Tatva Practice Book

Chemistry
CLASS 12 NEET

Carboxylic Acids and Derivatives Amines

Biomolecules p -block Elements (group 15-18) d and f Block Elements

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MASTER INDEX
VOLUME 1:
Solutions
General Organic Chemistry (Revision) & Isomerism
Haloalkanes and Haloarenes
Alcohols, Phenols and Ethers
Aldehydes and Ketones

VOLUME 2:
Carboxylic Acids and Derivatives
Amines
Biomolecules
p -Block Elements (group 15-18)
d and f Block Elements

VOLUME 3:
Practical Organic Chemistry
Coordination Compounds
Chemical Kinetics
Electrochemistry
TABLE OF CONTENTS

Carboxylic Acids and Derivatives

Theory........................................................................................................................................................................................ 7

Exercise - 1 : Basic Objective Questions.................................................................................................................. 26

Exercise - 2 : Previous Year Questions.................................................................................................................... 42

Exercise - 3 : Achiever’s Section ................................................................................................................................ 48

Answer Key ............................................................................................................................................................................ 234

Amines

Theory........................................................................................................................................................................................ 54

Exercise - 1 : Basic Objective Questions.................................................................................................................. 71

Exercise - 2 : Previous Year Questions.................................................................................................................... 87

Exercise - 3 : Achiever’s Section ................................................................................................................................ 93

Answer Key ............................................................................................................................................................................ 236

Biomolecules

Theory........................................................................................................................................................................................ 98

Exercise - 1 : Basic Objective Questions.................................................................................................................. 119

Exercise - 2 : Previous Year Questions.................................................................................................................... 132

Exercise - 3 : Achiever’s Section ................................................................................................................................ 136

Answer Key ............................................................................................................................................................................ 238

p -Block Elements (group 15-18)

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

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

Exercise - 2 : Previous Year Questions.................................................................................................................... 184

Exercise - 3 : Achiever’s Section ................................................................................................................................ 188

Answer Key ............................................................................................................................................................................ 240

d and f Block Elements

Theory........................................................................................................................................................................................ 193

Exercise - 1 : Basic Objective Questions.................................................................................................................. 212

Exercise - 2 : Previous Year Questions.................................................................................................................... 226

Exercise - 3 : Achiever’s Section ................................................................................................................................ 230

Answer Key ............................................................................................................................................................................ 242

CARBOXYLIC ACID AND ITS DERIVATIVES
Chapter 06 7

Carboxylic Acid And Its Derivatives

1. Introduction Important Aromatic Acids

Carboxylic acids are the compounds containing the carboxy

functional group.

Fig. 8.1: 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.
The general formula for carboxylic acids is C n H 2n O 2 These are further classified as mono, di, tri carboxylic acids
depending upon number of carboxylic groups present in their
Carboxylic acids are used in the production of polymers,
molecules.
pharmaceuticals, solvents, and food additives. Industrially
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), ethylenediaminetetraacetic acid (chelating
HCOOH CH3COOH
agent), fatty acids (coatings), maleic acid (polymers), propionic
Formic acid Acetic acid Benzoic acid
acid (food preservatives), terephthalic acid (polymers). Esters
and fatty acids are the main components of lipids and polyamides Di Carboxylic Acids
and aminocarboxylic acids are the main components of proteins.
The carboxylic acids ionize in water to give H  ions and hence
they are acidic in nature.

Important Aliphatic Acids

HCOOH Formic Acid
CH 3 COOH Acetic Acid 2. Physical Properties And Acidic
CH 2  CHCOOH Acrylic Acid
Character
CH 3COCOOH Pyruvic Acid

2.1 Boiling Point

Fig. 8.2: Comparison of boiling points of carboxylic acid,

alcohol and aldehyde of comparable molecular
masses.

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8 CARBOXYLIC ACID AND ITS DERIVATIVES
The high boiling points of carboxylic acids result from formation Carboxylate ion exists as two equivalent canonical structures A
of a stable, hydrogen-bonded dimer. This dimer contains an eight- and B. Due to more stability of carboxylate ion, carboxylic acid is
membered ring joined by two hydrogen bonds, effectively acidic in nature because the equilibrium in reaction favors the
doubling the molecular weight of the molecules leaving the liquid formation of stable ion.
phase.
Effect of Substituents on Acidity
Electron withdrawing groups ( -I effect) stabilise the anion and
hence increase acidic nature. As the number of -I effect groups
increases, acid strength increases and vice versa.
Fig. 8.3: Hydrogen-bonded Acid Dimer

2.2 Melting Point and Physical State

Aliphatic acids upto nine carbon atoms are colourless liquids at Strength of -I group decreases with increase in distance with -
room temperature with unpleasant odours. The higher acids are COOH group.
wax-like solids and are practically odourless due to low volatility.
They exist as dimer in aprotic and non-polar solvents.
Unbranchcd acids made up of an even number of carbon atoms
have melting points higher than the odd numbered homologues
having one more or one less carbon. This oscillating behaviour
in melting point is explained by the differences in the Negative inductive effect of halogens is in order:F > Cl > Br > I
intermolecular attractive forces in the crystalline state.
Hence acid strength is

2.3 Solubility F-CH 2 COOH >Cl-CH 2 COOH >Br-CH 2 COOH >I-CH 2 COOH
Carboxylic acids form hydrogen bonds with water, and the lower- Relative acid strength is as follows :
molecular weight carboxylic acids (upto 4 carbon atoms) are RCOOH > HOH > ROH > HC  CH > NH3 > RH
miscible with water. As the length of the hydrocarbon chain
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
form hydrogen bonds with alcohols. Also, alcohols are not as
polar as water, so the longer-chain acids are more soluble in 3.1 Alkanes
alcohols than they are in water. Most carboxylic acids are quite
soluble in relatively nonpolar solvents such as chloroform because Long chain alkanes are oxidized by air at 120 C in presence of
the acid continues to exist in its dimeric form in the nonpolar catalyst manganese acetate or manganous stearate.
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
Monosubstituted alkenes give carboxylic acid on oxidative
ozonolysis.
Fig. 8.4: Resonating structures of carboxylate ion

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CARBOXYLIC ACID AND ITS DERIVATIVES 9
acid catalyst. The similar effect is observed when Ni(CO) 4 is
treated independently.

3.2.2 Oxidation
Oxidising agents used are acidified or hot alkaline KMnO 4 and
K 2 Cr2 O7 .
K Cr O /H SO
RCH  CHR ' 4  O 
2 2 7 2 4  RCOOH

 R 'COOH
Cyclic alkenes can be oxidized to dicarboxylic acids.

Number of carbons is one more than parent alkene.

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 3.3 Alkynes
group.
2. The terminal -CH 2 group of 1-Alkene is completely oxidized 3.3.1 Ozonolysis
to CO 2 and H 2 O . Alkynes on ozonolysis give carboxylic acids.

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, H2 O at high temperature and
pressure causes carbonylation. Usually, H 3 PO 4 is used as the

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10 CARBOXYLIC ACID AND ITS DERIVATIVES

3.4 Alkyl Halides 3.4.2 Hydrolysis of terminal trihalogen derivatives

of Alkanes
3.4.1 KCN + Hydrolysis

3.4.3 Grignard Reagent + CO2

NOTE :
1. In acidic medium, the products are RCOOH and
NH 4 while in alkaline hydrolysis, RCOO  and NH3 are
products.
2. The acid formed contains one more C than parent alkyl
halide. The order of reactivity of alkyl halides is
1° > 2° > 3°.
3. In case of 3° alkyl halide, elimination takes place.
4. 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 :
1. Strong Oxidizing Agents : K 2 Cr2 O 7 / H  or KMnO 4 / H  .
2. 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 used
for preparing unsaturated acids.

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CARBOXYLIC ACID AND ITS DERIVATIVES 11
3.7 Carboxylic Acid Derivatives
Acyl halide, carboxylic ester, anhydride and amide all on acidic or
basic hydrolysis give carboxylic acids.
1° amide on treatment with nitrous acid.

3.6 Aldehydes and Ketones H ,H O

2  RCOOH  R 'OH
RCOOR ' 
OH, H O
2  RCOO   NH
RCONH 2 
3.6.1 Oxidation  3

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.

3.8 Preparation of Aromatic Acids

3.8.1 Oxidation of Alkyl Benzenes

*
[O] * Alkyl side chain of benzene ring can be easily oxidized to
CH 3 C OCH 2 CH 2 CH3 
  CH 3 C OOH carboxylic group, irrespective of the length with acidic or alkaline
 CH 3 CH 2 COOH KMnO4 chromic acid or conc HNO3.

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.

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12 CARBOXYLIC ACID AND ITS DERIVATIVES
3.8.2 Kolbe - Schmidt Reaction CH 3 COONa + HCl  CH 3 COOH  NaCl
Sodium phenoxide is carboxylated by treatment of CO 2 in the
ortho-position, mostly. 4.1.3 Reaction with Carbonates & Bicarbonates
This reaction is laboratory test of carboxylic group
(-COOH) due to effervescence of CO 2 .

2CH3 COOH + Na 2 CO3  2CH 3 COONa+CO 2 +H 2 O

CH 3COOH + NaHCO3  CH 3 COONa+CO 2 +H 2 O

NOTE :
CO 2 evolves from carbonate or bicarbonate, not from acid.

4.2 Nucleophilic Acyl Substitution

Fig. 8.5: Methods of preparation of carboxylic acids 4.2.1 Formation of Esters

Conc.
4. Reactions Of Carboxylic Acids 

R  COOH  HOR '  RCOOR ' H 2 O
H2SO4

This reaction is called esterification and is catalyzed by small

4.1 Reactions as an Acid amount of inorganic acids.
In esterification C-OH bond of acid and O-H bond of alcohol
4.1.1 Reaction with Strongly Electropositive Metals breaks.
Monocarboxylic acids react with strong electropositive metals
(such as Na, K, Zn etc.) evolving hydrogen and forming
corresponding salts (acidic character).
Hydroxy acids undergo intramolecular esterification and makes
2RCOOH  Na  2RCOONa  H 2 cyclic esters called as Lactones.
Acid Sodium salt
of Acid

4.1.2 Reaction with Alkalies

Monocarboxylic acids neutralize hydroxides to form
corresponding salt and water.
CH 3COOH + NaOH  CH 3 COONa + H 2 O
These salts, on being treated with dilute mineral acids regenerate
carboxylic acids.

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Carboxylic Acid and Its Derivatives
CARBOXYLIC ACID AND ITS DERIVATIVES 13

5 membered ring is called  -lactone and 6 membered ring is

called  -lactone.

4.2.2 Formation of Acid Chlorides

Dicarboxylic acids on heating give cyclic anhydride (5 and 6
membered rings).

NOTE :
Formic Acid (HCOOH) does not form anhydride.

4.2.4 Formation of Amides

Out of these three, SOCl 2 , method is preferred because here 4.3 Reduction
other two products are gases that can easily escape.
4.3.1 Reduction to Alcohols
Reducing Agents: LiA1H 4 in ether solution or with H2 in
4.2.3 Formation of Acid Anhydrides
presence of copper chromite ( CuCr2O4 ) catalyst or BH 3 /THF
(or diborane, B2 H 6 ) or H 2 , Ru etc.

H ,Ru-C
2
CH 3  CH 2  CH 2 COOH 

 CH3CH 2 CH 2 CH 2 OH

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Carboxylic Acid and Its Derivatives
14 CARBOXYLIC ACID AND ITS DERIVATIVES
4.4 Carboxyl Group Reactions β- unsaturated acids decarboxylate on heating giving alkenes.

4.4.1 Decarboxylation    Heat H C  CH  CH  CO 

H 2 C  C H  C H 2  COOH  2 3 2
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 
4.4.2 Dry Distillation of Calcium Salts of Carboxylic
2 3
Sodium Salt Heat Alkane Acids
The reaction proceeds through carbanion intermediate. Greater
(RCOO) 2 Ca 
 RCOR + CaCO 3
the stability of carbanion, greater will be rate of decarboxylation.
Calcium Salt Ketone

When calcium formate is heated, formaldehyde is evolved.

Hcat  HCHO  CaCO
(HCOO) 2 Ca  3

Gem dicarboxylic acids decarboxylate simply on heating. Formaldehyde

When a mixture of calcium salt of an acid (other than formic acid)
and calcium formate is heated an aldehyde is formed.
Heat
 CH3COO 2   HCOO  2 Ca   2CH 3 CHO  CaCO3
Calcium Acetate Calcium Formate Acetaldehyde

4.4.3 Kolbe’s Synthesis

Electrolysis of sodium or potassium salts (concentrated aq.
solution) of fatty acids yield alkanes.
 RCOO  Na 
RCOONa 
At Anode :2RCOO  R  R  2CO 2  2e
 2H O
2  2NaOH  H
At Cathode :2Na   2e  2Na  2
β- keto acids undergo decarboxylation through a cyclic transition Reaction involves radical intermediates.
state, giving ketone. O
||
2CH 3 CH 2  C ONa  CH 3 CH 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 give
corresponding alkynes.

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Carboxylic Acid and Its Derivatives
CARBOXYLIC ACID AND ITS DERIVATIVES 15
4.4.4 Hunsdiecker Reaction
An alkyl halide is formed when the silver salt of monocarboxyl
acid is heated with halogen. This is a step down reaction.

CCl
4 CH Br  AgBr  CO 
CH3 COOAg  Br  3 2
Heat Methyl Bromide

4.4.5 Simonini Reaction

The reaction of silver salts of carboxylic acids with iodine is
called Simonini Reaction.
I2
2RCOOAg  
 RCOOR
CO2

NOTE : 4.4.8 Oxidation

The ratio of reagents play an important role in determination Prolonged heating with powerful oxidising agents oxidises acids
of products, namely. into CO 2 and H 2 O .
1: 1 ratio of salt and I 2 - RI is formed
With 3% H2O2 , they are oxidised to β- hydroxy acids.
2: 1 ratio of salt and I 2 - RCOOR is formed

3: 1 ratio of salt and I 2 - Both the products are obtained

4.4.6 Schmidt Reaction

It involves treatment of hydrazoic acid with carboxylic acids.
Alkyl isocyanate is the intermediate. Primary amine formed
contains one carbon less than parent acid.

4.4.9 Conversion to Nitriles

When mixture of acid and NH3 are passed over heated alumina,
alkane nitrile forms.
4.4.7 Hell-Volhard Zelinsky Reaction
When carboxylic acid containing an α- hydrogen is treated with
Cl 2 or Br2 in presence of a catalyst. The  -hydrogen is replaced
by chlorine or bromine atoms.

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Carboxylic Acid and Its Derivatives
16 CARBOXYLIC ACID AND ITS DERIVATIVES

Fig. 8.6: Chemical reactions of carboxylic acids

(C) Dehydration
5. Important Carboxylic Acids
5.1 Formic Acid (HCOOH)
Naturally it occurs in sting of bees, wasps, redant stinging nettles (D) Action of Heat on Formates
and fruits.
It was first prepared by the distillation of red ants and hence it is  COONa
(a)
2HCOONa o
 |  H2
called as Formic Acid (Latin formica : ant) 360 C COONa


5.1.1 Preparation (b) HCOONa  NaOH  Na 2 CO 3  H 2
CaO
Industrial Preparation 
(c)
(HCOO) 2 Ca   HCHO  CaCO3
Formaldehyde

(d) HCOONH 4  
 HCONH 2  H 2 O
(E) Reducing Properties
Acid is regenerated by the action of H 2SO 4 .

(a)
5.1.2 Chemical Properties
(A) Acidic Nature (b)

(B) Action of Heat

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Carboxylic Acid and Its Derivatives
CARBOXYLIC ACID AND ITS DERIVATIVES 17
(c) HCOOH  2HgCl 2  HgCl 2  2HCl  CO 2 5.2 Acetic Acid ( CH3COOH )
HCOOH  Hg 2 Cl 2  2Hg  2HCl  CO 2 In free state it is found in fermented fruit juices and in bound
Black
state it is found in biological fluids and plant extracts.
(d) Tollen’s Reagent
  2Ag  CO  H O
It is a by-product of alcohol industry.
HCOOH  Ag 2 O  2 2
Silver
Mirror
5.2.1Preparation
(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 Tollen’s reagent.
3. It forms black ppt with HgCl2 .

4. Heated with H 2SO 4 , it evolves CO which burns with blue

flame on mouth of test tube.
5. On reacting with neutral solution of FeCl3 , it gives red colour
which converts in brown ppt on heating.
Fresh Heating
HCOOH 
 Re d Colour  Brown ppt
FeCl
3 5.2.2 Chemical Properties
Acetic Acid is a typical member of fatty acids. It shows all the
5.1.4 Uses general characteristics of mono carboxylic acids listed earlier.
1. In lab preparation of CO.
2. Textile dyeing and finishing. 5.2.3 Tests for CH 3COOH
3. Leather tanning. 1. Its aqueous solution turn blue litmus red.
4. Coagulating agent for rubber latex.
2. Its aqueous solution gives effervescences of CO 2 with
5. As an antiseptic and treatment for gout.
Neutral NaHCO3
6. As a strong irritant.
3. It does not affect Tollen’s reagent, Fehling solution and
HgCl2 . These reactions are used to differentiate it form
NOTE :
HCOOH.
1. It is the strongest carboxylic acid.
2. Its unique nature is due to the presence of both
carboxyl and carbonyl group.
5.2.4 Uses
1. Good solvent and lab reagent.
2. As vinegar and table purposes in houses.
3. In manufacturing pickles.
4. Making Al, Cr, Fe acetates which are used as mordants dyeing.

5.3 Benzoic Acid (C6H5COOH)

Naturally it is obtained from Benzoin resin. It is a benzene
derivative and aromatic compound.

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Carboxylic Acid and Its Derivatives
18 CARBOXYLIC ACID AND ITS DERIVATIVES
5.3.1 Preparation -COOH group attached to benzene nucleus in m-directing and a
deactivating group. It also gives electrophilic aromatic
KMnO
4 3 H O substitution (EAS) reactions.
(A) Ph  CH 3  Ph  COOK  PhCOOH
KOH,

(B)
Co Mn Acetate
2C6 H5 CH3  3O2  2C6 H5 COOH  2H 2 O
170ºC
(C)

(D)

Fig. 8.8: Chemical reactions of benzoic acid

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
of benzoic acid are also similar to the properties of aliphatic
acids.

5.3.3 Uses
1. Used as food preservative.
2. Used as precursor for many compounds.
3. Used in making medicines for fungal diseases.

