)
(a) A and C only (b) A and D only
(a) I 2 & IO3 (b) IO3 & I 2 (c) B and D only (d) B and C only
(c) IO3 & IO3 (d) I2 & I 2 69. Given below are two statements : one is labelled as
2 Assertion (A) and the other is labelled as Reason (R).
64. Nd  (JEE Main 2023)
Assertion (A): Cu 2 in water is more stable than
(a) 4f 6 s2 2
(b) 4f 4
Cu  .
(c) 4f 3 (d) 4f 4 6 s 2
Reason (R): Enthalpy of hydration for Cu 2 is
65. The correct order of basic nature of oxides of
vanadium is (JEE Main 2023) much less than that of Cu  .
(a) V2 O3  V2 O 4  V2 O5 In the light of the above statements, choose the
(b) V2 O3  V2 O5  V2 O 4 correct answer from the options given below :
(JEE Main 2023)
(c) V2 O5  V2 O 4  V2 O3 (a) Both (A) and (R) are correct and (R) is the
(d) V2 O4  V2 O3  V2 O5 correct explanation of (A)
66. Given below are two statements: one is labelled as (b) (A) is correct but (R) is not correct
Assertion (A) and the other is labelled as Reason (R) (c) (A) is not correct but (R) is correct
Assertion (A): The first ionization enthalpy of 3 d (d) Both (A) and (R) are correct but (R) is not the
series elements is more than that of group 2 metals correct explanation of (A)
Reason (R): In 3 d series of elements successive 70. Strong reducing and oxidizing agents among the
filling of d-orbitals takes place. following, respectively, are (JEE Main 2023)
In the light of the above statements, choose the (a) Ce 4  and Eu 2  (b) Ce3 and Ce 4 
correct answer from the options given below: (c) Ce 4  and Tb 4  (d) Eu 2  and Ce 4 
(JEE Main 2023)
71. In chromyl chloride, the number of d-electrons 75. Given below are two statements: one is labelled as
present on chromium is same as in (Given at no. of Assertion A and the other is labelled as Reason R.
Ti : 22, V : 23, Cr : 24, Mn : 25, Fe : 26 ) Assertion A: 5f electrons can participate in bonding
(JEE Main 2023) to a far greater extent than 4f electrons.
(a) V (IV) (b) Ti (III) Reason R: 5f orbitals are not as buried as 4f orbitals
(c) Fe (III) (d) Mn (VII) In the light of the above statements, choose the
72. Prolonged heating is avoided during the preparation correct answer from the options given below
of ferrous ammonium sulphate to (JEE Main 2023) (JEE Main 2023)
(a) prevent reduction (a) A is true but R is false
(b) prevent hydrolysis (b) Both A and R are true and R is the correct
(c) prevent oxidation explanation of A
(d) prevent breaking (c) Both A and R are true but R is NOT the correct
73. Which of the following statements are correct? explanation of A
(A) The M 3 / M 2 reduction potential for iron is (d) A is true but R is false
76. The mismatched combinations are
greater than manganese.
A. Chlorophyll - Co
(B) The higher oxidation states of first row d-block
B. Water hardness - EDTA
elements get stabilized by oxide ion.
C. Photography -  Ag(CN) 2 

(C) Aqueous solution of Cr 2 can liberate hydrogen
from dilute acid. D. Wilkinson catalyst   Ph 3 P 3 RhCl 
(D) Magnetic moment of V 2  is observed between
E. Chelating ligand - D-Penicillamine
4.4-5.2 BM.
(a) D and E only (b) A and E only
(a) (C), (D) only
(c) A and C only (d) A, C and E only
(b) (A), (B), (D) only
77. The pair of lanthanides in which both elements have
(c) (A), (B) only
high third - ionization energy is: (JEE Main 2023)
(d) (B), (C) only
(a) Dy, Gd (b) Eu, Yb
74. Given below are two statements:
Statement I: Aqueous solution of K 2 Cr2 O7 is (c) Eu,Gd (d) Lu, Yb
78. How many of the following metal ions have similar
preferred as a primary standard in volumetric
value of spin only magnetic moment in gaseous
analysis over Na 2 Cr2 O7 aqueous solution.
state?
Statement II: K 2 Cr2 O7 has a higher solubility in (Given: Atomic number: V, 23;Cr, 24; Fe, 26; Ni, 28 )
water than Na 2 Cr2 O7
V 3 .Cr 3 , Fe 2  , Ni 3 (JEE Main 2023)
In the light of the above statements, choose the 79. The number of electrons involved in the reduction of
correct answer from the options given below: permanganate to manganese dioxide in acidic
(JEE Main 2023) medium is (JEE Main 2023)
(a) Statement I is true but Statement II is false
(b) Statement I is false but Statement II is true
(c) Both Statement I and Statement II are true
(d) Both Statement I and Statement II are false