6. Functional Derivatives Of Acids

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.
General Mechanism of Nucleophilic Acyl Substitution

Fig. 8.7: Chemical reactions of benzoic acid

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CARBOXYLIC ACID AND ITS DERIVATIVES 19
Step 1 : Addition of Nucleophile (B) Conversion to Amides

Step 2 : Loss of Leaving Group

Leaving groups L: Cl  , NH 2 , RO  , RCOO 

The weaker is the base, the better is the leaving group. The basic
nature of the above groups is in the order : (C) Conversion to Anhydrides

Cl   RCOO   OH   RO   NH 2 
Hence, the leaving tendency of the groups is in order
(D) Conversion to Alcohols
NH 2   RO   OH   RCOO   Cl 
(i) Grignard Reagent
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 

(B) RCOOH  SOCl2  RCOCl  SO 2   HCl 

(ii) Metal Hydrides
(C) RCOOH  PCl3  RCOCl  H 3 PO3
6.1.2 Reactions
(A) Esterification

(E) Conversion to Aldehydes

(i) Rosenmund’s Reduction

(ii) Metal Hydride LiAl(OMe3)3H

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20 CARBOXYLIC ACID AND ITS DERIVATIVES
(F) Conversion to Ketones 6.2 Acid Anhydrides
(i) Dialkyl Cadmium 6.2.1 Preparation

(ii) Gilman’s Reagent

(A)

(G) F riedel-Craft’s Acylation

(B)

(H) Curtius Reaction

(I) Hydrolysis

(C)

(J) Formation of  -Keto Adds

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CARBOXYLIC ACID AND ITS DERIVATIVES 21
(E) Friedel-Craft’s Acylation

6.2.2 Reactions
(A) Esterification (F) Perkin Reaction

(B) Conversion to Amides

(G) Hydrolysis

6.3 Esters
6.3.1 Preparation
(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
(C) Conversion to Acyl Chlorides as Esterification.

Mechanism
(D) Conversion to Alcohols

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22 CARBOXYLIC ACID AND ITS DERIVATIVES
Since a tetrahedral intermediate occupies more space than a planar formed is resonance stabilised.
carbonyl group, we would expect the rate of this reaction to be (B) Conversion to Acyl Chloride
retarded when bulky reactants are used. When the esterification
of acetic acid was compared with that of 2, 2 -dimethylpropanoic
acid, (CH 3 )3 C  COOH the relatively small methyl group of acetic
acid is replaced by a larger tert-butyl group, and the bulkier acid
(C) Conversion to Amides
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) (D) Conversion to Alcohols
(i) Metal Hydrides

(C)

(ii) Bouveault-Blanc Reduction

Na
RCOOR '  RCH 2 OH  R 'OH
C2H5OH
(iii) Grignard Reagent
(D) R  CH  C  O  R 'OH  RCH 2 COOR '
(E) Baeyer-Villiger Oxidation of Ketones

O O
|| ||
Peroxy Acid
R  C  R '   R  C  OR '
Oxygen is introduced on that side which has more electron
donating alkyl group.

(F) Carbonylation of Ethers

BF ,150  200 C (E) Transesterification
R  O  R  CO 
3 R  COOR Transesterification is the process of exchanging the alkoxy group
Pressure
of an ester compound by another alcohol. These reactions are
(G) Diazomethane CH2N2 often catalyzed by the addition of an acid or base.
R-COOH + CH 2 N 2  RCOOCH 3 +N 2

6.3.2 Reactions
(A) Hydrolysis

Base catalysed hydrolysis is not reversible as carboxylate ion

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CARBOXYLIC ACID AND ITS DERIVATIVES 23
(F) Acyloin Formation (C)

(G) Claisen Condensation

(D)

6.4.2 Reactions

(A) Hydrolysis
Intramolecular claisen condensation is called as Dieckmann
Condensation. H SO
2 4  RCOOH  NH
RCONH 2  H 2 O  3
H O
2  RCOONa  NH
RCONH 2  NaOH  3

This is typical of 1 amides to give off NH3

6.4 Amides
Table 8.1:Types of Amides
RCONH2 RCONHR RCONR2 (B) Conversion to Cyanides
1 amides
o
2 amides
o
3o amides
P O
4 10  RC  N  H O
RCONH 2 
Alkanamides N-Alkyl N, N-Dialkyl  2

Alkanamides Alkanamides
Dehydrating Reagents such as P2 O5 , SOCl2 or POCl3 is used.

6.4.1 Preparation
(C) Conversion to Amines
(A) RCOOH  NH 3  RC OONH 4   RCONH 2 Amides are reduced to amines by reaction with reducing agents
NH
3  RCONH such as LiAlH 4 or Na/C2 H5 OH.
(B) RCOOH  PCl5  RCOCl  2

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24 CARBOXYLIC ACID AND ITS DERIVATIVES

6.5 Carbonic Acid Derivatives

Aqueous carbonic acid ( CO 2 gas dissolved in H 2 O ) is unstable
and behaves as dibasic acid.
(D) Reaction with HNO 2

RCONH 2  HNO 2  RCOOH  N 2   H 2 O

(E) Hofmann Bromamide Degradation

RCONH 2  4NaOH  Br2

RNH 2  2NaBr  Na 2 CO3  2H 2 O
(F) Conversion to Imides Derivatives of Carbonic Acid
Cyclic anhydrides are converted first into an amide on reaction
with NH3 and then heated to form Imides.

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CARBOXYLIC ACID AND ITS DERIVATIVES 25

Summary
Methods of preparation of carboxylic acids

Chemical reactions of carboxylic acids

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26 CARBOXYLIC ACID AND ITS DERIVATIVES

Exercise – 1: Basic Objective Questions

Introduction to Carboxylic Acid and Its (b) 3-carboxy-3-methylpent-2-en-3-one
Derivatives (c) 4-carboxy-3-methylpent-3-en-2-one
(d) 2,3-dimethyl-4-oxopent-2-en-1-oic acid
O
|| 7. The IUPAC name of
1. H  C  Cl is called:
(a) Acetyl chloride (b) Formyl chloride
(c) Chloretone (d) Oxochloromethane
2. The IUPAC name for

is:
(a) N-Cyclohexylbenzamide
is :- (b) N-Phenyl-N-cyclohexylmethanamide
(a) 1-Hydroxy-4-methylpentanoic acid (c) N-Phenylcyclohexanecarboxamide
(b) 1-Methyl-3-hydroxypentanoic acid (d) N-Cyclohexyl-N-phenylmethanamide
(c) 4-Hydroxy-2-methylpentanoic acid 8. The general formula for monocarboxylic acids is
(d) 4-Carboxypentan-2-ol. (a) CnH2nO (b) CnH2n+1O2
3. The IUPAC name of C6H5COCl is
(c) CnH2n+2O2 (d) CnH2nO2
(a) chlorobenzyl ketone
9. Monocarboxylic acids are functional isomers of
(b) benzenechloroketone
(a) Alcohols (b) Ethers
(c) benzenecarbonyl chloride
(c) Esters (d) Aldehydes and ketones.
(d) chlorophenyl ketone
10. How many acids and esters are possible for the
4. The IUPAC name of
compound with molecular formula C4H8O2
(a) Two acids + Two esters
(b) Two acids + Four esters
(c) Four acids + Two esters
is: (d) Three acids + Three esters
(a) 2-Bromo-3-methylbutanoic acid 11. How many stereoisomers (geometrical and optical) are
(b) 2-Methyl-3-bromobutanoic acid possible for the following compound ?
(c) 3-Bromo-2-methylbutanoic acid CH3CH=CHCH2CH(OH)COOH
(d) 3-Bromo-2,3-dimethylpropanoic acid (a) 1 (b) 2
5. The IUPAC name of is (c) 3 (d) 4
12. Which of the following is a polyprotic acid
(a) Acetic acid (b) Benzoic acid
(c) Salicylic acid (d) Oxalic acid
(a) but-3-enoic acid (b) but-1-enoic acid 13. A tribasic acid is
(c) pen-4-enoic acid (d) prop-2-enoic acid (a) Oxalic acid (b) Tartaric acid
6. The IUPAC name of the molecule (c) Lactic acid (d) Citric acid
14. Saturated fatty acids are represented by which of the
formula?
(a) CnHnO2 (b) CnH2nO3
(c) CnH2n+1 (d) CnH2nO
15. The general formula CnH2nO2 could be for open chain
is:
(a) diketones (b) carboxylic acids
(a) 4-oxo-2,3-dimethylpent-2-en-1-oic acid
(c) diols (d) dialdeydes
CARBOXLIYC ACID AND ITS DERIVATIVES 27

16. Which of the following does not represent the natural (c) CO2 and H2O (d) None of these
source of the corresponding acids ? 26. Identify Z in the following reaction sequence
(a) Formic acid : Red ant Mg Dry ice Cl
CH 3 I   X  2 Z
 Y 
(b) Acetic acid : Vinegar Ether H O Red P
3
(c) Butyric acid : Rancid butter (a) CH3COOH (b) CH3MgI
(d) Isobutyric acid : Automobile exhausts
(c) CH3COCl (d) ClCH2COOH
17. Which one of the following acid is present in lemon?
(a) Acetic acid (b) Tartaric acid 27. The compound formed as a result of oxidation of ethyl
(c) Citric acid (d) Oxalic acid benzene by KMnO4 is
18. Vinegar is a solution of acetic acid which is (a) benzophenone (b) acetophenone
(a) 15-20% (b) 20-25% (c) benzoic acid (d) benzyl alcohol
(c) 6-8% (d) 2-4% 28. p-cresol reacts with chloroform in alkaline medium to
give the compound A which adds hydrogen cyanide to
Preparation of Carboxylic Acid form the compound B. The latter, on acidic hydrolysis
gives chiral carboxylic acid. The structure of the
19. Ethanoic acid is prepared commercially from carboxylic acid is
(a) Ethyne (b) Ethanol
(c) Methanal (d)Both ethyne and ethanol.
20. In the following reaction sequence.
CuCN/Pyridine Dil. H SO
2 4 Y
C6 H5 Br  X 
523K 523K
The product Y is
(a)
(a) Benzonitrile (b) Benzene
(c) Benzoic acid (d) Benzamide.
21. Acetic acid is obtained when
(a) Methyl alcohol is oxidised with potassium
permanganate
(b) Formaldehyde is oxidised with potassium
dichromate and sulphuric acid (b)
(c) Acetonitrile is hydrolysed with a dilute mineral acid
(d) Glycerol is heated with sulphuric acid.
22. Hydrolysis of hydrogen cyanide results in the
formation of
(a) Formic acid (b) Oxalic acid
(c) Formaldehyde (d) Acetaldehyde
23. The acid (D) obtained through the following sequence (c)
of reactions is
[Link] Br KCN H O
C2 H5 Br  2
 A  B  3 D
CCl  excess   C 
4
(a) Succinic acid (b) Malonic acid
(c) Maleic acid (d) Oxalic acid
(d)
24. Hydrolysis of acetamide produces
(a) Acetic acid (b) Acetaldehyde 29. CH3COOH is formed by hydrolysis of
(c) Methylamine (d) Formic acid (a) CH3NH2 (b) CH3CN
25. When benzyl alcohol is oxidised with KMnO4, the
(c) CH3CH2CN (d) CH3CH2NH2
product obtained is
(a) Benzaldehyde (b) Benzoic acid
28 CARBOXYLIC ACID AND ITS DERIVATIVES

30. For the following reaction. 37. Select correct statement (s) :
(a) Carboxylic acids have higher boiling points than
isomeric esters because of dimer formation by
intermolecular H-bonding.
(a) there is protonation of the electronegative nitrogen
followed by attack of water at the electron-deficient
carbon
(b)
(b) an amide is formed as an intermediate
molecules are associated by H-bonding
(c) nitrogen atom is expelled as ammonium ion
(c) The presence of carbonyl group in acid derivative
(d) all of the above are true
makes them polar compounds
31. In which case yield of the carboxylic acid is
(d) All of the above statements are correct
maximum?
38. Carboxylic acids exist as … in the vapour phase or in
KCN, DMSO
3  H O
(a) CH 3 CH 2 CH 2 CH 2 Br   the aprotic solvents.
Fill in the blank with best suitable word.
KCN, DMSO H O
3 
(b) CH 3 CH(Br)CH 2 CH 3  (a) dimer
(c) (b) trimer
(c) tetramer
CH
3 (d) All of the above.
| H3O
KCN, DMSO
CH 3  C  Br    39. Higher carboxylic acids are insoluble in water due to
|
CH (a) increased hydrophobic interaction of the
3
hydrocarbon part
(d) Equivalent yield (b) decreased hydrophobic interaction of the
32. Which of the following will give carboxylic acid on hydrocarbon part
oxidation with heat and alkaline KMnO4 followed by (c) Both (a) and (b)
acidification? (d) None of the above
(a) Ethylbenzene (b) Toluene 40. Benzoic acid is nearly insoluble in cold water.
(c) Propylbenzene (d) All of these Carboxylic acids are soluble in less polar organic
33. Which of the following compounds will react with solvents like benzene, ether, alcohol, chloroform.
NaHCO3 solution to give sodium salt and carbon The above statement is
dioxide (a) True (b) False
(c) Sometimes True (d) Sometime false
(a) Phenol (b) n-hexanol 41. Carboxylic acids have higher boiling point due to
(c) Acetic acid (d) Both (a) and (b) presence of ….
34. The major product obtained on interaction of phenol Fill in the blank with best suitable word.
with sodium hydroxide and carbon dioxide is (a) Van der waals interactions
(a) benzoic acid (b) salicyladehyde (b) Intermolecular hydrogen bonding
(c) salicylic acid (d) phthalic acid (c) Dispersion forces
(d) None of these.
Physical Properties of Carboxylic Acid Chemical Properties of Carboxylic Acid
35. Which of the following has the highest boiling point? 42. The weakest acid among the following is
(a) CH3OCH2CH3 (b) CH3CH2CH2OH (a) CH3COOH (b) Cl2CHCOOH
(c) CH3COOH (d) CH3CH2CH2CH3 (c) ClCH2COOH (d) Cl3CCOOH
36. The carboxylic acid which has maximum solubility in 43. Which acid is strongest or Which is most acidic
water is (a) Cl2CHCOOH (b) ClCH2COOH
(a) Phthalic acid (b) Succinic acid
(b) CH3COOH (d) Cl3CCOOH
(c) Malonic acid (d) Salicylic acid
CARBOXLIYC ACID AND ITS DERIVATIVES 29

44. Which of the following is the weakest acid 51. Which of the following para-substituted benzoic acids
is the most acidic
(a) Cl – C6H4COOH (b) NO2 – C6H4COOH
(c) HO – C6H4 – COOH (d) CH3 – C6H4 – COOH
(a) 52. In the anion HCOO– the two carbon-oxygen bonds are
(b) CH3COOH found to be of equal length. What is the reason for it.
(c) HCOOH (a) Electronic orbitals of carbon atom are hybridised
(b) The C = O bond is weaker than C – O bond
(c) The anion HCOO– has two resonating structures.
(d) The anion is obtained by removal of a proton form
the acid molecule
(d)
53. What is the main reason for the fact that carboxylic
45. The acidic nature of carboxylic acids,
acids can undergo ionization
is due to
(a) High degree of ionization of carboxylic acids (a) Absence of -hydrogen
(b) Greater resonance stabilization of the carboxylic (b) Resonance stabilization of the carboxylate ion
acid over the carboxylate ion (c) High reactivity of -hydrogen
(c) Greater resonance stabilization of the carboxylate (d) Hydrogen bonding
ion over the carboxylic acid 54. Increasing value of the dissociation constant Ka of the
(d) Solubility of carboxylic acids in water. given acids is of the order
46. Which of the following would be expected to be the
most highly ionized in water ?
(a) ClCH2CH2CH2COOH (b) CH3CCl2CH2COOH
(c) CH3CH2CCl2COOH (d) CH3CH2CHClCOOH
47. Rewrite the following in the increasing order of acidity
?
(i) Benzoic acid
(ii) p-methoxybenzoic acid
(iii) o-methoxybenzoic acid
(a) (i) < (ii) < (iii) (b) (iii) < (i) < (ii)
(c) (ii) < (i) < (iii) (d) (iii) < (ii) < (i). (a) I < II < III (b) II < III < I
48. The increasing order of acidity of ,  and – (c) III < II < I (d) I < III < II
chlorobutyric acids is CCl ,Reflux
55. The reaction: RCOOAg + Br2  4 
(a) << (b) << R – Br + AgBr + CO2
(c) << (d) << is called
49. Which one of the following orders of acid strength is (a) Wurtz reaction
correct (b) Hunsdiecker reaction
(a) RCOOH > HC  CH > HOH > ROH (c) Friedel-Crafts reaction
(b) RCOOH > ROH > HOH > HC  CH (d) Kolbe’s reaction
56. The principal organic product formed in the reaction
(c) RCOOH > HOH > ROH > HC  CH
CH  CH(CH ) COOH  HBr  Peroxide
(d) RCOOH > HOH > HC  CH > ROH 2 2 8

50. Acetic acid is weak acid than sulphuric acid because is:
(a) It decompose on increasing temperature (a) CH3CHBr(CH2)8COOH
(b) It has less degree of ionisation (b) CH2=CH(CH2)8COBr
(c) It has – COOH group
(c) CH2BrCH2(CH2)8COOH
(d) None of these
(d) CH2=CH(CH2)7CHBrCOOH
30 CARBOXYLIC ACID AND ITS DERIVATIVES

57. Among the following, the acid which undergoes fastest 66. Consider the acidity of the carboxylic acids :
decarboxylation is (i) C6H5COOH (ii) o–NO2C6H4COOH
(iii) p–NO2C6H4COOH (iv) m–NO2C6H4COOH
Which of the following order is correct ?
(a) (b) (a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iv) > (iii) > (i)
(c) PhCOOH (d) PH CHOH COOH (c) (ii) > (iv) > (i) > (iii) (d) (ii) > (iii) > (iv) > (i)
58. Treatment of benzoic acid with Cl2/FeCl3 will give 67. What will be the product, when carboxy phenol,
(a) p-chlorobenzoic acid (b) o-chlorobenzoic acid obtained by Reimer-Tiemann’s process, is deoxidised
(c) 2,4-dichlorobenzoic acid (d) m-chlorobenzoic acid with Zn-powder?
59. Which of the following will not undergo Hell - volhard
Zelinsky (HVZ) reaction ?
(a) HCOOH (b) CH3COOH
(c) CH3CH2COOH (d) CH3CHBrCOOH
60. The elimination of CO2 from a carboxylic acid is (a) (b)
known as
(a) hydration (b) dehydration
(c) decarboxylation (d) carboxylation
61. Which has maximum value of equilibrium constant ?
(a) CH3COOH  H 2 O  CH3COO  H 3O (c) (d)
(b) HCOOH  H 2 O  HCOO  H3 O  68. Silver benzoate reacts with bromine to form

(c) C6 H5COOH  H2 O  C6 H5 COO  H3 O

(d) CF3COOH  H 2 O  CF3 COO  H3O
62. Propanoic acid or its sodium salt can be converted into
alkanes by reduction with HI/red P or decarboxylation (a) (b)
reaction or kolbe’s electrolysis. Which of the following
alkanes is not formed in any of these reactions ?
(a) Methane (b) Ethane
(c) Propane (d) Butane
63. Which is false in case of carboxylic acids?
(a) They are polar molecules (c) (d)
(b) They form H-bonds 69. Which of the following undergoes hydrolysis when
(c) They are stronger than mineral acids dissolved in water
(d) They have higher b.p. than corresponding alcohols (a) CH3COONa (b) CH3CONH2
64. Among the following the strongest acid is (c) Both (a) & (b) (d) C6H5CH3
(a) CH3COOH (b) C6H5COOH
70. Benzoic acid gives benzene on being heated with X
(c) m-CH3OC6H4COOH (d) p-CH3OC6H4COOH and phenol gives benzene on being heated with Y.
65. The strongest acid amongst the following compounds Therefore X and Y are respectively
is (a) Sodalime and copper
(a) CH3COOH (b) Zn dust and NaOH
(b) HCOOH (c) Zn dust and sodalime
(c) CH3CH2CH(Cl)CO2H (d) Sodalime and zinc dust
(d) ClCH2CH2CH2COOH
CARBOXLIYC ACID AND ITS DERIVATIVES 31

71. An optically active compound ‘X’ has molecular (c) Both

formula C4H8O3. It evolves CO2 with aq. NaHCO3. ‘X’ (d) None
reacts with LiAlH4 to give an achiral compound. ‘X’ is 74. The yield of ester in esterification can be increased by
CH CH OH + CH COOH ⇋ CH COOCH CH + H O
(a) 3 2 3 3 2 3 2

(a) removing water

CH 3 CH 2 CHCOOH
| (b) taking ethanol in excess
OH (c) taking acetic acid in excess
(b) (d) all the above factors
CH3 CH COOH 75. Sulphonation of benzoic acid produces mainly
| (a) o–sulphobenzoic acid
OMe (b) m–sulphobenzoic acid
(c) p–sulphobenzoic acid
(c)
(d) o–and p–sulphobenzoic acid
CH3 CH COOH
| 76. The major product in the reaction
CH 2 OH
(d)
CH 3 CHCH 2 COOH
|
OH
72.

(a) (b)

(c) (d)
SOCl2
LiAlH 4
77. CH 3 CH 2 COOH  A  
CH 2OH
(a) |
CH 2OH
B 
 C is

(b) (a)
(b) CH3CH2COCl
(c) CH3CH2CH2NH2
(d) None of the above
78. In the reaction,
LiAlH [Link]
5 B  PCl
(c) 4  A 
CH 3 COOH  C
(d) None the product C is :
73. CH3Br can be prepared by (a) Acetylene (b) Ethylene
 (c) Acetyl chloride (d) Acetaldehyde
(a) CH3COOAg  Br2 
P/Br
2   soda lime, 
(b) CH 3 COOH  
32 CARBOXYLIC ACID AND ITS DERIVATIVES

79. In the anion HCOO the two carbon-oxygen bonds are

–
83. Arrange the following acids in the decreasing order of
found to be of equal length. What is the reason for it? the acidic strength.
(a) Electronic orbitals of carbon atom are hybridised HC  C  COOH  I  , C 6 H 5 COOH  II  ,
(b) The C=O bond is weaker than the C–C bond CH 2  CH  COOH  III  , CH 3 COOH  IV 
(c) The anion HCOO has two resonating structures
–
Choose the correct option.
(d) The anion is obtained by removal of a proton from (a) I > II > III > IV (b) I < II < III < IV
the acid molecule (c) I > III > II > IV (d) I > IV > III > II
80. Propionic acid and KOH reacts to produce which one 84. Why the aromatic carboxylic acids do not undergo
of the following? Friedel-Crafts reaction?
(a) Potassium propionate (b) Propyl alcohol (a) Carboxyl group acts as an activating and meta-
(c) Propionaldehyde (d) Does not react directing group
81. Name the end product in the following series of (b) Carboxyl group act as a deactivating and meta-
reactions directing group
NH 3 (c) Carboxyl group act as an activating and ortho-
CH 3 COOH    A  
B
P2 O 5
directing group
(a) CH4 (b) CH3OH (d) Carboxyl group acts as deactivation and the catalyst (lewis
(c) Acetonitrile (d) Ammonium acetate acid) gets bonded to the carbonyl group
82. In a set of the given reactions, acetic acid yields a 85. Alkali metal salts of carboxylic acids also undergo
product C. decarboxylation on electrolysis of their aqueous
CH3COOH  PCl5  A solutions and form hydrocarbons having twice the

C H C H MgBr number of carbon atoms present in the alkyl group of

6 6
A     B 2 5  
C
[Link]
3 Ether the acid. The reaction is known as

Product C would be (a) Kolbe electrolysis

(b) decarboxylation
(a) CH3CH OH C6H5
(c) HVZ reaction
C2H5 (d) Friedel-Crafts reaction
(b) |
86. Which of the – COOH is lost during heating?
CH 3  C  OH  C 6 H 5

(c) CH3CH OH C2H5

(d) CH3COC6 H5

(a) I (b) II
(c) III (d) IV
CARBOXLIYC ACID AND ITS DERIVATIVES 33

87. (b) R  CH2  COX

(c)
X
|
R  C  COOH
|
X
(d)
R  CH  CH 2  COOH
|
X
90. Diborane easily reduce the functional group such as
(a) acid (b) ester
Identify ‘X’ and ‘Y’ for the above reaction. (c) nitro (d) halo
91. Direct attachment of groups such as phenyl or vinyl to
the carboxylic acid, increases the acidity of
corresponding carboxylic acid because
(a) of greater electronegativity of sp hybridized carbon
(a) to which carboxyl carbon attached
(b) of greater electronegativity of sp2 hybridized
carbon to which carboxyl carbon is attached
(c) of ions electronegativity of sp hybridized carbon to
which carboxyl carbon is attached
(d) None of the above
Preparation of Carboxylic Acid Derivatives
(b)
92. Acetyl chloride cannot be obtained by treating acetic
acid with
(a) CHCl3 (b) SOCl2
(c) PCl3 (d) PCl5
93. A Carboxylic Acids and Their Derivatives is converted
(c) into its anhydride using -
(a) Thionyl chloride (b) Sulphur chloride
(c) Sulphuric acid (d) Phosphorus pentoxide
94. Two moles of acetic acid are heated with [Link]
product formed is
(d) (a) 2 moles of ethyl alcohol
88. Select the incorrect match. (b) Formic anhydride
(a) pKa values < 1 → strong acids (c) Acetic anhydride
(b) pKa values between 1 and 5 → moderately strong (d) 2 moles of methyl cyanide
acids 95. Heating a mixture of ethyl alcohol and acetic acid in
(c) pKa values between 5 and 15 → weak acids presence of conc. H2SO4 produces a fruity smelling
(d) pKa values > 15 → extremely strong acids
compound. This reaction is called
89. The product formed during Hell-Volhard-Zelinsky
(a) Neutralisation
reaction is
(b) Ester hydrolysis
(a)
R  CH  COOH (c) Esterification
| (d)Williamson’s synthesis
X
 34 CARBOXYLIC ACID AND ITS DERIVATIVES

96. Which reagent will bring about the conversion of (b) H2SO4
carboxylic acids into esters (c) HOCl
(a) C2H5OH (d) CH3COONa
(b) Dry HCl + C2H5OH 103. Complete the synthesis by giving the missing product.
(c) LiAlH4
(d) Al(OC2H5)3
97. In esterification, OH ion for making H2O comes from:
(a) Acid (a)
(b) Alcohol
(c) Ketone
(d) Carbohydrate
98. The product D of the reaction

(b)
is
(a) CH3CH2NH2 (b) CH3CN
(c) HCONH2 (d) CH3CONH2
99. (c)

(d)

Reagents I and II given in the reactions are:

 
(a) Pt / H2, H3O
 
(b) Li / NH3, H3O
 104. Which of the reagent(s) is/are used for the conversion
(c) H2 / Lindlar catalyst, H3O
of ethanoic acid to ethanoic anhydride?

(d) H2O/Na, H3O (a) SOCl2 , (b) PCl3 ,
100. Which is not the source of carbonyl compounds ? (c) P2O5 , (d) All of the above
LiAlH4
(a) RCOCl 
2
(b) RCOCl 
R CuLi Chemical Properties of Carboxylic Acid
H /Pd  BaSO
Derivatives
(c) RCOCl 2
4
Li  t  BuO  AlH
3 
105. Resonance stabilisation is maximum in :
(d) RCOCl   
200K, H3O O O
 
101. Benzoyl chloride is prepared from benzoic acid by
(a) R  C Cl (b) R  C  CH
(a) Cl2, hv (b) SO2Cl2 3

(c) SOCl2 (d) Cl2,H2O O O

 
102. Acetic anhydride is obtained from acetyl chloride by (c) R  C  OH (d) R  C  NH
2
the reaction of
(a) P2O5
CARBOXLIYC ACID AND ITS DERIVATIVES 35

106. Maximum keto-enol tautomerism is shown by 112. Acyl SN reaction is not possible
(a) CH3COOCH3
when :
(b) CH3COCH2CH3
O
(c) CH3CH2COOCH2CH3 
(d) CH3COCH2COOC2H5 R  C X  Y 
107. Which is more basic oxygen in an ester (a) X is NH2 and Y is Cl (b) X is OH and Y is NH2
β (c) X is Cl and Y is OH (d) X is OR and Y is NH2
O
 113. Select correct statements for the following base-
R  C O R
α catalysed reaction
(a) O denoted by  O O
(b) O denoted by   18 OH  
(c) Both equally R  C  O  CH3  R  C  O   CH 3OH
(d) None of the oxygen atoms is basic
(a) It is a straight forward nucleophilic acyl substitution
108. The decreasing order of reactivity of
(i) CH3COCl (ii) CH3COOC2H5 (addition and then elimination)
(iii) CH3CONH2 (iv) (CH3CO)2O (b) O18 appears in methanol CH3OH
Towards nucleophilic acyl substitution is (c) The reaction is not reversible
(a) (i) > (iv) > (iii) > (ii)
(d) All are correct statements
(b) (i) > (iv) > (ii) > (iii)
(c) (iv) > (iii) > (i) > (ii) 114. Benzoyl chloride on treatment with ammonia gives
(d) (iii) > (i) > (iv) > (ii) (a) Benzamide (b) Acetamide
H
109. CH 3 COCl   2  CH 3 CHO  HCl; (c) Benzylamine (d) Benzoic acid
Pd / BaSO
4
115. Acetic anhydride reacts with excess of ammonia to
The above reaction is called
(a) Reimer-Tiemann reaction form
(b) Cannizzaro reaction (a) 2CH3COONH4
(c) Rosenmund reaction
(d) Reformatsky reaction (b) 2CH3CONH2

(c) CH3CONH2 + CH3COONH4

O O
|| || (d) 2CH3COOH
110. CH3  C Cl  Nu   CH3  C Nu  Cl
Reactivity order of different nucleophiles 116. Which will not give acetamide on reaction with
(NH2-, CH3COO-, OH-) is in order ammonia
(a) NH2- <CH3COO- < OH-
(a) Acetic acid (b) Acetyl chloride
(b)CH3COO- < OH- <NH2-
(c) NH2- <OH-<CH3COO- (c) Acetic anhydride (d) Methyl formate
(d) CH3COO- <NH2- <OH- 117. Sodium ethoxide has reacted with ethanoyl chloride.
111. Which is hydrolysed to a maximum extent ? The compound that is produced in the above reaction is
(a) diethyl ether (b) 2-butanone

(a) (b) (c) ethyl chloride (d) ethyl ethanoate

(c) (d)
36 CARBOXYLIC ACID AND ITS DERIVATIVES

118. Which is hydrolysed to the maximum extent? (b) Aniline

(c) Acetamide
(d) Acetoxime
124.
(a)

, A is
(b)

(c)
(a)

(d)
119. The reaction,
H or OH
RCOOR   R OH  excess  
 RCOOR  (b)
 R OH
is called
(a) Esterification
(b) Trans-esterification
(c) Saponification
(d) Hydrolysis (c)
120. The reaction, CH3COOH + CH3OH → CH3COOCH3 +
H2O is called
(a) Acidification reaction
(b) Dehydration reaction
(c) Dehydrogenation reaction (d)
(d) Esterification reaction
121. Hydrolysis of an ester gives acid A and alcohol B. A
reduces Fehling solution and oxidation of B gives A. 125.
The ester is
(a) Methyl formate
(b) Ethyl formate
(c) Methyl acetate
(d) Ethyl acetate
Above ester has chiral carbon (*). Alkaline hydrolysis
122. Ethyl acetate reacts with CH3MgBr to form
gives an acid salt and an alcohol. Select correct
(a) Tertiary Alcohol
statement about alcohol.
(b) Secondary Alcohol (a) Configuration about chiral carbon is retained
(c) Primary Alcohol and Acid
(b) Configuration about chiral carbon is inverted
(d) Acid
(c) Product (alcohol) loses chirality
123. Which of the following substances when boiled with
(d) None of the statements is correct
caustic soda solution will evolve ammonia
(a) Ethylamine
CARBOXLIYC ACID AND ITS DERIVATIVES 37

126.

A is (c)
(a)

(d)
130. Acidic hydrolysis is least that of :
(b)

(a)
(c) Both are correct
(d) None is correct
127. Acid hydrolysis of an ester is reversible because :
(b)
(a) alcohol and acid react together to form ester
(b) protonation of ester makes carbonyl carbon more
reactive for nucleophilic attack
(c) proton being strong nucleophile, favours hydrolysis (c)
(d) H3O+ is a nucleophile as well as electrophile
128. In the reaction sequence :
SOCl LiAlH O Bu 
3 B
2  A 
CH 3CH 2 COOH 
HOCH CH OH (d)
2 2
 C 131. What are the organic products formed
‘C’ is most likely to be : C6 H5 – COO – CH3 
1.LiAlH4

2.H3 O

(a) C6H5COOH and CH4

(b) C6H5CH2OH and CH4
(c) C6H5CH3 and CH3OH
(a)
(d) C6H5CH2OH and CH3OH
132. In the Hofmann bromamide degradation reaction, the
number of moles of NaOH and Br2 used per mole of
(b) amine produced are :
(a) Four moles of NaOH and two moles of Br2
(c) CH3CH2CHO (b) Two moles of NaOH and two moles of Br2
(c) Four moles of NaOH and one mole of Br2
(d)
129. Alkaline hydrolysis is maximum in : (d) One mole of NaOH and one mole of Br2

(a)

(b)
38 CARBOXYLIC ACID AND ITS DERIVATIVES

133. Give the order of ease of the esterification of the (b) nucleophilic acyl substitution
following acids (c) electrophilic acyl addition
(d) nucleophilic acyl addition
138. Ease of esterification of the following alcohols
CH3CH2OH(I), (CH3)2CHOH(II) and (CH3)3COH(III)
(I)
with HCOOH is:
(a) III < II < I
(b) I < II < III
(II) (c) II < I < III
(d) III = II = I
139. In the following reaction, T is

(III)

(a)

(IV)
(a) I > II > III > IV (b) IV > III > II > I
(c) II > I > IV > III (d) I > II > IV > III
134. Sodium ethoxide has reacted with ethanoyl chloride.
The compound that is produced in the above reaction is
(a) diethyl ether (b) 2-butanone
(b)
(c) ethyl chloride (d) ethyl ethanoate
135. The reaction,
O
 H or OH
CH3  C  OCH3  C2 H5OH  
O (c)

CH3  C  OC2 H5  CH3OH
is called
(a) Perkin’s reaction
(b) Claisen Schmidt reaction
(c) Esterification
(d) trans-esterification (d)
136. Which of the following types of hydrolysis of esters
give directly carboxylic acids and carboxylates
respectively statement?
(a) Acidic hydrolysis and basic hydrolysis
(b) Basic hydrolysis and acidic hydrolysis 140. Amides on heating with P2O5 from
(c) Acidic hydrolysis and acidic hydrolysis (a) Amine (b) Nitrile
(d) Basic hydrolysis and basic hydrolysis (c) Aldehyde (d) Ketone
137. The esterification of carboxylic acids with alcohols is a
kind of
(a) electrophilic acyl substitution
CARBOXLIYC ACID AND ITS DERIVATIVES 39

141. Predict the product formed on the hydrolysis followed 143. Hydrolysis of an ester gives a carboxylic acid which on
by heating of the given reactant and choose the correct kolbe’s electrolysis yields ethane. The ester is
option. (a) methyl ethanoate (b)ethyl ethanoate
(c) propyl amine (d) ethyl amine

Tests of Carboxylic Acid and Its Derivatives

(a) 144. HCOOH shows a test of aldehyde because

(a) It has one aldehyde group
(b) It is member of aldehyde
(c) All acids show tests of aldehyde
x (d) Does not show any test
(b) 145. 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.
146. Tollen’s reagent in not reduced by
(a) Formic acid (b) Acetaldehyde
(c) (c) Benzaldehyde (d) Acetic acid
147. Which one of the following compounds forms a red
coloured solution on treatment with neutral
FeCl3solution
(a) CH3COCH3 (b) CH3OCH3
(d) (c) CH3CH2OH (d) CH3COOH
148. Formic acid can reduce
(a) Tollen’s reagent (b) Mercuric chloride
(c) Fehling reagent (d) All of these
149. Which acid derivative on hydrolysis will give brown
142. Identify ‘A’ and ’B’ in the given reaction precipitate with Nessler’s reagent?
(a) Acid anhydride (b) Acid amide
(c) Acid chloride (d) All of these
150. Tollen’s reagent is
(a)
(a) ammoniacal CuSO4
(b) ammoniacal AgNO3
(c) alkaline solution containing complex of copper
(b) nitrate
(d) none of these

(c)

(d)
40 CARBOXYLIC ACID AND ITS DERIVATIVES

Assertion Reason & Statement Type Questions 155. Assertion (A): Ester hydrolysis is fast in the beginning
and becomes slow after sometime.
151. The following steps are given for the mechanism of Reason (R): The rate of ester hydrolysis increases with
esterification of carboxylic acids. the increase in the amount of carboxylic acid produced.
I. The protonated esters looses a proton to give the ester (a) Both A and R are correct, R is the correct
II. Protonation of the carbonyl oxygen activates the explanation of A.
carbonyl group towards nucleophilic addition of the (b) Both A and R are correct, R is not the correct
alcohol. explanation of A.
III. Proton transfer in the tetrahedral intermediate (c) A is correct, R is incorrect.
occurs. (d) A is incorrect, R is correct.
Arrange the following steps in their correct sequence. 156. Given below are two statements:
(a) I, II and III (b) I, III and II Statement-I: The higher acids are wax like solids and
(c) II, III and I (d) III, II and I are practically odourless due to their low volatility.
152. Assertion (A): A carboxylic acids are higher boiling Statement-II: Carboxylic acids upto nine carbon atoms
liquids than aldehydes, ketones and even alcohols of are higher boiling point liquids than carbonyl
comparable molecular masses. compounds and even alcohols of comparable molecular
Reason (R): More extensive association of carboxylic masses.
acid molecules through intermolecular hydrogen In the light of the above statements, choose the most
bonding. appropriate answer from the options given below:
(a) Both A and R are correct, R is the correct (a) Both statement I and II are correct.
explanation of A. (b) Both statement I and II are incorrect.
(b) Both A and R are correct, R is not the correct (c) Statement I is correct but statement II is incorrect
explanation of A. (d) Statement I is incorrect but statement II is correct.
(c) A is correct, R is incorrect. 157. Assertion (A): IUPAC name of HOOC—(CH2)2—
(d) A is incorrect, R is correct. COOH is butanedioic acid.
153. Assertion (A): The melting points and boiling points of Reason (R): Compounds containing more than one
aliphatic acids are usually higher than those of aromatic carboxyl group, the ending‘-e’ of the alkane is retained.
acids of comparable molecular masses. Prefix ‘di’ is added to the term ‘oic’
Reason (R): The planar benzene ring in the aromatic (a) Both A and R are correct, R is the correct
acids can fit more closely in the crystal lattice than zig– explanation of A.
zag structure of aliphatic acids. (b) Both A and R are correct, R is not the correct
(a) Both A and R are correct, R is the correct explanation of A.
explanation of A. (c) A is correct, R is incorrect.
(b) Both A and R are correct, R is not the correct (d) A is incorrect, R is correct.
explanation of A. 158. Assertion (A): The molecular mass of acetic acid in
(c) A is correct, R is incorrect. benzene is 120 instead of 60.
(d) A is incorrect, R is correct. Reason (R): The carboxylic acids exist as cyclic
154. Assertion (A): Carboxylic acid are more acidic than dimers.
phenols. (a) Both A and R are correct, R is the correct
Reason (R): The carbooxylate ion is less than explanation of A.
phenoxide ion. (b) Both A and R are correct, R is not the correct
(a) Both A and R are correct, R is the correct explanation of A.
explanation of A. (c) A is correct, R is incorrect.
(b) Both A and R are correct, R is not the correct (d) A is incorrect, R is correct.
explanation of A.
(c) A is correct, R is incorrect.
(d) A is incorrect, R is correct.
CARBOXLIYC ACID AND ITS DERIVATIVES 41