Objective Questions I [Only one correct option] 11. Hybridization of Cr in K2Cr2O7 is
(a) sp3 (b) sp2
1. The compound in which nickel has the lowest oxidation
state is : (c) dsp2 (d) dsp3
(a) Ni(CO)4 (b) (CH3COO)2Ni 12. Which of the following statements regarding copper salts
(c) NiO (d) NiCl2(PPh3)2 is not true ?
2. Spiegeleisen is an alloy of : (a) Copper (I) ion disproportionates to copper metal and
copper (II) ion in aqueous solution.
(a) Cu + Zn + Ni (b) Ni + Cr
(b) Copper (I) ion can be stablised by the formation of
(c) Mn + Fe + C (d) Fe + Cr + Ni
insoluble complex compounds such as CuC l 2 and
3. Wilkinson’s catalyst consists of
(a) (C2H5)3 Al and TiCl4 Cu(CN) 2 .
(b) RhCl3 and Ph3P (c) Copper (II) oxide is red powder.
(c) HCo(CO)4 (d) The water of crystallization of copper sulphate is five
(d) trans-[(Rh(CO)(H)(PPh3)3] 13. Mercury is transported in the containers made of :
4. Which of the following is known as Adams’ catalyst ? (a) Ag (b) Pb
(a) Pt/PtO (b) V2O5/TiCl4 (c) Al (d) Fe
(c) Cu/V (d) Pt/Rh 14. When steam is passed over red hot iron, the substances
5. Malachite and azurite are used respectively are : formed are :
(a) Blue and green pigment (a) Fe2O3 + H2 (b) Fe3O4 + H2
(b) Red and green pigment (c) FeO + H2 (d) FeO + H2 + O2
(c) Green and blue pigment 15. Fe is made passive by :
(d) Green and red pigment (a) dil. H2SO4 (b) dil. HCl
6. Chloroplatinic acid is : (c) conc. HNO3 (d) conc. H2SO4
(a) monobasic (b) dibasic 16. Mark the correct statements :
(c) tribasic (d) tetrabasic (a) Hg forms an amalgam with iron
(b) Hg vapour is non-poisonous
7. The solubility of silver bromide in hypo solution is due to
the formation of : (c) Hg is monovalent in mercurous compound
(a) Ag2SO3 (b) Ag2S2O3 (d) Oxysalts of mercury are thermally unstable
(c) [Ag(S2O3)] –
(d) [Ag(S2O3)2]3– 17. Chemically philosopher’s wool is :
8. Sodium thiosulphate is used to remove the unexposed AgBr (a) ZnO (b) BaO
from photographic films by forming a complex. In this (c) HgCl (d) Hg2Cl2
complex of silver, the coordination number of silver is : 18. Philosopher’s wool when heated with BaO at 1100ºC gives
(a) 2 (b) 4 the compound :
(c) 6 (d) 8 (a) BaCdO2 (b) Ba + ZnO2
9. Na2CO3 + Fe2O3  A + CO2 what is A in the reaction ? (c) BaO2 + Zn (d) BaZnO2
(a) NaFeO2 (b) Na3FeO3 19. Which of the following is the correct formula for a
(c) Fe3O4 (d) Na2FeO2 compound of scandium and oxygen ?
10. The formula of azurite is : (a) Sc2O (b) ScO
(a) CuCO3 . Cu(OH)2 (b) 2CuCO3 . Cu(OH)2 (c) Sc3O2 (d) Sc2O3
(c) CuCO3 .2Cu(OH)2 (d) CuSO4 .Cu(OH)2 20. Dilute and slightly alkaline KMnO4 is called
(a) Fenton’s reagent (b) Lucas reagent
(c) Baeyer’s reagent (d) Tollens reagent
21. When acidified K2Cr2O7 solution is added to Sn+2 salt then 30. Ferrous sulphate on heating gives :
Sn+2 changes to (a) SO2 and SO3 (b) SO2 only
(a) Sn (b) Sn+3 (c) SO3 only (d) H2S only
(c) Sn+4 (d) Sn+ 31. Fe(OH)2 is precipitated from Fe(II) solutions as a white
22. Silver nitrate solution is kept in brown bottles in laboratory solid but turns dark green and then brown due to the
because : formation of :
(a) it reacts with ordinary white bottles (a) Fe(OH)2 and Fe(OH)3 (b) only Fe(OH)3
(b) brown bottles cut the passage of light through (c) Fe2O3 . (H2O)n (d) Fe2O3 . 2H2O
(c) brown bottles do not react with it 32. Which of the following mixture is known as Fenton’s
reagent ?
(d) ordinary bottles catalyse its decomposition
23. Sodium thiosulphate, Na2S2O3.5H2O is used in photography (a) FeSO4 + K4[Fe(CN)6] (b) FeSO4 + PdCl2
to : (c) FeSO4 + H2O2 (d) TiCl4 + (C6H5)3P
(a) Reduce the silver bromide to metallic silver 33. Oxide of metal cation which is not amphoteric?
(b) Convert the metallic silver to silver salt (a) Al3+ (b) Cr3+
(c) remove undercomposed AgBr as soluble silver (c) Cr2+ (d) Zn2+
thiosulphate complex 34. The false statement about iron (III) hydroxide is that :
(d) remove reduced silver
(a) it is a weaker base than Fe(OH)2
24. When AgNO3 comes in contact with skin, it leaves a black
(b) with concentrated KOH, it forms a complex K3[Fe(OH)6]
stain. This is because of :
(c) it gradually loses water and transforms into Fe2O3
(a) HNO3 prorduced by hydrolysis of AgNO3
(b) AgOH produced by hydrolysis of AgNO3 (d) it exhibits amphoteric properties with acid ones
predominating
(c) Its reduction of silver
35. A blood red colour is obtained when ferric chloride solution
(d) Its oxidation to silver oxide reacts with :
25. A white precipitate of AgCl dissolves in excess of : (a) KCN (b) KSCN
(I) NH3 (aq) (II) Na2S2O3 (c) K4[Fe(CN)6] (d) K3[Fe(CN)6]
(III) NaCN 36. Calomel is the name of :
(a) III only (b) I, II, III (a) HgCl2 (b) Hg2Cl2
(c) I, II (d) I only (c) HgCl2 + Hg (d) Hg2Cl2 + Hg
26. Boiling CuCl2 with Cu in conc. HCl gives : 37. HgCl2 is a covalent compound, sparingly soluble in water,
(a) CuCl (b) CuCl2 the solubility increases by the addition of chloride ions
(c) H[CuCl2] (d) Cu2Cl due to :
27. Verdigris is : (a) common ion effect
(a) Basic copper acetate (b) Basic lead acetate (b) formation of complex [HgCl4]2–
(c) Basic lead (d) None (c) weakening of Hg – Cl bonds
28. The oxidation state of copper changes when aqueous (d) strong ion – dipole forces
copper (II) ions react with : 38. Identify P in given reaction
(I) NaOH (aq) (II) Fe(s) 
KI  MnO 4 
OH
 IO3  P
(III) KI (aq)
(a) MnO2 (b) Mn+2
(a) I, II, III (b) II only
(c) II, III (d) I only (c) Mn+3 (d) None of these.
29. Copper is very slowly oxidised on the surface in moist air, 39. ZnO shows yellow colour on heating due to :
giving a green coating. The formula of this green coating (a) d-d transition
is : (b) C-T spectra
(a) Cu2O (b) CuCO3
(c) Higher polarisation caused by Zn2+ ion
(c) Cu(CH3COO)2.Cu(OH)2 (d) CuSO4
(d) F-centres
40. Zinc (II) ion on reaction with NaOH first give a white (d) W =Ag2O X = N2 Y=AgNO3 Z= Na[Ag(S2O3)2]
precipitate which dissolves in excess of NaOH due to the
47. Which of the following ores is known as pyrolusite ?
formation of :
(a) ZnO (b) Zn(OH)2 (a) Fe2O3
(c) [Zn(OH)4]2– (d) [Zn(H2O)4]2+ (b) SnO2
41. Mercury on heating with aqua-regia gives : (c) MnO2
(a) Hg(NO3)2 (b) HgCl2 (d) PbS
(c) Hg(NO2)2 (d) Hg2Cl2
42. Gold dissolves in a aqua-regia forming : Objective Questions II
(a) Auric chloride (b) Aurous chloride [One or more than one correct option]
(c) Chloroauric acid (d) Aurous nitrate 48. Choose correct statement(s) regarding the following
reaction.
43. KMnO4 oxidizes thiosulphate to SO 24  as per reaction
Cr2 O 72  (aq)  3SO 32  (aq)  8H  