Match the following questions 160. Match the column

Column I Column II
159. Match the following Column I with the Column II and (Transformations) (Reagents)
choose the correct option from the codes given below. a. R–COOH  p. NH3/
R–CH2OH
Column I (Starting Column II (Reagent b. Ph  COOH  q. Cl2/Red P, H2O
material) with product) O
A. Cyclohexene 1. ||
Ph  C  NH 2
c. R–CH2COOH  r. P2O5, 
R  C H  COOH
B. Bromobenzene 2. |
Cl
d. CH3COOH  s. B2H6/H3O
(CH3CO)2O
(a) a – p, b – s, c – r, d – q
C. 4- 3. (b) a – r, b – p, c – s, d – q
methylacetop (c) a – s, b – q, c – r, d – p
henone (d) a – s, b – p, c – q, d – r
(a) A – 1, B – 2, C – 3 (b) A – 3, B – 1, C – 2
(c) A – 3, B – 2, C –1 (d) A – 2, B – 3, C – 1
42 CARBOXYLIC ACID AND ITS DERIVATIVES

Exercise – 2: Previous Year Questions

1. Self-condensation of two moles ethyl acetate in 8. The reagent which does not give acid chloride on
presence of sodium ethoxide yields treating with a carboxylic acid is
(CBSE AIPMT 2006) (AFMC 2007)
(a) ethyl butyrate (b) acetoacetic ester (a) PCl5 (b) Cl2
(c) methyl acetoacetate (d) ethyl propionate (c) SOCl2 (d) PCl3
2. Sodium formate on heating gives 9. Methyl acetate and ethyl acetate can be distinguished
(AFMC 2006) by
(a) oxalic acid and H2 (AIIMS 2007)
(b) sodium oxalate and H2 (a) hot alkaline KMnO4 (b) neutral FeCl3
(c) sodium oxalate (c) iodoform test (d) None of these
(d) CO2 and caustic soda 10. Claisen condensation is not given by
3. Which of the following represents soap? (CPMT 2007)
(AMU 2006)
(a) C17H35COOK (b) C17H35COOH
(c) C15H31COOH (d) (C17H35COO)2Ca (a)
4. Acetamide gives on the reaction with HNO2
(MP PMT 2006)
(a) acid (b) amine (b)
(c) alcohol (d) ketone
5. Which reaction is used for the preparation of
acetophenone ? (c)
(RPMT 2006)
(a) Reimer-Tiemann reaction
(b) Wurtz-Fittig reaction
(d)
(c) Friedel-Craft’s reaction
11. Which of the following process will give soap?
(d) Cannizzaro’s reaction
(Haryana PMT 2007)
6. CH3CO2C2H5 on reaction with sodium ethoxide in
(a) Hydrolysis (b) Saponification
ethanol gives A, which on heating in the presence of (c) Neutralisation (d) Acidification
acids gives B. Compound B is 12. Adipic acid on heating form
(AIIMS 2006) (CPMT 2008)
(a) CH3COCH2COOH
(b) CH3COCH3
(a)

(c)

(b)

(d)
7. Oleic, stearic, palmitic acids are
(BHU 2007) (c)
(a) nucleic acids (b) amino acids
(c) fatty acids (d) None of these
(d)
CARBOXLIYC ACID AND ITS DERIVATIVES 43

13. The end product ‘C’ in the following sequence of (CBSE AIPMT 2009)
chemical reactions is (a) CH2Br—CHBr—COOH
(Manipal 2008)
(b) CHBr2—CH2—COOH
CaCO 3  A Δ NH OH
CH 3 COOH   B  2 C (c) CH2Br—CH2—COBr
(a) acetaldehyde oxime (d) CH3—CBr2—COOH
(b) formaldehyde oxime
20.
(c) methylnitrate
(d) acetoxime
14. Carboxylic acids readily dissolve in aqueous sodium
bircarbonate, liberating carbon dioxide. Which one of
the following is correct?
Here, the compound X can be
(Manipal 2008)
(AFMC 2009)
(a) The free carboxylic acid and its conjugate base are
(a) acetic acid (b) formaldehyde
of comparable stability.
(c) formic acid (d) propionic acid
(b) The free carboxylic acid is more stable than its
21. The correct set of reagents for the following conversion
conjugate base
is:
(c) The conjugate base of the carboxylic acid is more
(AIIMS 2009)
stable than the free carboxylic acid
(d) The conjugate acid of the carboxylic acid is more
stable than the free carboxylic acid.
15. Waxes are esters of
(KCET 2008)
(a) glycerol
(b) long chain alcohols
(c) glycerol and fatty acid (a) P4/I2, Na, conc. H2SO4
(d) long chain
(b) P2O5, LiAlH4
16. The relative reactivities of acyl compounds towards
nucleophilic substitution are in the order of (c) P2O5/, H2O, P4/I2, Na
(CBSE AIPMT 2008) (d) P4/I2, Na, P2O5/
(a) acyl chloride > acid anhydride > ester > amide 22. Identify ‘Z’ in the following sequence of reactions.
(b) ester> acyl chloride > amide > acid anhydride NH   Y  P O
3  X 
CH 3 COOH  2 5
Z
(c) acid anhydride > amide > ester > acyl chloride
(d) acyl chloride > ester > acid anhydride > amide (CPMT 2009)
17. Acid hydrolysis of which of the following compounds (a) CH4 (b) CH3CHO
yields two different organic compounds? (c) CH3CN (d) CH3COO–NH4+
(AIIMS 2008) 23. The acidic nature of carboxylic acids
(a) CH3COOH (b) CH3CONH2 RCOOH  RCOO  H is due to
(c) CH3COOC2H5 (d) (CH3CO)2O (Manipal 2009)
18. Ethyl acetate is obtained when methyl magnesium (a) high degree of ionization of carboxylic acids.
bromide reacts with (b) greater resonance stabilization of the carboxylic
(Manipal 2008) acid over the carboxylate ion.
(a) ethyl formate (c) greater resonance stabilization of the caboxylate ion
(b) ethyl chloroformate over carboxylic acid.
(c) acetyl chloride (d) solubility of carboxylic acids in water.
(d) carbon dioxide
19. Propionic acid with Br2/P yields a dibromo product the
structure would be
44 CARBOXYLIC ACID AND ITS DERIVATIVES

24. When propionic acid is treated with aqueous sodium 31. In HCOO–, the two carbon-oxygen bonds are found to
bicarbonate, CO2 is liberated. The ‘C’ of CO2 comes be of equal length. What is the reason for this?
from (RPMT 2010)
(Manipal 2009) (a) The anion is obtained by the removal of a proton
(a) methyl group from the acid molecule.
(b) carboxylic acid group (b) Electronic orbitals of carbon atoms are hybridised.
(c) methylene group (c) The CO bond is weaker than C—O bond.
(d) bicarbonate (d) The anion HCOO– has two resonating structures.
25. In the following reaction, 32. In a set of reactions, acetic acid yielded product D.
SOCl Benzene
2  A 
CH 3 COOH  
Conc. H SO 4 Anhy. AlCl
3
C 2 H 5 OH  CH 3 COOH   2  CH 3 COOC 2 H 5
 H 2O HCN HOH
B  C  D.
C2H5OH acts as
The D would be
(AFMC 2009)
(RPMT 2010)
(a) electrophile (b) nucleophile
(c) dehydrating agent (d) All of these
26. Oxalic acid on heating with conc. H2SO4 gives
(AFMC 2010)
(a) CO only (b) CO2 only (a)
(c) CO2 + H2O (d) CO+ CO2 + H2O
27. Which acid is present in vinegar? (MP PMT 2010)
(a) CH3COOH (b) H2SO4
(c) HCl (d) HNO3
(b)
28. CH3COOH when reacts with C2H5OH give a product.
The same product is obtained by which reaction.
(MHCET 2010)
(a) Acetic acid + Methanol
(b) Acetic anhydride + Water (c)
(c) Acetic anhydride + Ethanol
(d) Acetamide + Methanol
29. The product formed as a result of reaction of CH3MgBr
and CO2, on further hydrolysis gives
(d)
(RPMT 2010)
33. Which of the following is most acidic?
(a) CH3COOH (b) HCOOH
(Haryana PMT 2010)
(c) oxalic acid (d) acetic acid (a) BrCH2COOH (b) ClCH2COOH
30. The reaction,
(c) FCH2COOH (d) ICH2COOH
Red P
RCH 2 CH 2 COOH   RCH 2 CHCOOH is: H O H 
Br |
2
Br 34. RCOOH 3  
 X   RCH 2 NH 2
(RPMT 2010) Identify the X in the above reaction.
(a) Reimer-Tiemann reaction (Haryana PMT 2010)
(b) Hell-Volhard-Zelinsky reaction (a) Alkane nitrile (b) Alkyl isonitrile
(c) Cannizzaro’s reaction (c) Aldoxime (d) Alkyl nitrile
(d) Sandmeyer’s reaction
CARBOXLIYC ACID AND ITS DERIVATIVES 45

35. In a set of reactions, ethyl benzene yielded at product 41. Write the IUPAC name of the following compounds.
D. (MHCET 2014)

‘D’ would be
(RPMT 2011)

(a) 2-amino-4-hydroxy benzoic acid

(b) 6-amino-4-hydroxy benzoic acid
(a) (c) 3-amino-4-carboxyphenol
(d) 2-carboxy-4-hydroxyaniline
42.
(b)

(c) Identify the compound D in the above mentioned series

of reactions. (MHCET 2014)

(d)
36. The correct order of decreasing acid strength of (a)
trichloroacetic acid (1), trifluoroacetic acid (2), acetic
acid (3) and formic acid (4) is (AIPMT 2012)
(a) (2) > (1) > (4) > (3) (b) (2) > (4) > (3) > (1)
(c) (1) > (2) > (3) > (4) (d) (1) > (3) > (2) > (4) (b)
37. Rosenmund reduction is used for the preparation of
(Manipal 2012)
(a) aldehydes (b) ketones
(c)
(c) ethers (d) fatty acids
38. When salicylic acid is distilled with Zn-dust, the
product obtained is (KCET 2013)
(a) zinc salicylate (b) salicylaldehyde
(d)
(c) phenol (d) benzoic acid
39. Among the following compounds the one that is most (i)NH
3 NaOBr
43. C6 H5COOH   P  
reactive towards electrophilic nitration is (ii) Δ
(AIPMT 2014) (i) Conc.H SO
2 4 R
(a) benzoic acid (b) nitrobenzene Q  , R is
(ii) Heat to 460 K
(c) toluene (d) benzene (KCET 2014)
40. Methyl acetate will be obtained by reacting CH3OH (a) o-bromo sulphanilic acid
with (Manipal 2014) (b) sulphanilamide
(a) CH3COOH (b) CH3COCl (c) sulphanilic acid
(d) p-bromo sulphanilamide
(c) (CH3CO)2O (d) All of these
46 CARBOXYLIC ACID AND ITS DERIVATIVES

44. In the following reaction,

LiAlH
C 6 H 5 COOCH 3 4
 A  B
H 2O
(d)
49. Consider the following acids :
A and B are respectively (i) F3C –– COOH, (ii) CH3COOH,
(CPMT 2016) (iii) C6H5COOH, (iv) CH3CH2COOH
(a) C6H5CH2OH + HCOOH Correct order of pKa value is
(b) C6H5CH2OH + CH3OH (AIIMS 2019)
(c) C6H5OH + CH3COOH (a) (i) > (iii) > (ii) > (iv)
(b) (iv) > (ii) > (iii) > (i)
(d) C6H5COOH + CH3OH
(c) (iv) > (iii) > (ii) > (i)
45. The correct order of strengths of the carboxylic acids (d) (i) > (ii) > (iv) > (iii)
(NEET 2016) 50. Carboxylic acids have higher boiling points than
aldehydes, ketones and even alcohols of comparable
molecular mass. It is due to their (NEET 2020)
(a) more extensive association of carboxylic acid via
van der Waals’ force of attraction
Is (b) formation of carboxylate ion
(a) I > II > III (b) II > III > I (c) formation of intramolecular H-bonding
(c) III > II > I (d) II > I > III (d) formation of intermolecular H-bonding
46. Which of the following reagents is used to distinguish 51. RMgX  CO2 
dry
 Y 
H3 O 
 RCOOH
ether
phenol and benzoic acid?
(AIIMS 2017) What is Yin the above reaction? (NEET 2022)
(a) aq. NaOH (b) Tollen’s reagent (a) RCOO–Mg+X (b) R3CO–Mg+X
(c) Molisch reagent (d) Neutral FeCl3 (c) RCOO– X+ (d) (RCOO)2Mg
47. The product of acid hydrolysis of (P) and (Q) can be 52. Complete the following reaction :
distinguished by

[C] is
(NEET 2023)

(JIMPER 2017)
(a) Lucas reagent (a)
(b) 2, 4-DNP
(c) Fehling’s solution
(d) NaHSO3 (b)
48. The reaction that does not give benzoic acid as the
major product is (NEET 2019)

(c)

(a)
(d)

(b)

(c)
CARBOXLIYC ACID AND ITS DERIVATIVES 47

53. Match List I with List I (NEET 2024)

List I (Reaction) List II (Reagents Conditions)

(A)

I. +
Anhyd.AlCl3
(B) II. CrO3

(C) III. KMnO4/KOH, Δ

(D) IV. (i) O3, (ii) Zn-H2O

Choose the correct answer from the options given below:

(a) A-III, B-I, C-II, D-IV
(b) A-IV, B-I, C-II, D-III
(c) A-I, B-IV, C-II, D-III
(d) A-IV, B-I, C-III, D-II
48 CARBOXYLIC ACID AND ITS DERIVATIVES

Exercise – 3: Achiever’s Section

Single Answer Type Questions (d) methylamine salt and ethanoic acid
1. Picric acid is 4. The end product B in the sequence of reactions,
 CN A  NaOH  B
(a) (b) R  X  is
(a) a alkane
(b) a carboxylic acid
(c) sodium salt of carboxylic acid
(d) a ketone
5. Through which of the following reactions number of
carbon atoms can be increased in the chain?
(i) Grignard reaction
(ii) Cannizzaro’s reaction
(iii) Aldol condensation
(iv) HVZ reaction
Choose the correct option.
(c) (d) (a) Only (iii) and (i)
2. Structure of the compound whose IUPAC name is 3- (b) Only (iii) and (ii)
ethyl-2-hydroxy-4-methylhex-3-en-5-ynoic acid is: (c) Only (iii) and (iv)
(a) (d) (i), (ii), (iii) and (iv)
6.

Here Z is
(b) (a)

(b) (CH3)3CCOOH

(c) (c)

(d) Both (a) and (b)

7. Identify the correct order of boiling points of the
(d)
following compounds
(A) CH3CH2 CH2CH2 OH
(B) CH3CH2CH2CHO
(C) CH3CH2CH2COOH
(a) A > B > C (b) C > A > B
3. Ethyl isocyanide on hydrolysis in acidic medium
(c) A > C > B (d) C > B > A
generates
(a) ethylamine salt and methanoic acid
(b) propanoic acid and ammonium salt
(c) ethanoic acid and ammonium salt
CARBOXLIYC ACID AND ITS DERIVATIVES 49

8.