xMnO 4  3S2 O32   H 2 O  xMnO 2  6SO 42   2OH  2Cr 3  (aq)  3SO 24  (aq)  4H 2 O
Find the value of x in above reaction (a) Cr2 O 72  is oxidising agent
(a) 8 (b) 4
(b) SO 32  is reducing agent
(c) 2 (d) 1
44. Mercury is the only metal which is liquid at 0ºC. This is (c) The oxidation number per ‘S’ atom in 3SO 32  is
due to its : increase by two
(a) Very high ionisation energy and weak metallic bond
(d) The oxidation number per ‘Cr’ atom in Cr2 O 72  is
(b) Low ionisation potential decreased by three
(c) High atomic weight 49. An element of 3d-transition series shown two oxidation
(d) High vapour pressure states x and y, differ by two units then:
45. Give the correct order of initials T or F for following (a) compounds in oxidation state x are ionic if x > y
statements. Use T if statement is true and F if it is false.
(b) compounds in oxidation state x are ionic if x < y
(I) Sulphide ions reacts with Na2 [Fe(CN)5(NO)] to form a
(c) compounds in oxidation state y are covalent if x < y
purple coloured compound Na4 [Fe(CN)5 (NOS)]. In the
reaction, the oxidation state of iron changes . (d) compounds in oxidation state y are covalent if y < x
(II) Pt(IV) compounds are relatively more stable than 50. Which statements about mercury are correct?
Ni(IV) compounds (a) Hg is a liquid metal
(III)The welding of magnesium can be done in the (b) Hg forms two series of salts
atmosphere of Helium (c) Hg forms no amalgam with iron and platinum
(IV) LiAlH4 on hydrolysis will give H2 (d) Anhydrous Hg does not show variable valency
(a) FFTT (b) FTTT 51. Identify the correct statements :
(c) TFTF (d) TFTT (a) Iron belongs to first transition series of the periodic
46. 
AgNO 3   (W )  (X)  O 2 table
(b) The purest form of commerical iron is wrought iron
(X)  H 2 O 
 HNO2  HNO3 (c) Anhydrous ferrous sulphate is called as yellow vitriol
(d) Iron is the most abundant transition metal
(W)  HNO 3 
 Y  NO  H 2 O
52. The metal oxide which decomposes on heating is/are :
(Y)  Na 2 S 2 O 3 (excess) 
 (Z)  NaNO 3 (a) ZnO
Identify (W) to (Z). (b) Al2O3
(a) W = Ag X = N2O Y = AgNO3 Z = Na2[Ag(S2O3)2] (c) Ag2O
(d) HgO
(b) W = Ag2O X= NO Y=AgNO3 Z = Na3[Ag(S2O3)2]
(c) W = Ag X = NO2 Y=AgNO3 Z = Na3[Ag(S2O3)2]
53. Pick out the correct statement(s) : 58. Assertion : KMnO4 has different equivalent weights in
(a) MnO2 dissolves in conc. HCl, but does not form Mn4+ acid, neutral or alkaline medium.
ions Reason : In different medium, change in oxidation number
(b) Decomposition of acidic KMnO4 is not catalysed by shown by manganese is altogether different.
sunlight (a) A (b) B
(c) MnO 24  is strongly oxidising and stable only in very (c) C (d) D
strong alkali. In dilute alkali, water or acidic solutions 59. Assertion : KMnO4 is purple in colour due to charge
it disproportionates transfer.
(d) KMnO4 does not act as oxidising agent in alkaline Reason : There is no electron present in d-orbitals of
medium manganese in MnO 4 .
54. To an acidified dichromate solution, a pinch of Na2O2 is
added and shaken. What is observed? (a) A (b) B
(a) Blue colour (c) C (d) D
(b) Orange colour changing to green 60. Assertion : AgNO3 reacts with KCN to form white ppt. of
AgCN. This white ppt. disappears when excess KCN is
(c) Evolution of oxygen
added.
(d) Bluish-green precipitate
Reason : AgCN decomposes to form silver-carbide and
evolve N2 gas.
Assertion Reason (a) A (b) B
(A) If both assertion and reason are correct and (c) C (d) D
reason is the correct explanation of assertion. 61. Assertion : CrO3 reacts with HCl to form chromyl chloride
gas.
(B) If both assertion and reason are true but Reason : Chromyl chloride (CrO2Cl2) has tetrahedral shape.
reason is not the correct explanation of (a) A (b) B
assertion. (c) C (d) D
(C) If assertion is true but reason is false. 62. Assertion : Zn gives H2 gas with dil. HCl and also with dil.
H2SO4.
(D) If assertion is false but reason is true.
Reason : NO3 ion is reduced in preference to hydronium
55. Assertion : Melting point of Mn is more than that of Fe.
ion.
Reason : Mn has higher number of unpaired e– than Fe in
atomic state. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 63. Assertion : Zn(OH)2 is dissolved in both NH4OH and
NaOH solution.
56. Assertion : CuSO4.5H2O and FeSO4.7H2O are blue and
green colour compounds respectively. Reason : Both NaOH and NH4OH being basic can dissolve
amphoteric Zn(OH)2.
Reason : Both compounds have their specific colour due
to phenomenon of polarisation of anion. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 64. Assertion : Cu is more stable than Cu+.
2+
57. Assertion : Cu+ is less stable than Cu2+ but Fe3+ is more Reason : Electrode potential is more important in
stable than Fe2+. determining stable oxidation state than electronic
configuration.
Reason : Half filled and completely filled subshells are
more stable. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D
Paragraph Type Questions Use the following passage, to solve Q. 68 to Q. 70
Use the following passage, to solve Q. 65 to Q. 67 Passage
Passage A white substance ‘X’ when heated in a test tube, it pro-
A certain metal (X) is boiled in dilute HNO3 to give a salt duces a colourless, odourless gas, leaving a residue,
(Y) and an oxide of nitrogen (Z). An aqueous solution of yellow when hot and white when cold. The residue was
(Y) with brine solution gives a white precipitate (P). When dissolved in dil. HCl, made alkaline with NH4Cl and NH4OH
(Y) was treated with Na2S2O3 solution a white precipitate and H2S gas was passed through it. A white. ppt ‘Y’ was
(Q) was obtained which on standing turns to a black com- formed. It was dissolved in dil. HCl to give ‘Z’ which on
pound (R). treatment with K4[Fe(CN)6] gave bluish white precipitate.
65. Salt (Y) and the oxide of nitrogen (Z) is 68. ‘X’ is
(a) AgNO3 + NO2 (b) AgNO3 + NO (a) ZnO (b) ZnSO4 . 7H2O
(c) AgNO3 + N2 (d) AgNO3 + NH3 (c) Cu2Cl2 (d) ZnCO3
66. The precipitate (Q) formed is 69. ‘Y’ and ‘Z’ are respectively
(a) Ag2S (b) Ag2S2O3 (a) ZnO, ZnSO4 (b) ZnS, ZnCl2
(c) Ag2O (d) Ag2SO3 (c) ZnCl2 Zn(OH)2 (d) ZnO, ZnS
67. The compound (R) formed is 70. Bluish white precipitate formed is
(a) Ag2O (b) Ag (a) Zn2[Fe(CN)6] (b) K2[Zn(CN)4]
(c) Ag2S (d) Ag2SO3 (c) Zn3[Fe(CN)6]2 (d) None of these