(d)
9. 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
10. When CH2 = CH – COOH is reduced with LiAlH4 ,
the compound obtained will be:
(a) CH3 – CH2 – COOH
(b) CH2 = CH – CH2OH
(c) CH3—CH2—CHO
(d) CH3 – CH2 – CH2 – OH
11. End product of the following reaction is
(a) Cl alc. KOH
CH 3 CH 2 COOH 
2
 A  B
red P

(a) (b)

(c) (d)
12. The strongest acid among the following is –
(a) Salicylic acid
(b) m-hydroxybenzoic acid
(b) (c) p-hydroxybenzoic acid
(d) Benzoic acid
13. An enantiomerically pure acid is treated with racemic
mixture of an alcohol having one chiral carbon. The
ester formed will be
(a) optically active mixture (b) pure enantiomer
(c) meso compound (d) racemic mixture
14. Which of the following is correct order of acidity?
(a) HCOOH > CH3COOH > ClCH2COOH >
C2H5COOH
(b) ClCH2COOH > HCOOH > CH3COOH >
(c) C2H5COOH
(c) CH3COOH > HCOOH > ClCH2COOH >
C2H5COOH
(d) C2H5COOH > CH3COOH > HCOOH >
ClCH2COOH
50 CARBOXYLIC ACID AND ITS DERIVATIVES

15. The correct order of increasing acid strength of the (a) IV > I > II > III > V (b) V > II > III > I > IV
compounds (c) V > II > IV > III > I (d) V > II > IV > I > III
(A) CH3CO2H 19. Hydrogenation of benzoyl chloride in the presence of
(B) MeOCH2CO2H Pd-BaSO4 gives
(C) CF3CO2H (a) benzyl alcohol (b) benzaldeyde
(c) benzoic acid (d) phenol
(i)CH 3 MgBr (excess)
20. Ethyl Acetate  P, the product will
(D) is (ii) H O 
3

be
(a) D < A < B < C (b) A < D < B < C
(c) B < D < A < C (d) D < A < C < B
(a) (b)
16. In a set of the given reactions, acetic acid yielded a
product C.
C6H6
CH 3 COOH  PCl5  A  (c) (d)
[Link]
3 21. Benzoyl chloride is prepared from benzoic acid by
(i) C H MgBr
2 5
B 
C (a) Cl2, hv (b) SO2Cl2
(ii) H O
3 (c) SOCl2 (d) Cl2, H2O
Product C would be
22. In the following sequence of reactions:
KMnO SOCl H /Pd
Toluene  4  A  2  B 
2 C,
(a) BaSO
4
(b) CH3CH(OH)C2H5 the product C formed will be :
(c) CH3COC6H5 (a) C6H5CH2OH (b) C6H5CHO
(d) CH3CH(OH)C6H5
(c) C6H5COOH (d) C6H5CH3
17. Which of the following represents the correct order of
the acidity in the given compounds? 23. Acetamide is treated separately with the following
(a) FCH2COOH > CH3COOH > BrCH2COOH > reagents. Which one of these would give methyl amine?
ClCH2COOH (a) PCl5 (b) NaOH + Br2
(b) BrCH2COOH > ClCH2COOH > FCH2COOH > (c) Sodalime (d) Hot conc. H2SO4
CH3COOH 24. Benzamide on treatment with POCl3 gives
(c) FCH2COOH > ClCH2COOH > BrCH2COOH > (a) aniline (b) benzonitrile
CH3COOH (c) chlorobenzene (d) benzyl amine
(d) CH3COOH > BrCH2COOH > ClCH2COOH > 25. In the given reaction,
FCH2COOH H O
2 I
18. The correct order for the acidic character of the  C6 H5CO 2 O 
following carboxylic acids is 2
H O
C 6 H 5 COOCOCH 3   II
Identify the product(s) formed in the given reaction.
I II
(a) 2 moles of benzoic acid 2 moles of ethanoic acid
(b) 2 moles of benzoic acid 1 moles of benzoic acid and
1 mole of ethanoic acid
(c) 1 mole of ethanoic acid 1 mole of benzoic acid
(d) 1 mole of benzoic acid 1 mole of butanoic acid
CARBOXLIYC ACID AND ITS DERIVATIVES 51

Assertion and Reason Type Questions 28. Assertion: Acetic acid does not give haloform reaction.
(A) If both assertion and reason are correct and reason is the Reason: Acetic acid has no -hydrogen.
correct explanation of assertion. (a) A (b) B
(B) If both assertion and reason are true but reason is not the (c) C (d) D
correct explanation of assertion. 29. Assertion: Formic acid reduces mercuric chloride.
(C) If assertion is true but reason is false. Reason: Formic acid is stronger than acetic acid.
(D) If reason is true but assertion is false. (a) A (b) B
26. Assertion: p–hydroxybenzoic acid has a lower boiling (c) C (d) D
point than o–hydroxybenzoic acid. 30. Assertion: Acid catalysed hydrolysis of ester is
Reason: o–hydroxybenzoic acid has intramolecular reversible on the other hand base catalysed hydrolysis is
hydrogen bonding. irreversible.
(a) A (b) B Reason: In acid catalysed ester hydrolysis carboxylic
(c) C (d) D acid is formed on which nucleophile attack of alcohol is
27. Assertion: (CH3)3C–COOH does not give HVZ possible while in base catalysed ester hydrolysis
reaction. carboxylate anion is formed on which nucleophillic
Reason: It does not have any -hydrogen attack is not possible.
(a) A (b) B (a) A (b) B
(c) C (d) D
(c) C (d) D
52 CARBOXYLIC ACID AND ITS DERIVATIVES

Notes:

Find Answer Key and Detailed Solutions at the end of this book

CARBOXYLIC ACID AND ITS

DERIVATIVES
AMINES
Chapter 07 54

Amines

1. Introduction 2. Classification of Amines

Amines are organic derivatives of ammonia with one or more Amines are classified as primary (1°), secondary (2°) , or tertiary
alkyl or aryl groups bonded to the nitrogen atom. Amines serve (3°), corresponding to one, two or three alkyl or aryl groups
many functions in living organisms, such as bioregulation, bonded to nitrogen.
neurotransmission, and defense against predators. Because of Quaternary ammonium salts have four alkyl or aryl bonds to a
their high degree of biological activity, many amines are used as nitrogen atom. The nitrogen atom bears a positive charge Just as
drugs and medicines. it does in simple ammonium salts such as ammonium chloride.
The alkaloids are an important group of biologically active amines, The following are examples of quaternary (4°) ammonium salts.
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.

Table - 9.1 : Classification of Amines

SCAN CODE
Amines
AMINES 55

3. Nomenclature of Amines
Table - 9.2 : Nomenclature of alkyl Amines
Amine Common name IUPAC Name
Ethylamine Ethanamine
n-Propylamine Propan - 1 - amine
Isopropylamine Propan - 2 - amine

Ethylmethylamine N-Methylethanmine

Trimethylamine N,N- Dimethylmethanamine

N, N - Diethylbutylamine N, N - Diethylbutan - 1 - amine

Allylamine Prop-2-en-1-amine
Hexamethylenediamine Hexane - 1, 6 - diamine

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 107° from the “ideal” sp 3 bond angle of 109.5°.
Trimethylamine shows less angle compression because the bulky
methyl groups open the angle slightly.

A tetrahedral amine with three different substituents (and a lone

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
56 AMINES

In case of quaternary ammonium salts with a symmetrical nitrogen 5.1 Alkyl Halides
atoms, inversion of configuration is not possible because there
is no lone pair to undergo nitrogen inversion. 5.1.1 Hoffmann’s Ammonolysis Method
It is an ammonolysis. An alkyl halide and an ethanolic solution of
ammonia are heated in a sealed tube at 100°C.
(a) The process gives a mixture of products.
(b) Tertiary alkyl halide is not suitable as it gives an alkene.
(c) Reaction follows bimolecular substitution (SN2).
For Example:

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
the 120° bond angles that facilitate inversion

5. Preperation of Amines

5.1.2 Gabriel’s Phthalimide Synthesis

Phthalamide is treated with KOH first and then potassium
phthalamide is heated with alkyl halide to yield alkyl phthalamide.
The subsequent hydrolysis produces exclusively 1° amine.
Alkyl phthalamide is also treated with hydrazine to get a better
yield of 1° amine.

SCAN CODE
Amines
AMINES 57
For Example: 5.3 Carbonyl Compounds
5.3.1 Reductive Amination
Several aldehydes and ketones are converted into amines by
reduction in the presence of ammonia.
Reduction can be accomplished catalylically. (hydrogen (20 –
150 atm) over Raney nickel at 40° – 150°C or by use of sodium
cyanohydridoliorute, NaBH3CN).
For Example:
NH3 ,H2 ,Ni
CH3  CH 2 5 CHO   CH3  CH 2 5 CH 2 NH 2
Heptanal 1  Aminoheptane
For Example:

For Example:

5.1.3 Grignard Reagent

Grignard reagent or a trialkyl borane on treatment with chloramine For Example:
gives the primary amine. O
|| H ,Ni
RMgX  ClNH 2  R  NH 2  MgXCl 2
R — C— H  CH 3CH 2 NH 2  R — CH 2 — NHCH 2 CH 3
2Amine
5.2 Alcohols
5.2.1 Sabatier Reaction 5.4 Carboxylic Acids & Derivatives
Alcohols and ammonia are heated underpressure in the presence
of a catalyst e.g., copper chromite or alumina. A mixture of products 5.4.1 Schmidt Reaction
is obtained. A treatment of cold conc. H2SO4 to the mixture of carboxylic acid
and hydrazoic acid gives 1° amine.
For Example:
RCOOH + N 3 H 
Cold conc.
H 2SO 4
 RNH 2 + CO 2 + N 2

NOTE:
1. The product molecule contains one carbon atom less than
that in acid.
2. Isocyanate is formed as an intermediate in the reaction.

SCAN CODE
Amines
58 AMINES

For Example: For Example:

5.4.2 Curtius Reaction

The reaction involves the pyrolysis of acyl azide to produce
isocyanates. The subsequent hydrolysis gives amine.
For Example:

5.4.4 Hydrolysis of Amides & Isocyanides

N-substituted amide and isocyanide on hydrolysis give 1° amine.
For Example:

For Example:

For Example:
KOH, H O
R–NC   2 
 R–NH 2 +HCOOK

Hydrolysis of Isocyanates also yields amines.


5.4.3 Hofmann Degradation of Amides H3O
R — N  C  O  R — NH 2
Amide is warmed with bromine and concentrated aqueous KOH 
Alkyl Isocyanate
or NaOH solution.
(a) Product is 1° amine having one carbon less than amide. 5.4.5 Decarboxylation of Amino Acids
(b) Alkyl isocyanate is the intermediate and rearrangement is Amino acids on heating with barium hydroxide gives 1° amine.
intramolecular. Quaternary ammonium hydroxide on heating gets decomposed
into alcohol if  -hydrogen is not present in the alkyl group but
if there is  -hydrogen, Hofmann elimination proceeds.

SCAN CODE
Amines
AMINES 59
5.5 Nitrogen Compounds NOTE:
5.5.1 Reduction of Cyanides, Isocyanides, Oximes, 1. 1° aromatic amines are usually prepared by the reduction of
corresponding nitro compounds by tin, iron or zinc with
Nitrile (–CN), oxime (=NOH), imine (= NH), enamine HCl or CH3COOH.
etc. on catalytic reduction with H 2/Ni give the 2. Aqueous ethanolic ammonium hydrogen sulphide, aqueous
corresponding amine. sodium sulphide or mcthanoic sodium hydrogen sulphide
selectively reduce one nitro group into a polynitro compound.
NOTE: For Example:
1. The reduction of nitrile by Na/C2H5OH is known as Mendius Sn,HCl
CH 3 CH 2 NO 2  6[H]    CH 3 CH 2 NH 2
reaction. Pt
CH CH NO  3H    CH CH NH
2. In most of the cases LiAlH4 is also effective for reduction. 3 2 2 2 3 2 2

3. Reduction of alkyl isocyanidcs with Na/C2H5OH or H2/Pt For Example:

gives 2° amine.

For Example:
H2 ,Ni,
CH3CH2 C  N 
or  CH3CH2 CH2 NH2
Na,C2 H5OH
For Example:
H2 ,Ni For Example:
CH 3 — C  NOH 
or Na,C2 H5OH
 CH 3 — CH — NH 2
| |
CH3 CH3
Acetonoxime
For Example:
H 2 ,Ni
Ph — CH  NH   PhCH 2 — NH 2
Imine
For Example:

For Example:

5.5.2 Reduction of Nitro Compounds

Nitroalkanes are usually reduced by tin and hydrochloric acid or
lithium aluminium hydride into corresponding amine, H2 and
catalyst is also used for such a reduction.

SCAN CODE
Amines
60 AMINES

For Example:
6. Physical Properties

6.1 State
The lower aliphatic amines are gases with fishy odour. Primary
amines with three or more carbon atoms are liquid and higher
ones are solid.
Aniline and other aryl amines are usually colourless but gets
coloured on storage due to atmospheric oxidation.

6.2 Dipole Moment

Amines are strongly polar because the large dipole moment of
the lone pair of electrons adds to the dipole moments of the
and bonds.

For Example:

6.3 Solubility
Primary and secondary amines have N—H bonds, allowing them
to form hydrogen bonds. Having no N—H bonds, pure tertiary
amines cannot engage in hydrogen bonding. They can, however,
accept hydrogen bonds from molecules having O—H or N—H
bonds.

1° or 2° Amine
Hydrogen Bond Donor and Acceptor

3° Amine
Hydrogen Bond Acceptor only

SCAN CODE
Amines
AMINES 61
Therefore, lower aliphatic amines are soluble in water because Basic strength of amines in gaseous phase increases with number
they can form hydrogen bonds with water. However, solubility of alkyl group (+ I effect) attached with nitrogen atom.
decreases with increase in molar mass of amines due to increase
in size of the hydrophobic alkyl part. Higher amines are essentially Basic strength in aqueous phase
insoluble in water.
Basic character of amine depends upon the ease of formation of
6.4 Boiling Point the cation by accepting a proton and stability of this cation.
Because nitrogen is less electronegative than oxygen, the N—H Greater the extent of H-bonding in water and more the basic
bond is less polar than O—H bond. Therefore, amines form weaker strength.
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.
Table - 9.3 : Comparison of boiling points of
Amines, Alcohols & Alkanes of Similar Molecular
Masses
[Link]. Compound Molar mass b.p./K
1. n-C4H9NH2 73 350.8
More the steric hindrance, lesser the basic strength of amine.
2. (C2H5)2NH 73 329.3
3. C2H5N(CH3)2 73 310.5
4. C2H5CH(CH3)2 72 300.8
5. n-C4H9OH 74 390.3

6.5 Basic character of Amines

Amines are basic in nature like ammonia
The basic nature of an amine is due to the presence of an unshared Less + I Moderate + I More + I
pair (lone pair) of electrons on N atom. More Moderate Less
solvation solvation solvation
Less steric Moderate steric More steric
Basic strength in gaseous phase hindrance hindrance hindrance
Alkylamines (1°, 2° and 3°) are stronger bases than ammonia. Overall order of basic strength in aqueous phase.
Basic strength explained in terms of electron releasing inductive Methyl substituted amine
effect of alkyl group. The electron density on the nitrogen atom  CH3 2 NH  CH 3 NH2   CH3 3 N  NH3
increases by + I effect. Alkylamines can donate the lone pair of
2 1 3 Ammonia
electrons more easily than ammonia.
Ethyl substituted amine
 C2 H5 2 NH   C2 H5 3 N  C2 H5 NH 2  NH3
2 3 1 Ammonia

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6.6 Basic Strength of Aromatic Amines 7. Chemical Properties of Amine

Aniline is less basic than ammonia and aliphatic amines. Because
lone pair of e- is less available for protonation due to resonance. 7.1 Alkylation
Amines undergo alkylation on reaction with alkyl halides.

7.2 Acylation
Aliphatic and aromatic primary and secondary amines react with
acid chlorides, anhydrides and esters by nucleophilic substitution
reaction to form amide.
The reaction is carried out in the presence of a base (generally
pyridine).
Fig. 9.1 : Resonating structures of Aniline Base removes HCl so formed and shifts the equilibrium to the
right hand side.
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
For Example: Order of basic strength

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.

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7.4 Cope Elimination For Example

Tertiary amine oxides having  -hydrogen atom on heating form

an alkene and N, N-disubstituted hydroxylamine.
The alkene formed is the Hofmann elimination product.

For Example:

7.5 Hofmann’s Exhaustive Methylation and

Elimination

8. Introduction of Aniline
One of the starting materials used for preparing sulpha drugs is
Quarternary Ammonium Iodides are converted to hydroxides with aniline. Aniline is a primary aromatic amine which consists of an
moist Ag2O. The hydroxide on heating undergo elimination to –NH2 group attached to the benzene ring.
give 3° amines and alkenes. The important aspect of this
elimination is that the least substituted alkene is the major product
(Hofmann Rule). This is known as Hofmann’s Elimination.

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8.1 Nomenclature of Aryl Amines

Table - 9.4 : Nomenclature of Aryl Amines

Amine Common name IUPAC Name

Aniline Aniline or Benzenamine

o-Toluidine 2- Methylaniline

p-Bromoaniline 4-Bromobenzenamine
or
4- Bromoaniline

N, N- Dimethylaniline N, N - Dimethylbenzenamine

9. Preparation of Aromatic Amines 9.1.2 Catalytic Hydrogenation Reducing Agents:

Besides the methods in the preparation of aliphatic amines, H 2 , Pd  C / Et  OH
following methods can also be used for the preparation of aromatic
amines.

9.1 Reduction of Nitro Compounds

9.1.1 Vapour-Phase Reduction
Reducing Agents:
CuO on SiO2 or V – Pt Catalyst
For Example:
9.2 Ammonolysis of Aryl Halides

NOTE:
If deactivating groups (–NO2 etc.) are at ortho or para position,
rcaction becomes quite easy to carryout.

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AMINES 65
9.3 Phenol and Ammonia 10.2 Halogenation
Amine group (NH2) is a very strong activating group and an
ortho/para director. It forms 2,4,6-tribromo aniline on normal
bromination in H2O.

9.4 Reducing of Azo Compound

ortho and para derivatives can be made by decreasing the

activating power of amino group by acetylation of aniline.
–NHCOCH3 group is a mild ortho and para director.
For Example:

10. Reactions of Aromatic Amines

10.1 Oxidation
Aromatic amines are readily oxidised to various products
depending on conditions. Under controlled oxidation using 10.3 Nitration
Na2Cr2O7 and H2SO4 aniline is oxidised to p-benzoquinone. In
The normal nitration of aniline is not done as nitrating mixture is
fact, on standing in air, p-benzoquinone is formed.
oxidising and NH2 is a strong activating group. Moreover, at
If oxidation is not controlled, a black dye, aniline black is formed.
288K aniline is protonated to form the anilinium ion which is meta
directing. That is why besides the ortho and para derivatives, a
significant amount of meta derivative is also formed.

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10.4 Sulphonation

However, by protecting the –NH2 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.

NOTE:
Usually –NH2 group attached to benzene is unable to form zwitter
ion but here –SO3H is very strongly acidic. Hence sulphanilic
acid forms zwitter ion. For example when –NH2 group is attached
to benzoic acid in any position, zwitter ion is not formed.

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11. Diazonium Salt & Reactions

Fig. 9.2 : Reactions of Diazonium salt

12. Test of Amines 12.1 Sulphonylation-Hinsberg Test

Treatment with benzene sulphonyl chloride (Hinsberg reagent)
1. Sulphonylation-Hinsberg Test
or p-toluene sulphonyl chloride.
2. Nitrous Acid Test
(a) The reaction is used to separate the amine mixture.
3. Carbylaminc Reaction
(b) 1° and 2° amine, due to the presence of active hydrogen react
4. Treatment with CS2/HgCl2 and give corresponding sulphonamidc while 3° amine does
not react.
(c) 1° amine product N-alkyl benzene sulphonamide is soluble in
KOH forming a water-soluble salt.

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12.3 Carbylamine Reaction

1° amine on treatment with chloroform and alcoholic KOH gives
out unpleasant or pungent vapours of alkyl carbylamine
(isocyanide).
The reaction is known as a test for 1° amine.
CHCl3 + OH  :CCI 2 + H 2 O

12.4 Treatment with CS2/HgCl2

(a) 1° amine on warming with CS2 produces dithiocarbamic acid,
12.2 Nitrous Acid Test which is decomposed by mercuric chloride to alkyl
(a) 1° amine on reaction with HNO2 gives usually an alcohol. isothiocyanate. It is called as Hofmann’s Mustard Oil
The reaction involves the formation of diazonium salt as an Reaction.
intermediate. (b) Although 2° amine gives dithiocarbamic acid but is not
(b) 2° amine gives nitrosoamine which is a yellow oily liquid. decomposed by mercuric chloride.
(c) 3° amine dissolves in cold HNO2 to form an unstable salt (c) 3° amine don’t react with CS2
which on heating decomposes to give nitrosoamine and an
alcohol.
For Example:
HNO
2  CH CH OH  N  H O
CH 3CH 2 NH 2  3 2 2 2
For Example:

 CH3 2 NH 
HNO 2
  CH3 2 N  N  O  H 2 O

For Example:

 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.