Objective Questions I [Only one correct option]
8. Which of the following will not be oxidised by O3 ?
1. Amongst the following, identify the species with an atom
in +6 oxidation state (2000) (2005)
(a) KI (b) FeSO4
(a) MnO4 (b) Cr(CN)36
(c) KMnO4 (d) K2MnO4
(c) NiF62- (d) CrO2Cl2 9. Native silver metal forms a water soluble complex with a
dilute aqueous solution of NaCN in the presence of
2. In the process of extraction of gold.
(2008)
O2 (a) nitrogen (b) oxygen
Roasted gold ore + CN– + H2O  [X] + OH–
(c) carbon dioxide (d) argon
[X] + Zn 
 [Y] + Au
10. Among the following, the coloured compound is
Identify the complexes [X] and [Y] (2003) (2008)
(a) X = [Au(CN)2]–, Y = [Zn(CN)4]2– (a) CuCl (b) K3[Cu(CN)4]
(b) X = [Au(CN)4]3–, Y = [Zn(CN)6]4– (c) CuF2 (d) [Cu(CH3CN)4]BF4
(c) X = [Au(CN)2]–, Y = [Zn(CN)6]4– 11. The colour of light abosrbed by an aqueous solution of
(d) X = [Au(CN)4]–, Y = [Zn(CN)4]2– CuSO4 is (2011)
3. When MnO2 is fused with KOH, a coloured compound is (a) orange-red (b) blue-green
formed, the product and its colour is (2003)
(c) yellow (d) violet
(a) K2MnO4, purple green (b) KMnO4, purple
12. Which of the following combination will produce H2 gas?
(c) Mn2O3, brown (d) Mn3O4, black (2018)
4. (NH4)2Cr2O7 on heating gives a gas which is also given by (a) Fe metal and conc. HNO3
(2004)
(b) Cu metal and conc. HNO3
(a) heating NH4NO2 (b) heating NH4NO3
(c) Au metal and NaCN (aq) in the presence of air
(c) Mg3N2 + H2O (d) Na(comp.) + H2O2
(d) Zn metal and NaOH (aq)
5. The pair of compounds having metals in their highest
oxidation state is (2004)
(a) MnO2, FeCl3 (b) [MnO4]–, CrO2Cl2
(c) [Fe(CN)6]3–, [Co(CN)3] (d) [NiCl4]2–, [CoCl4]–
13. The correct statement(s) about Cr2+ and Mn3+ is (are)
6. When I– is oxidised by MnO4– in alkaline medium, I– [Atomic numbers of Cr = 24 and Mn = 25] (2015)
converts into (2004) (a) Cr2+ is a reducing agent
(a) IO3– (b) I2 (b) Mn3+ is an oxidizing agent

(c) Both Cr2+ and Mn3+ exhibit d4 electronic configuration
(c) IO –
4
(d) IO– (d) When Cr2+ is used as a reducing agent, the chromium
7. Which of the following pair is expected to exhibit same ion attains d5 electronic configuration
colour in solution ? (2005)
(a) VOCl2 ; FeCl2 (b) CuCl2 ; VOCl2
(c) MnCl2 ; FeCl2 (d) FeCl2 ; CuCl2
14. Fe3+ is reduced to Fe2+ by using (2015) Numerical Value Type Questions
(a) H2O2 in presence of NaOH
(b) Na2O2 in water 18. Consider the following list of reagents:
Acidified K2Cr2O7, alkaline KMnO4, CuSO4, H2O2, Cl2, O3,
(c) H2O2 in presence of H2SO4 FeCl3, HNO3 and Na2S2O3. The total number of reagents
(d) Na2O2 in presence of H2SO4 that can oxidise aqueous iodide to iodine is
15. Fusion of MnO2, with KOH in presence of O2 produces a (2014)
salt W. Alkaline solution of W upon electrolytic 19. In neutral or faintly alkaline solution, 8 moles of
oxidation yields another salt X. The manganese permanganate anion quantitatively oxidize thiosulphate
containing ions present in W and X, respectively are Y anions to produce X moles of a sulphur containing product.
and Z. Correct statement(s) is (are) The magnitude of X is (2016)
(2019) 20. Among the species given below, the total number of
(a) In both Y and Z,  -bonding occurs between p diamagnetic species is ___.
orbitals of oxygen and d-orbitals of manganese
H atom, NO2 monomer, O2 (superoxide), dimeric sulphur
(b) Both Y and Z are coloured and have tetrahedral
shape in vapour phase, Mn3O4, (NH4)2[FeCl4], (NH4)2[NiCl4],
(c) In aqueous acidic solution, Y undergoes K2MnO4, K2CrO4 (2018)
disproportionation reaction to give Z and MnO2 21. To measure the quantity of MnCl2 dissolved in an aqueous
(d) Y is diamagnetic in nature while Z is paramagnetic solution, it was completely converted to KMnO4 using the
16. Consider the following reaction (unbalanced) reaction.
MnCl2 + K2S2O8 + H2O  KMnO4 + H2SO4 + HCl
Zn + hot conc. H2SO4 G + R + X
(equation not balanced).
Zn + conc. NaOH  T + Q
Few drops of concentrated HCl were added to this solution
G + H2S + NH4OH  Z (a precipitate) + X + Y and gently warmed. Further, oxalic acid (225 mg) was added
Choose the correct option(s) (2019) in portions till the colour of the permanganate ion
(a) Bond order of Q is 1 in its ground state disappeared. The quantity of MnCl2 (in mg) present in the
initial solution is ____.
(b) The oxidation state of Zn in T is +1.
(Atomic weights in g mol–1: Mn = 55, Cl = 35.5)
(c) R is a V-shaped molecule
(2018)
(d) Z is dirty white in colour
22. An acidified solution of potassium chromate was layered
17. A mixture of two salts is used to prepare a solution S, which with an equal volume of amyl alcohol. When it was shaken
gives the following results: (2021) after the addition of 1 mL of 3% H2O2, a blue alcohol layer
was obtained. The blue color is due to the formation of
S Dilute HCl
 White ppt only a chromium (VI) compound ‘X’. What is the number of
 aq solution
of thesalt  Room temperature
oxygen atoms bonded to chromium through only single
S Dilute NaOH
 White ppt only bonds in a molecule of X? (2020)
 aq solution
of thesalt  Room temperature