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AMINES 69

Summary
Preparation of Amines Properties of Amines

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Properties of Aniline

Reaction of Diazonium Salt

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Exercise – 1: Basic Objective Questions

Introduction to Amines
8. Select the quaternary ammonium compound from the
1. Which IUPAC name of H2N – CH2 – CH2 – NH2 is given options.
(a) ethan-1-diamine (a) Trimethylphenyl ammonium bromide
(b) ethane-1, 2-diamine (b) triphenylamine
(c) ethanamine (c) dibenzyl amine
(d) ethane-2- diamine (d) None of the above
2. The correct IUPAC name for CH2=CHCH2NHCH3 is 9. Choose the arylamine(s) from the given options.
(a) Allylmethylamine (a) Benzylamine (b) dibenzyl amine
(b) 2-amino-4-pentene (c) triphenylamine (d) All of these
(c) 4-aminopent-1-ene 10. C3H9N represents
(d) N-methylprop-2-en-1-amine (a) Primary amine (b) Secondary amine
3. What is the common name of (c) Tertiary amine (d) All
11. Allyl isocyanide has
(a) 9 sigma bonds and 4 pi bonds
(b) 8 sigma bonds and 5 pi bonds
(a) 2-(N-methylamino)-4- methylpentane (c) 8 sigma bonds, 3 pi bonds and 4 non-bonding
(b) 5-(N-methylamino)-2-4, dimethylbutane electrons
(c) 4-(N-methylamino)-2,4-dimethylutane (d) 9 sigma bonds, 3 pi bonds and 2 non-bonding
(d) 4-(N-methylamino)-4-methylpentane electrons
4. Which of the following is a secondary amine? 12. How many primary amines are possible for the formula
(a) 2-Butanamine C4H11N?
(b) N-Methylpiperidine (a) 1 (b) 2
(c) N-Methyl-2-pentanamine (c) 3 (d) 4
(d) p-Anisidine 13. Select the incorrect match from the given options.
5. A secondary amine is (a) Position isomers  Butanamine and butan-2 amine
(a) An organic compound with two – NH2 groups (b) Chain isomers  Butan-2-amine and 2-
(b) A compound with two carbon atoms and an –NH2 methylpropan-2-amine
group (c) Metamers  N-methylpropanamine and N-
(c) A compound with an –NH2 group on the carbon methylpropan-2-amine
atom in number 2 position (d) Metamers  N-methylpropan-2-amine and N-
(d) A compound in which two of the hydrogens of NH3 ethylethanamine
have been replaced by organic groups 14. Among NH3 and (CH3)3N whose bond angle is more ?
6. CH2 = CH–CH2–NH–CH3 is a (a) (CH3)3N > NH3 (b) (CH3)3N < NH3
(a) Secondary amine (c) (CH3)3N = NH3 (d) None of the above
(b) Primary amine 15. The hybridization of nitrogen atom in amines is :
(c) Tertiary amine (a) sp (b) sp2
(d) None of these (c) sp3 (d) dsp2
7. Which of the following is a 3º amine? 16. Trimethylamine has :
(a) 1-methylcyclohexylamine (a) planar geometry
(b) Triethylamine (b) trigonalbipyramidal geometry
(c) tert-butylamine (c) pyramidal shape
(d) N-methylaniline (d) octahedral geometry
72 AMINES

17. Nitrogen atom of amines is …I… and carries …II… 24. Which of the following amides will not undergo
unshared pair of electrons. Hoffmann bromamide reaction?
Fill the blanks with appropriate words. (a) CH3CONH2 (b) CH3CH2CONH2
(a) I→ divalent; II → One
(c) C6 H5CONH2 (d) CH3CONHCH3
(b) I→ divalent; II → Two
(c) I→ trivalent; II → One 25. The best reagent for converting, 2-phenyl-propanamide
(d) I → trivalent; II → two into 1-phenylethanamine is ..................
18. Which is the hybridization and the geometry of the (a) excess H2/Pt (b) NaOH/Br2
amines? (c) NaBH4/methanol (d) LiAlH4/ether
(a) sp2 hybridized and pyramidal geometry 26. Acetamide is treated separately with the following
(b) sp3 hybridized and planar geometry reagents. Which one of these would give methylamine?
(c) sp2 hybridized and planar geometry (a) PCl5 (b) Sodalime
(d) sp3 hybridized and pyramidal geometry (c) NaOH + Br2 (d) Hot conc. H2SO4
19. Which of the following statement(s) is/are true about 27. Gabriel phthalimide reaction is used for preparation of
amines? (a) Primary aromatic amines (b) Secondary amines
(a) Amines are derived by replacing one or more (c) Primary aliphatic amines (d) Tertiary amines
hydrogen atoms of ammonia molecule by alkyl/aryl 28. The source of nitrogen in Gabriel synthesis of amines is
group(s) .................
(b) In nature, they occur among proteins, vitamins, (a) Sodium azide, NaN3
alkaloids and hormones
(b) Sodium nitrite, NaNO2
(c) Synthetic examples of amines are polymers,
dyestuffs and drugs (c) Potassium cyanide, KCN
(d) All of the above (d) Potassium phthalimide, C6H4 (CO)2 N–K+
20. Assertion (A): The angle of C–N–C in the 29. Best method for preparing primary amines from alkyl
trimethylamine is 108°. halides without changing the number of carbon atoms
Reason (R): There is unshared pair of electron in the in the chain is
trimethylamine which make the angle less than 109.5°. (a) Hoffmann Bromamide reaction
(a) Both A and R are correct; R is the (b) Gabriel phthalimide synthesis
correct explanation of A (c) Sandmeyer reaction
(b) Both A and R are correct; R is not the correct (d) Reaction with NH3
explanation of A. 30. Which of the following methods of preparation of
(c) A is correct; R is incorrect amines will not give same number of carbon atoms in
(d) R is correct; A is incorrect the chain of amines as in the reactant?
(a) Reaction of alkyl nitrile with LiAlH4.
Preparation of Amines (b) Reaction of amide with LiAlH4 followed by
treatment with water.
Na  C H OH
21. 2 5  X
CH 3 CN   (c) Heating alkyl halide with potassium salt of
phthalimide followed by hydrolysis.
The compound X is
(d) Treatment of amide with bromine in aqueous
(a) CH3CONH2 (b) CH3CH2 NH2
solution of sodium hydroxide.
(c) C2 H6 (d) CH3 NHCH3 31. Which of the following amines can be prepared by
22. Mendius reduction converts an alkyl cyanide to Gabriel synthesis?
(a) a primary amine (b) an aldehyde I. Isobutyl amine II. 2-Phenylethylamine
(c) a ketone (d) an oxime III. N-methylbenzylamine IV. Aniline
23. Which of the following gives primary amine on (a) Only I and II (b) Only II and III
reduction? (c) Only III and IV (d) Only I and IV
(a) CH3CH2NO2 (b) CH3CH2 – O – N = O
(c) C6H5N = NC6H5 (d) CH3CH2NC
AMINES 73

32. Indicate which nitrogen compound amongst the (d) Potassium phthalimide, C6H4(CO)2N–K+
following would undergo Hoffmann reaction (i.e., 39. The best reagent for converting 2-phenylpropanamide
reaction with Br2 and strong KOH) to furnish the into 2-phenylpropanamine is.
primary amine (R – NH2). (a) excesss H2
(a) RCONHCH3 (b) RCOONH4 (b) Br2 in aqueous NaOH
(c) RCONH2 (d) R — CO — NHOH (c) iodine in the presence of red phosphorus
33. Amongst the given set of reactants, the most (d) LiAlH4 in ether
appropriate for preparing 2º amine is. 40. An organic compound ‘A’ on treatment with NH3 gives
(a) 2º R—Br + NH3 ‘B’ which on heating gives ‘C’, ‘C’ when treated with
(b) 2º R—Br + NaCN followed by H2/Pt Br2 in the presence of KOH produces ethylamine.

(c) 1º R—NH2 + RCHO followed by H2/Pt Compound ‘A’ is

(a) CH3COOH
(d) 1º R—Br (2 mol) + potassium phthalimide followed
by H3O+/heat (b) CH3CH2CH2COOH

34. Benzylamine may be alkylated as shown in the (c)

following equation :
C6H5CH2NH2 + R–X → C6H5CH2NHR
Which of the following alkyl halides is best suited for (d) CH3CH2COOH
this reaction through SN1 mechanism?
(a) CH3Br (b) C2H5Br Physical & Chemical Properties of Amines
(c) C6H5CH2Br (d) None of these
35. Which is formed when (CH3)4NOH is heated? 41. Melting points are normally highest for
(a) CH3NH2 (b) C2H5NH2 (a) tertiary amides (b) secondary amides
(c) (CH3)3N (d) (CH2)3N (c) primary amides (d) amines
36. Assertion (A): There are several disadvantages in the 42. Lower aliphatic amines are …I… in water because they
ammonolysis. can form …II… with water molecules. Identify I and II
Reason (R): Ammonolysis yield a mixture of primary, in the above reaction.
secondary, and tertiary amines and also a quaternary (a) I → Soluble; II → Covalent bond
ammonium salt. (b) I → Soluble; II → Hydrogen bond
(a) Both A and R are correct; R is the correct (c) I → Insoluble; II → Covalent bond
explanation of A. (d) I → Insoluble; II → Hydrogen bond
(b) Both A and R are correct; R is not correct 43. Which of the following factor(s) affect the basic
explanation of A. strength of amines?
(c) A is correct; R is incorrect. (a) Solvation effect (b) Inductive effect
(d) R is correct; A is incorrect. (c) Steric hindrance (d) All of these
H 2 / Pt 44. Which is more basic?
37. (A)  1° Amine (a) benzylamine (b) aniline
H 2 / Pt
(B)  2° Amine (c) acetamide (d) none of these
(A) and (B) respectively are: 45. Which is most basic?
(a) RNC, RNC (b) RCN, RCN (a) C6H5NH2 (b) (C6H5)2 NH
(c) RCN, RNC (d) RNC, RCN (c) CH3NH2 (d) (CH3)2 NH
38. In order to prepare a 1º amine from an alkyl halide with 46. Mark the correct statement
simultaneous addition of one CH2 group in the carbon (a) Methylamine is slightly acidic
chain, the reagent used as source of nitrogen is ............. (b) Methylamine is less basic than ammonia
(a) Sodium amide, NaNH2 (c) Methylamine is a stronger base than ammonia
(b) Sodium azide, NaN3 (d) Methylamine forms salts with alkalis.
(c) Potassium cyanide, KCN
74 AMINES

47. What is the decreasing order of basicity of primary, 55. The correct order of the basicities of the following
secondary and tertiary ethylamines and NH3? compounds is
NH O
(a) NH3> C2H5NH2> (C2H5)2NH > (C2H5)3N || ||
CH 3 – C – NH 2 ,CH 3 – CH 2 – NH 2 ,  CH 3  2 NH, CH 3 – C– NH 2
(b) (C2H5)3N > (C2H5)2NH > C2H5NH2> NH3
1  2 3  4
(c) (C2H5)2NH > C2H5NH2 > (C2H5)3N > NH3 (a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4
(d) (C2H5)2NH > (C2H5)3N> C2H5NH2> NH3 (c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4
48. Among the following, the weakest base is 56. The boiling points of amines and their corresponding
(a) C6H5CH2NH2 (b) C6H5CH2NHCH3 alcohols and acids vary in the order:
(c) O2NCH2NH2 (d) CH3NHCHO (a) RCH2NH2 > RCOOH > RCH2OH
49. Pyridine is less basic than triethyl amine because (b) RCH2NH2 > RCH2OH > RCOOH
(a) pyridine has aromatic character (c) RCH2NH2 < RCOOH < RCH2OH
(b) nitrogen in pyridine is sp2-hybridised (d) RCH2NH2 < RCH2OH < RCOOH
(c) pyridine is a cyclic system 57. The order of strength of bases
(d) in pyridine lone pair of nitrogen is delocalised
50. A solution of ethylamine
(a) turns blue litmus red
(b) turns red litmus blue
(c) does not affect the litmus (a) R > Q > P > S
(d) bleaches the litmus (b) P > Q > R > S
51. Which of the following should be most volatile? (c) S > P > R > Q
(I) CH3CH2 CH 2 NH2 (d) S > P > Q > R
(II) (CH3 )3 N 58. Amines are reactive because
(a) of the difference in the electronegativity between
nitrogen and hydrogen atoms
(III) (b) of the presence of unshared pair of electrons over
(IV) CH3CH2CH3 the nitrogen atom
(a) II (b) IV (c) Both (a) and (b)
(c) I (d) III (d) None of these
52. Which has the highest pKb value? 59. The most reactive amine towards dilute hydrochloric
(a) R3C – NH2 (b) R2NH acid is ................
(c) RNH2 (d) NH3
53. Amongst the following, the strongest base in aqueous
medium is ............. (a) CH3—NH2 (b)
(a) CH3NH2 (b) NCCH2NH2
(c) (CH3)2NH (d) C6H5NHCH3
54. Which of the following is the weakest Bronsted base?
(c) (d)
60. What is the correct order of reactivity of halides with
amines?
(a) (b) (a) RCl > RBr > RI (b) RI > RBr > RCl
(c) RCl > RI > RBr (d) RI > RCl > RBr
61. Reaction of cyclohexanone with dimethylamine in the
presence of catalytic amount of an acid forms a
compound. Water during the reaction is continuously
(c) (d) CH3NH2 removed. The compound formed is generally known as
(a) an amine (b) an imine
(c) an enamine (d) a Schiff’s base
AMINES 75

62. CH3NH2 + CHCl3 + 3KOH → X + Y + 3H2O on treatment with NaNO2/HCl gives

compounds X and Y are : (a) 1º alcohol with retention of configuration
(a) CH3CN + 3KCl (b) CH3NC + 3KCl (b) 2º alcohol with inversion of configuration
(c) racemic mixture of 2º alcohols
(c) CH3CONH2 + 3KCl (d) CH3NC + K2CO3
(d) racemic mixture of 1º alcohols
63. On heating benzyl amine with chloroform and ethanolic 73. C4H11N on reaction with HNO2 forms a tertiary alcohol.
KOH, product obtained is Thus, C4H11N is
(a) benzyl alcohol (b) benzaldehyde
(a) primary amine
(c) benzonitrile (d) benzyl isocyanide
(b) secondary amine
64. Carbylamine test is performed in alc. KOH by heating a
(c) tertiary amine
mixture of
(d) quaternary ammonium salt
(a) chloroform and silver powder
74. Treatment of cyclobutylmethylamine with nitrous acid
(b) trihalogenated methane and a primary amine
does not give
(c) an alkyl halide and a primary amine
(d) an alkyl cyanide and a primary amine
65. Ethyl amine on heating with CS2 in presence of HgCl2
forms (a) (b)
(a) C2H5NCS (b) (C2H5)2S
(c) (C2H5)2CS (d) C2H5 (CS)2
66. Primary amines on heating with CS2 followed by excess
of mercuric chloride yields isothiocyanates. The (c) (d)
reaction is called
(a) Hofmann mustard oil reaction
75. The major product of the reaction is:
(b) Perkin reaction
(c) Fries reaction
(d) Diels-Alder reaction
67. Ethyl amine undergoes oxidation in the presence of
KMnO4 to form
(a) An acid (b) An alcohol
(c) An aldehyde (d) A nitrogen oxide
68. Methylamine reacts with HNO2 to form.
(a) CH3–O–N = O (b) CH3–O–CH3
(c) CH3OH (d) CH3CHO
(a)
69. Ethylamine reacts with nitrous acid to form :
(a) methyl alcohol (b) ethyl alcohol
(c) ethane (d) ethyl nitrite
70. The gas evolved when methylamine reacts with nitrous
acid is. (b)
(a) NH3 (b) N2
(c) H2 (d) C2H6
71. Which of the following will give N2 gas on treatment
with nitrous acid (NaNO2 + HCl)? (c)
(a) C2H5NH2 (b) CH3NH2
(c) (CH3)2CH–NH2 (d) All will give N2
72. The optically active compound (X)
(d)
76 AMINES

76. The compound which, on reaction with aqueous nitrous 83. Examine the following two structures for the anilinium
acid at low temperature, produces an oily nitrosoamine ion and choose the correct statement from the ones
is given below
(a) Diethylyamine (b) Ethylamine
(c) Aniline (d) Methylamine
H O or O
77. The given reaction, R 3 N 
or H SO  ?
2 2 3
2 5
Choose the product formed in the reaction.
(a) R3N – OH (b) R3N – NR3
 –
(c) R3N → NR3 (d) R 3 N  O (a) II is not an acceptable canonical structure because
78. The pyrolysis of quaternary ammonium hydroxide to carbonium ions are less stable than ammonium ions
produce alkene is/are called. (b) II is not an acceptable canonical structure because
(a) Satzeff elimination reaction it is non-aromatic
(b) Hofmann elimination reaction (c) II is not an acceptable canonical structure because
(c) Both (a) and (b) the nitrogen has 10 valence electrons
(d) All of the above (d) II is an acceptable canonical structure
79. By heating ammonium chloride with two equivalents of 84. Reduction of aromatic nitro compounds using Fe and
formaldehyde it forms: HCl gives ............. .
(a) dimethylamine (a) aromaticoxime
(b) ethylamine (b) aromatic hydrocarbon
(c) methylamine hydrochloride (c) aromatic primary amine
(d) ammonium formate (d) aromatic amide
80. Acid anhydrides on reaction with primary amines give. 85. Which of the following on reduction with hydrogen and
(a) amide (b) imide Raney nickel gives benzylamine?
(c) secondary amine (d) imine (a) Benzonitrile (b) Acetonitrile
81. Treatment of ammonia with excess of ethyl iodide will (c) Propionitrile (d) Butyronitrile
yield 86. What is the end product in the sequence of following
(a) Diethylamine reactions?
(b) Ethylamine HNO  H SO Sn/HCl
C6 H 6 
3
333 K
2 4  A  B
(c) Triethylamine
(d) Tetraethylammonium iodide (a) Nitrobenzene
(b) Aniline
(c) Benzonitrile
Introduction to Aniline, Preparation and
(d) Phenyl carbylamine
Properties of Aniline 87. X is

82. Triaminobenzene is a
(a) 2° amine
(b) 3° amine
(c) 1° amine
(d) Quarternary salt
(a) Na2S (b) Sn/HCl
(c) LiAlH4 (d) all of these
AMINES 77

88. In a set of reactions, m-bromobenzoic acid gave a

product D. Identify the product D.

(d)

92. The correct increasing order of basic strength for the

following compounds is

(a) (b)

(c) (d)
89. m-Bromoaniline can be prepared by
HNO Br (a) II < III < I (b) III < I < II
[Link]  HCl
(a) C6 H 6 
H SO  
3
2. NaOH,H O  
2
H O (c) III < II < I (d) II < I < III
2 4 2 2
Br2 HNO3 H2 93. Which of the following compounds is the weakest
(b) C 6 H 6 
FeBr3  
H 2SO4  
Pt  Bronsted base?
(c)
SOCl NH Br ,NaOH
m  BrC6 H 4 COOH 
2  
3 
2
H



NaNO ,HCl SOCl NaNH

(d) C 6 H 5 NH 2  2
 2  
  2 (a) (b)
CuBr
90. Nitrobenzene gives N-phenylhydroxylamine by
(a) Sn/HCl (b) H2/Pd-C
(c) Zn/NaOH (d) Zn/NH4Cl
(c) (d)
91. 94. Among the following amines, the strongest Bronsted
base is ..................... .
(a)

(a) (b) NH3

(b)

(c) (d)
(c)
78 AMINES

95. Arrange the following in increasing order of their basic 100. The correct order of increasing basic nature of the
strength: following bases is
CH3NH2 (I), (CH3)2NH (II), (CH3)3N (III),
C6H5CH2NH2 (IV).
(a) IV < III < II < I (b) IV < III < I < II
(c) I < II < III < IV (d) IV < III < I = II
96. The weakest base among the following is
(a) dimethylamine (b) aniline
(c) methylamine (d) ethylamine
97. Which of the following compounds is most basic?
(a)
(a) 2 < 5 < 1 < 3 < 4 (b) 5 < 2 < 1 < 3 < 4
(c) 2 < 5 < 1 < 4 < 3 (d) 5 < 2 < 1 < 4 < 3
101. Consider the following compounds,
(b)

(c)
What is the correct order of basicity of the above
compounds?
(a) I > II > III (b) III > I > II
(c) III > II > I (d) I > III > II
(d) 102. Correct order of increasing basicity is
(a) NH3 < C6H5NH2 < (C2H5)2NH < C2H5NH2 <
(C2H5)3N
(b) C6H5NH2 < NH3 < (C2H5)3N < (C2H5)2NH <
98. The strongest base in aqueous solution among the C2H5NH2
following amines is (c) C6H5NH2 < NH3 < C2H5NH2 < (C2H5)3N <
(C2H5)2NH
(a) N, N-diethylethanamine
(d) C6H5NH2 < (C2H5)3N < NH3 < C2H5NH2 <
(b) N-ethylethanamine (C2H5)2NH
(c) N-methylmethanamine 103. Aniline is a weaker base than ethylamine because
(d) Ethanamine (a) The phenyl group in aniline increases the electron
99. Strongest base is density on the nitrogen atom.
(b) The ethyl group in ethylamine decreases the
electron density on the nitrogen atom.
(c) The lone pair of electrons on the nitrogen atom in
aniline is delocalized over the benzene ring.
(a) (b) (d) Aniline is less soluble in water than ethylamine.
104. Which of the following is the strongest base?

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

(c) (d)
AMINES 79

105. Among the following, the strongest base is 111. Predict the product:
(a) C6H5NH2 (b) p-NO2C6H4NH2
(c) m-NO2.C6H4NH2 (d) C6H5CH2NH2
106. Leakage of which gas was responsible for the Bhopal
tragedy in
(a) CH3 -N=C=O (b) CH3 -N=C=S
(a)
(c) CHCl3 (d) C6 H5COCl
107. Which of the following amines will show carbylamine
reaction?
(b)

(c)

(a) (b)

(d)
112. Which of the following reaction(s) is/are electrophilic
substitution?
(c) (d)
(a) Bromination of aniline
108.
(b) Nitration of aniline
(c) Sulphonation of aniline
(d) All of these
113. …I… positions to the NH2 group in the aniline have the
high electron density and NH2 Group act as the
(a) Phenyl isocyanide (b) Benzyl amine powerful …II… group.
(c) Benzyl chloride (d) None of these Select an appropriate option to complete the above
109. Aniline on heating with conc. HNO3 + conc. H2SO4 statement.
mixture yields (a) I → ortho and para; II → deactivating
(a) o- and p-Nitroanilines (b) m-Nitroaniline (b) I → ortho and para; II → activating
(c) A black tarry matter (d) No reaction (c) I → ortho and meta; II → deactivating
110. In the following sequence of reactions, what is D? (d) I → meta and para; II → activating
114. Assertion (A): Monosubstituted aniline derivatives can
be prepared by controlling the activating effect of NH2
Group.
Reason (R): In electrophilic substitution reactions of
(a) Primary amine aromatic amines, substitution occur at ortho and para-
(b) An amide position due to the high reactivity of aromatic amines.
(c) Phenyl isocyanate (a) Both A and R are correct; R is the correct
(d) Chain lengthened hydrocarbon explanation of A.
(b) Both A and R are correct; R is not correct
explanation of A.
(c) A is correct; R is incorrect.
(d) R is correct; A is incorrect.
80 AMINES

115. Assertion (A): Aniline does not undergo alkylation and 119. Aniline on reaction with acetyl chloride gives
acetylation. (a) Phenol (b) Acetamide
Reason (R): Nitrogen of aniline acquires positive (c) Acetanilide (d) Benzene
charge, a strong activating group further reaction. 120. Aniline on heating with fuming sulphuric acid gives :
(a) Both A and R are correct; R is the correct (a) anilinesulphate
explanation of A. (b) sulphanilic acid
(b) Both A and R are correct; R is not correct (c) aniline 2,4-disulphonic acid
explanation of A. (d) nitrobenzene
(c) A is correct; R is incorrect. 121. Acetanilide on nitration followed by alkaline hydrolysis
(d) R is correct; A is incorrect. mainly gives
116. In the following reaction (a) o-Nitroacetanilide
(b) p-Nitroaniline
(c) m-Nitroaniline
(d) 2,4,6-Trinitroaniline
122. Aniline on treatment with aqueous bromine gives :
The structure of the major product X is (a) 2,4,6-tribromo aniline
(b) o-bromo aniline
(c) 2,4-dibromo aniline
(d) p-bromo aniline
(a) 123. Benenediazonium chloride is a name of
(a) C6 H 5 Cl – (b) C 6 H 5 N 2 Cl –
(c) C 6 H 5 N 2 (d) C6 H5 NH2
124. The diazotization of two feebly basic aromatic amines
is achieved by using
(b) (a) Sulphuric acid
(b) nitrosyl-sulphuric acid
(c) Nitrous acid
(d) Nitrosyl-hydrochloric acid
125. The reaction of diazonium salts can be divide into the
(c) categories base on the
(a) reactions involving displacement of nitrogen
(b) reaction involving retention of diazo group
(c) Both (a) and (b)
(d) None of the above
(d)
126. Diazonium group is a …I… leaving group which is
117. Toluene is nitrated and the resulting product is reduced
with tin and hydrochloric acid. The product so obtained substituted by Cl  , Br  , I  , CN  , OH  in the aromatic
is diazotised and then heated with cuprous bromide. ring and the …II… is escaped out from the reaction
The reaction mixture so formed contains mixture.
(a) mixture of o- and p-bromotoluenes Fill in the blanks I and II with appropriate words.
(b) mixture of o- and p-dibromobenzenes (a) I  good II  nitrogen gas
(c) mixture of o- and p-bromoanilines (b) I  bad II  Oxygen gas
(d) mixture of o- and m-bromotoluenes (c) I  good II  Oxygen gas
118. Reaction of aniline with benzaldehyde is : (d) I  bad II  nitrogen gas
(a) substitution (b) addition
(c) condensation (d) polymerisation
AMINES 81

127. Which of the following reaction belong to electrophilic

aromatic substitution?
(I) Bromination of acetanilide
(II) Coupling reaction of aryl Diazonium salts
(III) Diazotization of aniline
(IV)Acylation of aniline
Choose the correct option.
(a) Only I and II (b) Only II and III
(c) Only III and IV (d) Only I and IV (a)
128. Which of the following compound will not undergo azo
coupling reaction with benzene diazonium chloride?
(a) Aniline (b) Phenol
(c) Anisole (d) Nitrobenzene (b)
129. Aniline reacts with NaNO2 and HCl at room
temperature further react warm water to give
(a) Nitroaniline (b) Phenol (c)
(c) Chloroaniline (d) Diazonium chloride
130. In order to convert aniline into chlorobenzene the
reagent used is
(d)
(a) NaNO2/HCl, CuCl (b) Cl2/CCl4 133. In the chemical reactions
(c) Cl2/AlCl3 (d) CuCl2
131. The product(s) of the following reaction sequence is
(are)

Compounds A and B respectively are

(a) fluorobenzene and phenol
(b) benzenediazonium chloride and benzene
(c) nitrobenzene and chlorobenzene
(d) phenol and bromobenzene
134. In the diazotisation of aniline with sodium nitrite and
hydrochloric acid, an excess of hydrochloric acid is
used primarily to
(a) Suppress the concentration of free aniline available
for coupling
(b) Suppress hydrolysis of phenol
(c) Ensure a stoichiometric amount of nitrous acid
(a) (b)
(d) Neutralize the base liberated
135. In the chemical reactions,

(c) (d)
132. Aniline in a set of the following reactions yielded a
coloured product Y. the compounds ‘A’ and ‘B’ respectively are
The structure of Y would be (a) nitrobenzene and fluorobenzene
(b) phenol and benzene
(c) benzenediazonium chloride and fluorobenzene
(d) nitrobenzene and chlorobenzene
82 AMINES

136. Fluorobenzene (C6H5F) can be synthesized in the 142. In Hinsberg test the product of which amine does not
laboratory dissolve in NaOH?
(a) by heating phenol with HF and KF (a) CH3CH2 NH 2
(b) from aniline by diazotisation followed by heating (b) (CH3 )2 CHNH 2
the diazonium salt with HBF4
(c) CH3 NHCH3
(c) by direct fluorination of benzene with F2 gas
(d) CH3 N(CH3 )2
(d) by reacting bromobenzene with NaF solution
143. Which of the following pairs of compounds can be
137. In the reaction
distinguished using isocyanide test?
C6H5CHO + C6H5NH2 →C6H5N = HCC6H5 + H2O, (a)
the compound C6H5N = CHC6H5 is known as
(a) Aldol
(b) Schiff’s reagent
(c) Schiff’s base
(d) Benedict reagent (b) (CH3CH2)2NH and (CH3CH2)3N
(c)
Test of Amines and Uses
138. C2H5NH2 and C6H5NH2 can be best distinguished by
(a) NaOH (b) Azo dye test (d)
(c) CHCl3/KOH (d) Hinsberg's reagent
139. Primary amines are identified by :
(a) Hofmann’s reaction
(b) Carbylamine reaction 144. Which of the following method is generally not
(c) Friedel-Crafts reaction employed for the separation of primary, secondary and
(d) Biuret reaction tertiary amines?
140. Which of the following compounds will dissolve in an (a) Fractional distillation
alkali solution after it undergoes reaction with (b) Hinsberg’s method
Hinsberg’sreagent? (c) Hofmann’s method
(a) CH3NH2 (d) Filtration
(b) (CH3)3N 145. A mixture of 1°, 2° and 3° amines can be separated by
(c) (C2H5)2NH Hinsberg’s reagent which is
(a) Benzoyl chloride
(d) C6H5NHC6H5 (b) Acetyl chloride
141. Which of the following is soluble in sodium hydroxide (c) Benzensulphonyl chloride
(d) Benzyl chloride
146. Which of the following reacts with hinsberg’s reagent
(Benzene sulphonyl chloride) to form the product
(a) soluble in KOH?
(a) Primary amine (b) Secondary amine
(c) Tertiary amine (d) Quaternary amine
147. Which one of the following methods is neither meant
(b) for the synthesis nor for separation of amines?
(a) Curtius reaction (b) Wurtz reaction
(c) Hofmann method (d) Hinsberg method
148. Azo dye test is given by
(a) All amines
(c) (b) Only secondary amines
(c) Only primary aliphatic amines
(d) Only primary aromatic amines
149. In the explosive amatol, TNT is mixed with
(d) (a) Ammonium citrate (b) Ammonium nitrate
(c) Ammonium oxalate (d) Ammonium sulphate
AMINES 83

Assertion Reason & Statement Type Questions (b) Both A and R are correct; R is not the correct
explanation of A
150. I. Diazonium salts are very good intermediates for the (c) A is correct; R is incorrect
introduction of F, Cl, Br, I, CN, OH, NO2 groups into (d) R is correct; A is incorrect
the aromatic ring. 154. Assertion (A): Aliphatic amines are weaker bases than
II. Aryl fluorides and iodides can be prepared by direct ammonia and aromatic amines are stronger bases than
halogenation. ammonia.
III. Cyano group cannot be introduced by nucleophilic Reason (R): +I-effect of alkyl groups on aliphatic
substitution of chlorine in chlorobenzene. amines increase the electron density on nitrogen atom.
IV. The replacement of diazo group by other groups is Aromatic amines are weaker due to electron
helpful in preparing those substituted aromatic withdrawing nature of the aryl group.
compounds which cannot be prepared by direct (a) Both A and R are correct; R is the correct
substitution in benzene or substituted benzene. explanation of A
Select the incorrect statements, (b) Both A and R are correct; R is not the correct
(a) I and II (b) II and III explanation of A
(c) III and IV (d) I and IV (c) A is correct; R is incorrect
151. Some statements are given about following order of (d) R is correct; A is incorrect
basic strength in aqueous medium. 155. Assertion (A): MeNH2 is the weaker base than MeOH.
(CH3)2NH > CH3–NH2 > (CH3)3N > NH3 Reason (R): N is less electronegative than O, lone pair
(a) More substituted ammonium ion gets stablised due of electrons on N is more easily available for the
to +I effect of alkyl group. donation in MeNH2.
(b) The greater the size of ammonium ion, more will be (a) Both A and R are correct; R is the correct
solvation, so more stable ion so more basicity. explanation of A
(c) More the alkyl groups, more steric hindrance to H- (b) Both A and R are correct; R is not the correct
bonding in ammonium ion. explanation of A
(d) Basic strength in aqueous medium is explained by (c) A is correct; R is incorrect
more than one type of effects. (d) R is correct; A is incorrect
Correct statements is/are 156. Assertion (A): Benzenediazonium salts are soluble in
(a) a, b, c, d (b) a, b, d water.
(c) a, c, d (d) a and d only Reason (R): They are covalent in nature, so they are
152. Assertion (A): Aromatic primary amines cannot be soluble in water.
prepared by Gabriel phthalimide synthesis. (a) Both A and R are correct; R is the correct
Reason (R): Aryl halides do not undergo electrophilic explanation of A
substitution with anion formed by phthalimide. (b) Both A and R are correct; R is not the correct
(a) Both A and R are correct; R is the correct explanation of A
explanation of A (c) A is correct; R is incorrect
(b) Both A and R are correct; R is not the correct (d) R is correct; A is incorrect
explanation of A
157. Assertion (A): Tertiary butylamine can be prepared by
(c) A is correct; R is incorrect
(d) R is correct; A is incorrect the action of NH3 on tert-butylbromide.
153. Assertion (A): Order of basicity of amines in gaseous Reason (R): Tertiary butylbromide being 3° alkylhalide
phase is NH3 > primary amine > secondary amine > prefers to undergo elimination on the treatment with a
tertiary amine. base.
Reason (R): In gaseous phase the basic nature of (a) Both A and R are correct; R is the correct
aliphatic amine increases with the increase in number of explanation of A
alkyl groups. (b) Both A and R are correct; R is not the correct
(a) Both A and R are correct; R is the correct explanation of A
explanation of A (c) A is correct; R is incorrect
(d) R is correct; A is incorrect
84 AMINES

158. Assertion (A): p-fluoroanilinium ion is more acidic 161. Given below are two statements; one is labeled as
than anilinium ion. Assertion (A) and the other is labeled as Reason (R).
Reason (R): Electron density in the N—H bond of p- Assertion: Methyl amines react with benzoyl chloride
fluoroanilinium ion decreases and release of a proton to form N-methyl benzamide but forms salt with
from p-fluoroanilinium ion is much easier than from carboxylic acid.
anilinium ion. Reason: Amines are base as well as nucleophile.
(a) Both A and R are correct; R is the correct In the light of the above statements, choose the most
explanation of A appropriate answer from the options given below:
(b) Both A and R are correct; R is not the correct (a) Both (A) and (R) are correct and (R) is the correct
explanation of A explanation of (A).
(c) A is correct; R is incorrect (b) Both (A) and (R) are correct but (R) is not the
(d) R is correct; A is incorrect correct explanation of (A).
159. Given below are two statements; one is labeled as (c) (A) is correct but (R) is not correct.
Assertion (A) and the other is labeled as Reason (R). (d) (A) is not correct but (R) is correct.
Assertion: Acylation of Amine by acetyl chloride is 162. Given below are two statements; one is labeled as
carried out in presence of base like pyridine Assertion (A) and the other is labeled as Reason (R).
Reason: Pyridine removes HCl (by product) and shifts Assertion: The correct boiling point order of isomeric
the reaction equilibrium to the left hand side. amines is –
In the light of the above statements, choose the most Primary > Secondary > Tertiary
appropriate answer from the options given below: Reason: The intermolecular H-bonding in primary
(a) Both (A) and (R) are correct and (R) is the correct amine is maximum due to two hydrogen available for
explanation of (A). more association but in tertiary amine there is no
(b) Both (A) and (R) are correct but (R) is not the hydrogen available for H-bond.
correct explanation of (A). In the light of the above statements, choose the most
(c) (A) is correct but (R) is not correct. appropriate answer from the options given below:
(d) (A) is not correct but (R) is correct. (a) Both (A) and (R) are correct and (R) is the correct
160. Given below are two statements; one is labeled as explanation of (A).
Assertion (A) and the other is labeled as Reason (R). (b) Both (A) and (R) are correct but (R) is not the
Assertion: The alkyldiazonium salt are unstable but the correct explanation of (A).
arenediazonium salt are stable for a short time at low (c) (A) is correct but (R) is not correct.
temperature (0° – 5°C) (d) (A) is not correct but (R) is correct.
Reason: Due to resonance in arenediazonium salt 163. Given below are two statements:
carbon-nitrogen bond becomes stronger than Statement-I: Aromatic amines are less basic than
alkyldiazonium salt. ammonia and aliphatic amine.
In the light of the above statements, choose the most Statement-II: Generally in substituted aniline, it is
appropriate answer from the options given below: observed that electron releasing groups increase basic
(a) Both (A) and (R) are correct and (R) is the correct strength whereas electron withdrawing groups decrease
explanation of (A). it.
(b) Both (A) and (R) are correct but (R) is not the In the light of the above statements, choose the most
correct explanation of (A). appropriate answer from the options given below:
(c) (A) is correct but (R) is not correct. (a) Both Statement-I and Statement-II are correct.
(d) (A) is not correct but (R) is correct. (b) Both Statement-I and II are incorrect.
(c) Statement-I is correct but Statement-II is incorrect.
(d) Statement-I is incorrect but Statement-II is correct.
AMINES 85