(a) Pb(NO3)2 and Zn(NO3)2 23.
(b) Pb(NO3)2 and Bi(NO3)3
(B) Moist air
 MCl 4
Zn
 A
(c) AgNO3 and Bi(NO3)3 white fumes  M=Transition   purple colour 
with pungent smell  element colourless 
 
(d) Pb(NO3)2 and Hg(NO3)2
Identify the metal M and hence MCl4. Explain the difference
in colours of MCl4 and A. (2005)
Use the following passage, to solve Q. 24 to Q. 25 25. Among the following, the brown ring is due to the forma-
tion of (2021)
Passage 2 3
The reaction of K3[Fe(CN)6] with freshly prepared FeSO4 (a)  Fe  NO 2 SO 4  2  (b)  Fe  NO 2  H 2 O 4 
solution produces a dark blue precipitate called Turnbull's 2
blue. Reaction of K4 [Fe(CN)6] with the FeSO4 solution in (c)  Fe  NO 4  SO 4  2  (d)  Fe  NO  H 2 O 5 
complete absence of air produces a white precipitate X, 26. In the scheme given below, X and Y, respectively, are
which turns blue in air. Mixing the FeSO4 solution with
Metal halide 
aq.NaOH
 White precipitate (P) + Filtrate
NaNO3, followed by a slow addition of concentrated H2SO4
through the side of the test tube produces a brown ring. (Q) (2023)
aq.H 2 SO 4 PbO 2  excess 
P  heat
 X (a coloured species in solution)
24. Precipitate X is (2021)
 2
MnO OH Conc.H SO
Q  Y (gives blue-coloration with KI-
(a) Fe 4  Fe  CN 6  3
2 4
(b) Fe  Fe  CN 6  warm
starch paper)
(c) K 2 Fe  Fe  CN 6  (d) KFe  Fe  CN 6  (a) CrO42– and Br2 (b) MnO42– and Cl2
–
(c) MnO4 and Cl2 (d) MnSO4 and HOCl
27. H2S (5 moles) reacts completely with acidified aqueous
potassium permanganate solution. In this reaction, the
number of moles of water produced is x, and the number of
moles of electrons involved is y. The value of (x + y) is
____. (2023)
d AND f BLOCK ELEMENTS

ANSWER KEY 234
Answer Key
CHAPTER -6 CARBOXYLIC ACID AND ITS DERIVATIVES
EXERCISE - 1 :
BASIC LEVEL OBJECTIVE QUESTIONS
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
1. (d) 2. (b) 3. (c) 4. (c) 5. (c) 6. (a) 7. (d) 8. (c)
9. (b) 10. (a) 11. (a) 12. (a) 13. (c) 14. (c) 15. (d) 16. (c)
17. (c) 18. (c) 19. (a) 20. (c) 21. (c) 22. (c) 23. (c) 24. (a)
25. (b) 26. (b) 27. (d) 28. (d) 29. (c) 30. (b) 31. (a) 32. (c)
33. (c) 34. (b) 35. (a) 36. (d) 37. (c) 38. (b) 39. (b) 40. (c)
41. (a) 42. (b) 43. (b) 44. (a) 45. (d) 46. (c) 47. (b) 48. (d)
49. (b) 50. (a) 51. (c) 52. (d) 53. (a) 54. (b) 55. (b) 56. (c)
57. (c) 58. (c) 59. (a) 60. (c) 61. (d) 62. (c) 63. (d) 64. (a)
65. (d)
ANSWER KEY 235

EXERCISE - 2 : EXERCISE - 3 :
PREVIOUS YEAR JEE MAINS QUESTION ADVANCED OBJECTIVE QUESTIONS
DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.
1. (c) 2. (b) 3. (d) 4. (c) 5. (d) 1. (b) 2. (b) 3. (d) 4. (c) 5. (a)
6. (d) 7. (c) 8. (a) 9. (c) 10. (c) 6. (d) 7. (d) 8. (a) 9. (a) 10. (c)
11. (a) 12. (a) 13. (b) 14. (a) 15. (d)
11. (d) 12. (b) 13. (1.00) 14. (3.00) 15. (a) 16. (c) 17. (b) 18. (c) 19. (d) 20. (a)
16. (a) 17. (c) 18. (c) 19. (c) 20. 2 21. (a) 22. (d) 23. (c) 24. (c) 25. (d)
21. (a) 22. (d) 23. (d) 24. (a) 25. (c) 26. (d) 27. (a) 28. (a) 29. (d) 30. (a)
31. (b) 32. (a,b,c) 33. (a, d) 34. (c, d)
26. (a) 27. (a) 28. (d) 29. (d) 30. (c) 35. (a, d) 36. (a,c,d) 37. (d) 38. (c)
31. (d) 32. (d) 33. (c) 34. 3 39. (a) 40. (c) 41. (a) 42. (a) 43. (a)
44. (a) 45. (c)
ANSWER KEY 236

EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS
DIRECTION TO USE -
1. (c) 2. (b) 3. (a) 4. (a) 6. (b)

7. (d) 8. (c) 9. (a) 10. (c) 11. (18.00)
12. (d) 13. (a) 14. (b) 21. (b,c,d) 22. (a,b,c)
23. (b) 24. (c,d)
ANSWER KEY 237
CHAPTER -07 AMINES

BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

1. (b) 2. (b) 3. (d) 4. (d) 5. (d) 1. (c) 2. (c) 3. (c) 4. (c) 5. (b)
6. (d) 7. (a) 8. (a) 9. (c) 10. (b) 6. (b) 7. (b) 8. (c) 9. (d) 10. (d)
11. (c) 12. (b) 13. (b) 14. (d) 15. (a) 11. (d) 12. (c) 13. (c) 14. (b) 15. (a)
16. (d) 17. (b) 18. (c) 19. (c) 20. (c) 16. (c) 17. (c) 18. (c) 19. (c) 20. (d)
21. (d) 22. (d) 23. (d) 24. (b) 25. (c) 21. (c) 22. (a) 23. (c) 24. (c) 25. (b)
26. (a) 27. (c) 28. (d) 29. (a) 30. (b) 26. (a) 27. (b) 28. (d) 29. (d) 30. (c)
31. (b) 32. (b) 33. (b) 34. (a) 35. (b) 31. (b) 32. (d) 33. (c) 34. (a) 35. (a)
36. (c) 37. (d) 38. (a) 39. (d) 40. (d) 36. (b) 37. (a) 38. (b) 39. (a) 40. (d)
41. (a) 42. (a) 43. (a) 44. (b) 45. (d) 41. (d) 42. (3.00)43. (243.00)
46. (c) 47. (c) 48. (a) 49. (c) 50. (b) 44. (108.00) 45. (5.00)
51. (d) 52. (c) 53. (b) 54. (d) 55. (a) 46. (a) 47. (c) 48. (c) 49. (c) 50. (d)
56. (b) 57. (c) 58. (c) 59. (c) 60. (c) 51. (d) 52. (c) 53. (b) 54. (c) 55. (c)
61. (b) 62. (a) 63. (b) 64. (a) 65. (b) 56. (d) 57. (c) 58. (c) 59. (b) 60. (c)
66. (a) 67. (c) 68. (c) 69. (b) 70. (d) 61. (d) 62. (a) 63. (a) 64. (a) 65. (c)
71. (c) 72. (b) 73. (d) 74. (b) 75. (d) 66. (c) 67. (b) 68. (c) 69. (d) 70. (c)
76. (b) 77. (c) 78. (a) 79. (d) 80. (a) 71. (d) 72. (d) 73. (d) 74. (b) 75. (d)
81. (c) 82. (c) 83. (d) 84. (a) 85. (a) 76. (b) 77. (c) 78. (d) 79. (a) 80. (d)
81. (b) 82. (b) 83. (62250) 84. (6)
ANSWER KEY 238
CHAPTER -07 AMINES


1. (c) 2. (d) 3. (b) 4. (d) 5. (c) 1. (b) 2. (c) 3. (b) 4. (a,b,d) 5. (c,d)
6. (c) 7. (d) 8. (c) 9. (b) 10. (a) 6. (4.00) 7. (18.6gm)
11. (a) 12. (b) 13. (a) 14. (c) 15. (d) 8. (1.23) 9. (d)
16. (c) 17. (a) 18. (d) 19. (c) 20. (b) 10. (a) 13. (b) 16. (28) 17. 1791
21. (c) 22. (b) 23. (c) 24. (b) 25. (c) 18. (9) 19. (51)
26. (a) 27. (b)
28. (a,b,c) 29. (a,b,c) 30. (b,c,d)
31. (c,d) 32. (a,c,d) 33. (b,d)
34. (a,b,c,d) 35. (b,d) 36. (a,b,c)
37. (b,c,d) 38. (a,c) 39. (a,b,c)
40. (b,c,d) 41. (a) 42. (a)
43. (c) 44. (a) 45. (d)
46. (d) 47. (c) 48. (d)
49. (A-p,s; B-p,s; C-r; D-p,q,s)
ANSWER KEY 239
CHAPTER -8 BIOMOLECULES
BASIC LEVEL OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTION

1. (d) 2. (a) 3. (a) 4. (d) 5. (b) 1. (c) 2. (a) 3. (b) 4. (c) 5. (d)
6. (c) 7. (d) 8. (d) 9. (a) 10. (a) 6. (d) 7. (d) 8. (b) 9. (b) 10. (a)
11. (b) 12. (b) 13. (d) 14. (b) 15. (b) 11. (a) 12. (d) 13. (a) 14. (d) 15. (b)
16. (d) 17. (c) 18. (c) 19. (b) 20. (b) 16. (c) 17. (d) 18. (c) 19. (c) 20. (c)
21. (d) 22. (d) 23. (d) 24. (b) 25. (d) 21. (d) 22. (b) 23. (d) 24. (a) 25. (b)
26. (b) 27. (c) 28. (a) 29. (d) 30. (d) 26. (b) 27. (b) 28. (d) 29. (c) 30. (a)
31. (d) 32. (a) 33. (d) 34. (b) 35. (c) 31. (b) 32. (b) 33. (b) 34. (c) 35. (a)
36. (a) 37. (b) 38. (a) 39. (d) 40. (b) 36. (b) 37. (a) 38. (c) 39. (a) 40. (d)
41. (c) 42. (c) 43. (c) 44. (c) 45. (a) 41. (a) 42. (d) 43. 4 44. 25 45. 2
46. (a) 47. (b) 48. (a) 49. (b) 50. (c) 46. 9 47. 145 48. (d) 49. (d) 50. (b)
51. (b) 52. (c) 53. (c) 54. (a) 55. (b) 51. (b) 52. (c) 53. (a) 54. (b) 55. (c)
56. (b) 57. (d) 58. (d) 59. (c) 60. (c) 56. (a) 57. (d) 58. (a) 59. (c) 60. (c)
61. (a) 62. (c) 63. (b) 64. (c) 65. (d) 61. (c) 62. (a) 63. (b) 64. (d) 65. (b)
66. (c) 67. (c) 68. (d) 69. (b) 70. (b) 66. (d) 67. (d) 68. (25) 69. (8) 70. (6)
71. (c) 72. (b) 73. (a) 74. (c) 75. (c) 71. (2) 72. (10.00)
76. (c) 77. (b) 78. (b) 79. (d) 80. (b)
ANSWER KEY 240
CHAPTER -8 BIOMOLECULES
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTION

1. (a) 2. (d) 3. (d) 4. (c) 5. (c) 1. (b) 2. (a) 3. (c) 4. (a) 5. (b,c)
6. (d) 7. (b) 8. (b) 9. (a) 10. (c) 6. (a,b,c,d) 7. (c,d) 8. (5.00) 9. (c)
11. (b) 12. (d) 13. (d) 14. (d) 15. (a) 16. (c) 17. (a)
16. (b) 17. (b) 18. (b) 19. (a) 20. (b)
21. (c) 22. (a) 23. (b) 24. (c) 25. (d)
26. (a,b,c) 27. (c,d) 28. (a,b,c)
29. (a,b,d) 30. (a,b,c) 31. (5.00)
32. (3.00)33. (8000)34. (10.00) 35. (a)
36. (d) 37. (a) 38. (c) 39. (d) 40. (a)
41. (c) 42. (a) 43. (b) 44. (a) 45. (a)
46. (a) 47. (b) 48. (a) 49. (c) 50. (b)
51. (c) 52. (d) 53. (a) 54. (a) 55. (c)
56. (c) 57. (a) 58. (b) 59. (b) 60. (d)
61. (a) 62. (b) 63. (c) 64. (d) 65. (c)
66. (c) 67. (b) 68. (c) 69. (c) 70. (d)
ANSWER KEY 241
CHAPTER -9 p -BLOCK ELEMENTS (GROUP 15-18)

1. (c) 2. (a) 3. (c) 4. (c) 5. (b) 1. (a) 2. (d) 3. (b) 4. (d) 5. (a)
6. (a) 7. (a) 8. (a) 9. (b) 10. (d) 6. (a) 7. (b) 8. (d) 9. (b) 10. (d)
11. (a) 12. (a) 13. (c) 14. (c) 15. (b) 11. (d) 12. (d) 13. (d) 14. (b) 15. (a)
16. (c) 17. (a) 18. (c) 19. (c) 20. (d) 16. (1.00) 17. (1.00) 18. (19.00) 19. (3.00) 20. (3.00)
21. (a) 22. (d) 23. (c) 24. (d) 25. (c) 21. (c) 22. (d) 23. (b) 24. (a) 25. (a)
26. (a) 27. (b) 28. (a) 29. (c) 30. (d) 26. (a) 27. (b) 28. (b) 29. (c) 30. (b)
31. (c) 32. (b) 33. (c) 34. (a) 35. (d) 31. (a) 32. (d) 33. (b) 34. (d) 35. (c)
36. (a) 37. (a) 38. (d) 39. (c) 40. (b) 36. (a) 37. (b) 38. (b) 39. (d) 40. (b)
41. (c) 42. (c) 43. (a) 44. (d) 45. (c) 41. (d) 42. (c) 43. (c) 44. (c) 45. 2
46. (a) 47. (a) 48. (a) 49. (c) 50. (d) 46. 1 47. (b) 48. (b) 49. (c) 50. (a)
51. (d) 52. (a) 53. (a) 54. (d) 55. (a) 51. (c) 52. (d) 53. (a) 54. (a) 55. (b)
56. (c) 57. (d) 58. (d) 59. (a) 60. (b)
56. (b) 57. (b) 58. (a) 59. (b) 60. (a) 61. (b) 62. (8) 63. (4) 64. (4) 65. (12)
61. (d) 62. (a) 63. (d) 64. (b) 65. (a) 66. (11) 67. (6) 68. (4) 69. (5) 70. (1)
66. (b) 67. (c) 68. (d) 69. (c) 70. (d) 71. (2)
71. (a) 72. (a) 73. (c) 74. (c) 75. (c)
76. (d) 77. (b) 78. (c) 79. (c) 80. (b)
81. (d) 82. (d) 83. (d) 84. (c) 85. (c)
86. (c) 87. (b) 88. (d) 89. (a) 90. (c)
91. (b) 92. (a) 93. (b) 94. (a) 95. (b)
96. (a) 97. (b) 98. (d) 99. (b) 100. (a)
101. (d) 102. (a) 103. (a) 104. (d) 105. (b)
106. (a) 107. (a) 108. (c) 109. (c) 110. (b)
111. (d) 112. (c) 113. (c) 114. (a)
ANSWER KEY 242
CHAPTER -9 p -BLOCK ELEMENTS (GROUP 15-18)
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE -
DIRECTION TO USE -
1. (d) 2. (c) 3. (b) 4. (d) 5. (a) 1. (c) 2. (a) 3. (a) 4. (d) 5. (c)
6. (c) 7. (b) 8. (d) 9. (b) 10. (b) 6. (a) 7. (b) 8. (c) 9. (b) 10. (b)
11. (b) 12. (c) 13. (d) 14. (a) 15. (a) 11. (c) 12. (d) 13. (b) 14. (b) 15. (d)
16. (b) 17. (a) 18. (d) 19. (c) 20. (a) 16. (a) 17. (b) 18. (a,b,c)19. (b,c) 20. (b,d)
21. (a) 22. (d) 23. (d) 24. (a) 25. (c) 21. (a,c,d) 22. (a,d) 24.(a,b,c) 25. (a,b,d) 26. (5.00)
26. (c) 27. (b) 28. (b) 29. (c) 30. (b)
27. (4.00) 28. (6.00) 29. (6.00) 30. (a) 31. (c)
31. (b) 32. (b) 33. (b) 34. (d) 35. (a)
32. (a) 33. (c) 34. (c) 35. (b) 36. (2.38)
36. (a) 37. (d) 38. (a) 39. (a) 40. (b)
37. (a,d) 38. (2) 39. (c) 40. (d) 41. (6)
41. (A - r, B - p,s, C - q)
42. (A - p,r, B - p,s, C - q,r, D - q,r, E - q)
43. (A - p,q, B - p,s, C - r, D - r,s)
44. (white) 45. (6.00)
ANSWER KEY 243
CHAPTER -10 d AND f BLOCK ELEMENTS

1. (d) 2. (d) 3. (c) 4. (a) 5. (c) 1. (d) 2. (c) 3. (c) 4. (c) 5. (a)
6. (d) 7. (d) 8. (c) 9. (d) 10. (a) 6. (c) 7. (a) 8. (b) 9. (d) 10. (d)
11. (a) 12. (a) 13. (b) 14. (d) 15. (d) 11. (b) 12. (b) 13. (c) 14. (b) 15. (a)
16. (c) 17. (b) 18. (c) 19. (a) 20. (a) 16. (b) 17. (6.00) 18. (4.9) 19. (10.00) 20. (7.00)
21. (b) 22. (b) 23. (b) 24. (b) 25. (d) 21. (18.00) 22. (b) 23. (b) 24. (b)
26. (a) 27. (d) 28. (d) 29. (d) 30. (b)
25. (b) 26. (b) 27. (a) 28. (b) 29. (a)
31. (b) 32. (d) 33. (c) 34. (c) 35. (a) 30. (c) 31. (c) 32. (c) 33. (a) 34. (a)
36. (b) 37. (d) 38. (d) 39. (c) 40. (b) 35. (a) 36. (d) 37. (b) 38. (c) 39. (d)
41. (b) 42. (a) 43. (c) 44. (b) 45. (c) 40. (d) 41. (a) 42. (b) 43. 3 44. 0
46. (c) 47. (c) 48. (a) 49. (a) 50. (a) 45. 3 46. 3 47. 6 48. 6 49. 0
50. 5 51. 4 52. 5 53. 2 54. 4
51. (d) 52. (c) 53. (c) 54. (c) 55. (b)
55. (c) 56. (d) 57. (d) 58. (d) 59. (b)
56. (d) 57. (d) 58. (a) 59. (a) 60. (c)
60. (b) 61. (d) 62. (a) 63. (a) 64. (b)
61. (d) 62. (b) 63. (a) 64. (a) 65. (c) 65. (a) 66. (c) 67. (a) 68. (a) 69. (a)
66. (d) 67. (d) 68. (a) 69. (c) 70. (b) 70. (d) 71. (d) 72. (c) 73. (d) 74. (a)
71. (a) 72. (c) 73. (d) 74. (a) 75. (a) 75. (b) 76. (c) 77. (b) 78. (2.00) 79. (3.00)
76. (b) 77. (a) 78. (a) 79. (a) 80. (d)
81. (d) 82. (d) 83. (a) 84. (d) 85. (a)
86. (c) 87. (a) 88. (d) 89. (c) 90. (b)
91. (d) 92. (d) 93. (d) 94. (b) 95. (a)
96. (b) 97. (d) 98. (c) 99. (d) 100. (a)
ANSWER KEY 244
CHAPTER -10 d AND f BLOCK ELEMENTS
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

1. (a) 2. (c) 3. (b) 4. (a) 5. (c) 1. (d) 2. (a) 3. (a) 4. (a) 5. (b)
6. (b) 7. (d) 8. (b) 9. (a) 10. (b) 6. (a) 7. (b) 8. (c) 9. (b) 10. (c)
11. (a) 12. (c) 13. (d) 14. (b) 15. (c) 11. (a) 12. (d) 13. (a,b,c)14. (c,d) 15. (a,b,c)
16. (d) 17. (a) 18. (d) 19. (d) 20. (c) 16. (a,c,d)17. (a,b) 18. (7.00) 19. (6.00) 20. (1.00)
21. (c) 22. (b) 23. (c) 24. (c) 25. (b) 21. (126.00) 22. (4.00) 24.(c) 25. (d) 26. (c)
26. (a) 27. (a) 28. (c) 29. (c) 30. (a)
27. (18.00)
31. (c) 32. (c) 33. (c) 34. (d) 35. (b)
36. (b) 37. (b) 38. (a) 39. (d) 40. (c)
41. (b) 42. (c) 43. (a) 44. (a) 45. (b)
46. (c) 47. (c) 48. (a,b,c,d) 49. (b,c)
50. (a,b,c,d) 51. (a,b,d) 52. (c,d)
53. (a,c) 54. (a,b,c)55. (d) 56. (c) 57. (b)
58. (a) 59. (b) 60. (b) 61. (b) 62. (b)
63. (a) 64. (a) 65. (b) 66. (b) 67. (c)
68. (d) 69. (b) 70. (a)

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Vedantu’s

Vedantu’s Tatva Practice

CARBOXYLIC ACID AND ITS DERIVATIVES

Exercise - 1 : Basic Objective Questions.......................................................................................................................... 25

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 30

Exercise - 1 : Basic Objective Questions.......................................................................................................................... 60

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 69

Exercise - 1 : Basic Objective Questions.......................................................................................................................... 113

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 118

P -BLOCK ELEMENTS (GROUP 15-18)

Theory ............................................................................................................................................................................................... 141

Exercise - 1 : Basic Objective Questions.......................................................................................................................... 174

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 182

D AND F BLOCK ELEMENTS

Theory ............................................................................................................................................................................................... 194

Exercise - 1 : Basic Objective Questions.......................................................................................................................... 213

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................................... 220

CARBOXYLIC ACID AND ITS DERIVATIVES

1. INTRODUCTION Important Aromatic Adds

Structure of carboxylic acid group

CH 3 COOH Acetic Acid

CH 3COCOOH Pyruvic Acid

The high boiling points of carboxylic acids result from formation

Hydrogen-bonded Acid Dimer

Resonating structures of carboxylate ion 3.2.2 Oxidation

1. In oxidative cleavage, each C of multiple bond becomes the

3.2.3 Koch Reaction - Hydrocarbonylation

Number of carbons is one more than parent alkene.

 Mild Oxidising Agents: MnO, CuO (Fehling’s Solution),

3.6 Aldehydes and Ketones

Keto group (with C*) remains with smaller alkyl group.

Methyl ketone on treatment with X 2 / OH  gives carboxylate

For conversion to carboxylic group, presence of  -hydrogen is

3.8.2 Kolbe - Schmidt Reaction

4.1.3 Reaction with Carbonates & Bicarbonates

2CH 3 COOH + Na 2 CO3  2CH 3 COONa+CO 2 +H 2 O

4.2 Nucleophilic Acyl Substitution

Hydroxy acids undergo intramolecular esterification and makes

Gem dicarboxylic acids decarboxylate simply on heating.

Reducing Agents: LiA1H 4 in ether solution or with H2 in

CH3 CH2 CH2COOH  

β -unsaturated acids decarboxylate on heating giving alkenes.

4.4.3 Kolbe’s Synthesis  1 : 1 ratio of salt and I 2 - RI is formed

Electrolysis of salt of succinic acid and its derivative give alkene.

4.4.7 Hell-Volhard Zelinsky Reaction

Acid is regenerated by the action of H 2SO 4 .

5.1.2 Chemical Properties

With 3% H2O2 , they are oxidised to β -hydroxy acids.

(D) Action of Heat on Formates

5.1.3 Tests for HCOOH

1. In lab preparation of CO. 3 Neutral CH3COOH 

2. Textile dyeing and finishing.

In free state it is found in fermented fruit juices and in bound

5.3.2 Reactions of Benzoic Acid

5.3.3 Uses of Benzoic Acid

6. CARBOXYLIC ACIDS DERIVATIVES

Step 2 : Loss of Leaving Group

Leaving groups L: Cl , NH 2 , RO, RCOO (C) Conversion to Anhydrides

Cl   RCOO   OH   RO   NH 2  (D) Conversion to Alcohols

RCOCl>  RCO 2 O>RCOOH>RCOOR>RCONH 2