164. Given below are two statements: In the light of the above statements, choose the most
Statement-I: The chemical reaction of Amines with appropriate answer from the options given below:
benzene sulphonyl chloride in a different manner is (a) Statement-I and Statement-II are correct.
used for the distinction of primary, secondary and (b) Both Statement-I and II are incorrect.
tertiary amines and also for the separation of a mixture (c) Statement-I is correct but Statement-II is incorrect.
of these amines. (d) Statement-I is incorrect but Statement-II is correct.
Statement-II: In the reaction with Tertiary amine, N,N- 168. Given below are two statements:
diethyl benzene sulphonyl amide is formed, which does Statement-I: Aniline reacts with Bromine water to give
not contain any acidic hydrogen hence insoluble in a white precipitate of tribromoaniline.
alkali. Statement-II: Aniline gives monobromo aniline when
In the light of the above statements, choose the most reaction is carried out in following sequence.
appropriate answer from the options given below: (i) CH3–COCl/pyridine
(a) Statement-I and Statement-II are correct. (ii) Br2/CH3–COOH
(b) Both Statement-I and II are incorrect. (iii) H3O⊕
(c) Statement-I is correct but Statement-II is incorrect. In the light of the above statements, choose the most
(d) Statement-I is incorrect but Statement-II is correct. appropriate answer from the options given below:
165. Given below are two statements: (a) Both Statement-I and Statement-II are correct.
Statement-I: If we have to prepare mono bromo aniline (b) Both Statement-I and II are incorrect.
from aniline then the high activity effect of –NH2 group (c) Statement-I is correct but Statement-II is incorrect.
is controlled by acetylation. (d) Statement-I is incorrect but Statement-II is correct.
Statement-II: After acetylation, the lone pair of 169. Given below are two statements:
nitrogen of acetanilide is more available for donation to Statement-I: Reduction of ester with (i) LiAlH4 (ii)
ring. H2O gives 1° Alcohol while reduction of Amide gives
In the light of the above statements, choose the most 1° Amine
appropriate answer from the options given below: Statement-II: Hoffmann bromamide degradation gives
(a) Statement-I and Statement-II are correct. 1° Amine not 2° Amine.
(b) Both Statement-I and II are incorrect. In the light of the above statements, choose the most
(c) Statement-I is correct but Statement-II is incorrect. appropriate answer from the options given below:
(d) Statement-I is incorrect but Statement-II is correct. (a) Statement-I and Statement-II are correct.
166. Given below are two statements: (b) Both Statement-I and II are incorrect.
Statement-I: Aryl flouride and iodide cannot be (c) Statement-I is correct but Statement-II is incorrect.
prepared by direct halogenation of benzene. (d) Statement-I is incorrect but Statement-II is correct.
Statement-II: These are easily obtained by reaction of 170. Statement-I: Out of Butan-1-ol and butan-1- amine,
Benzene diazonium salt with potassium iodide and with Butan-1-ol is more soluble in water.
fluoroboric acid/∆ respectively. Statement-II: Alcohols are more polar than Amine so
In the light of the above statements, choose the most Amines form stronger intermolecular hydrogen bonds
appropriate answer from the options given below: than alcohol.
(a) Statement-I and Statement-II are correct. In the light of the above statements, choose the most
(b) Both Statement-I and II are incorrect. appropriate answer from the options given below:
(c) Statement-I is correct but Statement-II is incorrect. (a) Statement-I and Statement-II are correct.
(d) Statement-I is incorrect but Statement-II is correct. (b) Both Statement-I and II are incorrect.
167. Given below are two statements: (c) Statement-I is correct but Statement-II is incorrect.
Statement-I: Direct nitration of aniline gives good (d) Statement-I is incorrect but Statement-II is correct.
yield of paranitroaniline.
Statement-II: By acetylation of aniline, formation of
anilinium ion is decreased and good yield of meta
product is obtained.
86 AMINES

Match the following Questions Correct match is

(a) A – Q, B – P, C – S, D – R
171. Match the following Column I (reactant) with their (b) A – T, B – P, C – S, D – R
products given in Column II and choose the correct (c) A – Q, B – P, C – T, D – S
option from the codes given below. (d) A – T, B – Q, C – S, D – R
Column I Column II 174. Match the column.
A. H2C2NH2 + H3 CCOCl 1. Acetanilide Column I Reaction Column II
B. H5C2 – NH – C2H5 + 2. N,N-diethyl Name/Process
H3CCOCl ethanamide A.  P. Gatterman
Ar N 2 X 
Cu 2 Cl2

C. 3. N-ethyl HCl
reaction
ethanamide B.  Q. Coupling
Ar N 2 X 
Cu / HCl
reaction
(a) A – 1, B – 3, C – 2 C.  R. Sandymeyer
(b) A – 3, B – 1, C – 2 Ar N 2 X 
H3 PO2

H2 O
reaction
(c) A – 1, B – 2, C – 3 D.  S. Reduction
Ph  OH
(d) A – 3, B – 2, C – 1 Ar N 2 X 
0 5 C

172. Match the column. Correct match is:

Column I Column II (a) A – R, B – P; C –S, D – R
(Compound) (Pkb) (b) A – R, B – P; C –Q, D – S
(i) N,N-Dimethyl aniline (a) 9.38 (c) A – P, B – R; C –S, D – Q
(ii) Benzenamine (b) 8.92 (d) A – Q, B – R; C –P, D – S
(iii) N-Methyl (c) 3.38 175. Match the column.
methanamine Column I Type of Column II
(iv) Methanamine (d) 3.27 amine Reaction
(a) (i) → b, (ii) → a, (iii) → c, (iv) → d A. 1° Amine P. Gives yellow
(b) (i) → c, (ii) → d, (iii) → a, (iv) → b oily liquid with
(c) (i) → b, (ii) → a, (iii) → d, (iv) → c HNO2
(d) (i) → d, (ii) → a, (iii) → c, (iv) → b B. 2° Amine Q. Gives isocyanide
173. Match the column. test
Column I (Reaction) Column II C. 3° Amine R. Not reacts with
(Process) Hinsberg reagent
A. P. Acetylation Correct match is:
(a) A – P, B – Q; C – R
(b) A – R, B – P; C –Q
(c) A – Q, B – P; C – R
B. Q. Alkylation (d) A – Q, B – R; C –P

C. R. Diazotization

D. S. Carbonylamine
reaction

T. Halogenation
AMINES 87

Exercise – 2: Previous Year Questions

1. Acetamide is treated with the following reagents LiAlH
4
(c) CH3NC 
separately. Which one of these would yield methyl
LiAlH
amine? (CBSE AIMPT 2010) (d) CH3CONH2  4
(a) PCl5 (b) NaOH + Br2 9. The main product of the reaction
(c) Sodalime (d) Hot conc. H2SO4 CH3CONH2+ NaOH +Br2 →.....is (MP PMT 2010)
2. Arrange the folowing in the increasing order of their (a) CH3Br (b) CH4
basic strength. (c) CH3OBr (d) CH3NH2
CH3NH2 (I); (CH3)2NH(II); 10. Which one of the following has the most nucleophilic
(CH3)3N(III); C6H5NH2(IV) nitrogen? (KCET 2010)
(AMU2010)
(a) IV < III < II < I (b) IV < III < I < II
(c) I < II < III < IV (d) IV < III < I = II
3. Primary, secondary and tertiary amines can be
distinguished by (AFMC 2010) (a) (b)
(a) Schiff’s test (b) Fehling’
(c) Tollen’s test (d) Hinsberg’s test
4. Amines are basic in character because they have (c) (d)
(BVP 2010) 11. Why do 2° and 3° amines fail to undergo the
(a) a lone pair of electrons on the nitrogen atom carbylamine test? (Guj CET 2010)
(b) a hydroxyl group in the molecule (a) They combine with chloroform to give a stable
(c) replaceable hydrogen atom compound
(d) tetrahedral structure (b) They react with alcoholic KOH
5. Which of the following amines gives yellow oily liquid (c) The nitrogen atom of the amine group does not have
with HNO2? (MHT CET 2010) the required number of hydrogen atoms
(a) Ethyl methylamine (b) Aniline (d) All of the above
(c) 3-methylbenzylamine (d) Methylamine 12. Which of the following statements are correct?
HNO PCl NH (CMC Ludhiana 2010)
6. C2 H5 NH 2  3  B 
2  A  3 C (a) Aniline is a stronger base than ethyl amine
recognize the comound C from the following (b) Aniline is a stronger base than p -methoxyaniline
(c) Aniline must be acetylated before nitration with an
(MHT CET 2010)
acid derivative
(a) propane nitrile (b) metylamine (d) Aniline is soluble in an ammonium hydroxide
(c) ethyl amine (d) acetamide solution
7. Acetamide and ethylamine can be distinguished by 13. The strongest base in aqueous solution among the
reacting with (Manipal 2010) following amines is (Kerala CEE 2011)
(a) aqueous HCl and heat (a) N,N-diethylethanamine (b) N-ethylethanamine
(b) aqueous NaOH and heat (c) ethanamine (d) phenylmethanamine
(c) acidified KMnO4 14. Aniline is treated with bromine water to give an organic
(d) bromine water compound ‘X’ which when treated with NaNO2 and
8. Which of the following will not give a primary amine? HCl at 0ºC gives a water soluble compound ‘Y’.
(RPMT 2010) Compound ‘Y’ on treatment with Cu2Cl2 and HCl gives
compound ‘Z’. compound ‘Z’ is (Kerala CEE 2011)
Br .KOH
(a) CH3CONH2 

2 (a) o-bromochlorobenzene
LiAlH (b) p-bromochlorobenzene
4
(b) CH3CN  (c) 2,4,6-tribromochlorobenzene
(d) 2,4-dibromophenol
 88 AMINES

15. Anilinium hydrogen sulphate on heating with sulphuric 23. Unpleasant smell of carbylamine is obtained when
acid at 453-473 K produces (Kerala CEE 2011) chloroform and alcoholic KOH are heated with
(a) benzene sulphonic acid (b) anthranilic acid (KCET 2013)
(c) sulphanilic acid (d) aniline (a) any aliphatic amine
16. Compare boiling points of isomeric alkyl amines. (b) any amine
(Guj CET 2011) (c) any primary amine
(a) 1º > 2º > 3º (b) 1º > 2º < 3º (d) any aromatic amine
(c) 1º < 2º < 3º (d) 1º < 2º > 3º 24. Identify the alkene that is produced in the following
17. When CH3CONH2 is heated with P2O5, the product is series of reactions. (MHT CET 2014)
(UP CPMT 2012)
(a) CH3CCl2NH2 (b) CH3CN
(c) CH3COCl (d) CCl3CONH2
18. An organic compound(C3H9N) (A), when treated with
nitrous acid, gave an alcohol and N2 gas was evolved.
(A) on warming with CHCl3 and caustic potash gave (C) (a) (b)
which on reduction gave iso-propylmethyl amine. Predict
the structure of (A). (CBSE AIPMT 2012) (c) (d)
25. An organic compound X having molecular formula
C4H11N reacts with p-toluene sulphonyl chloride to form
(a) (b) CH3CH2–NH–CH3 a compound Y that is soluble in aqueous KOH.
Compound X is optically active and reacts with acetyl
chloride to form compound Z. Identify the compound Z.
(c) (d) CH3CH2CH2–NH2 (MHT CET 2014)
19. Reaction of aniline with acetyl chloride in the presence (a) CH3 CH 2 CH 2 CH2 NHCOCH3
of NaOH gives (Manipal 2012)
(a) acetanilide (b) p-chloroaniline
(c) a red dye (d) aniline hydrochloride (b)
20. The product formed by the reaction of acetamide with CH3
|
bromine in the presence of NaOH is (AIIMS 2013) (c) CH3 – CH CH2 NHCOCH3
(a) CH3CN (b) CH3CHO
(c) CH3CH2OH (d) CH3NH2
NaNO /H Cu  CN  ,H O/H
22 2 2
C6 H 5 NH 2 
 X 
Y (d)
21.
H O/H 26. Carbylamine test is not answered by
2
  Z,
(Kerala CEE 2014)
Z is defined as (Manipal 2013)
(a) C6H5NH2
(a) C6 H5  NH  CH3 (b) C6 H5  COOH
(b) (CH3)3 C–CH2–NH2
(c) C6 H5  CH 2 NH2 (d) C6 H5  CH 2  COOH (c) C6H5CH2NH2
22. In the reaction A is (NEET 2013) (d) (CH3)3N
NO 2 NO 2 27. The reagent that is used to distinguished between
secondary amine and tertiary amine is
A (Kerala CEE 2014)
(a) p-toluene sulphonyl chloride
Br Br (b) Lucas reagent
N2Cl (c) CHCl3 and alc. KOH
(a) HgSO4/H2SO4 (b) Cu2Cl (d) Borche’s reagent
(c) H3PO2 and H2O (d) H+/H2O
AMINES 89

28. Which one of the following isomeric amines has the 35. In pyrrole,
highest boiling point? (Kerala CEE 2014)
(a) CH3  CH 2  CH 2  NH  CH3
(b) CH3  CH 2  NH  CH 2  CH3

(c)  CH3 2 N  CH2  CH3

(d) CH3  CH2  CH2  CH2  NH2 the electron density is maximum on
29. Which one of the following reagent will convert (NEET Phase-II 2016)
acetamide into ethanamine? (Kerala CEE 2014) (a) 2 and 3 (b) 3 and 4
(a) Phosphorus pentoxide (c) 2 and 4 (d) 2 and 5
(b) Lithium aluminium hydride 36. The correct statement regarding the basicity of
(c) Potassium cyanide arylamines is (NEET 2016)
(d) Thionyl cyanide (a) Arylamines are generally more basic than
30. The source of nitrogen in Gabriel synthesis of amines is alkylamines because the lone pair of electrons on
(UK PMT 2014) nitrogen Is not delocalized by interaction with the
(a) NaN3 aromatic ring π-electron system
(b) NaNO2 (b) Arylamines are generally more basic than
(c) KCl alkylamines because of aryl group
(d) C6H5(CO)2N–K+ (c) Arylamines are generally more basic than
31. Hofmann bromamide degradation is shown by alkylamines, because the nitrogen atom in
(UK PMT 2014) alkylamines is sp-hybridised
(a) ArNH2 (d) Arylamines are generally less basic than alkylamines
(b) ArCONH2 because the lone pair of electron on nitrogen is
(c) ArNO2 delocalised by interaction with the aromatic ring π-
(d) ArCH2NH2 electron system.
32. An aromatic compound ‘A’ (C7H9N) on reacting with 37. A given nitrogen-containing aromatic compound A
NaNO2/HCl at 0ºC forms benzyl alcohol and nitrogen reacts with Sn/HCl followed by HNO2 to give an
gas. The number of isomers possible for the compound unstable compound B.B, on treatment with phenol, forms
‘A’ is (KCET 2014) a beautiful coloured compound C with the molecular
(a) 5 (b) 7 formula C12H10N2O. The structure of compound A is
(c) 3 (d) 6 (NEET Phase-II 2016)
33. The correct sequence of reaction to be performed to
convert benzene into m-bromoaniline is (KCET 2014)
(a) nitration, reduction, bromination
(a) (b)
(b) bromination, nitration, reduction
(c) nitration, bromination, reduction
(d) reduction, nitration, bromination
34. Which of the following will be most stable? (c) (d)
(CBSE AIPMT 2014) 38. Consider the reaction CH3CH2CH2Br + NaCN 

(a) CH3 N2 X CH3CH2CH2CN + [Link] used is ……
 
(b) C6 H5 N2 X (NEET Phase-II 2016)
 
(a) ethanol
(c) CH3CH2 N2 X (b) methanol
 
(d) C6 H5CH2 N2 X (c) N, N-dimethylformamide(DMF)
(d) water
 90 AMINES

39. The correct order of basic strength of the following are Reason: The colour of the compound formed in the
(JIPMER 2017) reaction of aniline with NaNO2/HCl at 0ºC followed by
coupling with β-naphthol is due to the extended
conjugation. (AIIMS 2017)
(a) Both A and R are correct and R is the correct
explanation of A
(b) Both A and R are correct but R is not the correct
explanation of A
(c) A is incorrect but R is correct
(d) Both A and R are incorrect
44. The main product formed in the following reaction is
(JIPMER 2017)

(a)
(a) I > II > III > IV (b) IV > II > III > I
(c) III > IV > II > I (d) III > II > IV > I
40. Consider the following reaction,
Bromination NaNO  HCl
X  2
 Y Z (b)
Boiling C H OH
Z  2 5  Tribromobenzene X is
(JIPMER 2017)
(a) benzoic acid (b) salicylic acid
(c) phenol (d) aniline (c)
41. The correct increasing order of basic strength for the
following compound is (NEET 2017)

(d)

(a) II < III < I (b) III < I < II

(c) III < II < I (d) II < I < III
42. Which of the following reactions is appropriate for
converting acetamide to methanamine? (NEET 2017) 45. Which of the following chemicals are used to
(a) Carbylamine reaction manufacture methyl isocyanate that caused “Bhopal gas
(b) Hofmann hypobromamide reaction tragedy”?
(c) Stephen’s reaction I. Methylamine II. Phosgene
(d) Gabriel phtalmide synthesis III. Phospine IV. Dimethylamine
(JIPMER 2018)
43. Assertion: Aniline on reaction with NaNO2/HCl at 0ºC (a) I and III (b) III and IV
followed by coupling with β-naphthol gives a dark blue (c) I and II (d) II and IV
coloured precipitate.
 AMINES 91

46. Nitration of aniline in strong acidic medium also gives

m-nitroaniline because (NEET 2018)
(a) in absence of substituents nitro group always goes to
m-position (a)
(b) in electrophilic substitution reactions amino group is
meta directive
(c) in spite of substituents, nitro group always goes to (b)
only m-position
(d) in acidic (strong) medium, aniline is present as
anilinium ion (c)
47.

(d)
51. Statement I: Primary aliphatic amines react with HNO2
to give unstable diazonium salts.
Statement II: Primary aromatic amines react with HNO2
to form diazonium salts which are stable even above 300
K.
Correct order of basic strength is (AIIMS 2019) Choose the most appropriate answer from the options
(a) III > II > IV > I given below : (NEET 2022)
(b) IV > III > II > I (a) Both Statement I and Statement II are correct.
(c) III > II > I > IV (b) Both Statement I and Statement II are incorrect.
(d) III > I > II > IV (c) Statement I is correct but Statement II is incorrect.
48. The correct order of the basic strength of methyl (d) Statement I is incorrect but Statement II is correct.
substituted amines in aqueous solution (NEET 2019) 52. The product formed from the following reaction
(a) (CH3)3N > CH3NH2 > (CH3)2NH sequence is
(b) (CH3)3N > (CH3)2NH > CH3NH2
(c) CH3NH2 > (CH3)2NH > (CH3)3N
(d) (CH3)2NH > CH3NH2 > (CH3)3N
49. Which of the following amine will give the carbylamine (NEET 2022)
test? (NEET 2020)

(a)

(a) (b)

(b)

(c)
(c) (d)
50. Identify the compound that will react with Hinsberg's
reagent to give a solid which dissolves in alkali.
(NEET 2021)
(d)
 92 AMINES

53. Identify the product in the following reaction : 56. Identify the major product C formed in the following
reaction sequence? (NEET 2024)

CH 3CH 2CH 2 I 
NaCN
 A  OH
partialhydrolysis
B 
NaOH
Br2
 C
( major )

(a) butylamine
(b) butanamide
(NEET 2023) (c) ɑ -bromobutanoic acid
(d) propylamine

(a) (b)

(c) (d)
54. Which of the following reactions will NOT give primary
amine as the product? (NEET 2023)
 i LiAlH
(a) CH 3 CN  4
ii  H O
 Product
3

 i  LiAlH 4
(b) CH3 NC 
ii  H 3O
 Product
 i LiAlH
(c) CH3 CONH 2  4
ii  H O 
 Product
3

(d) CH 3CONH 2 

 Product
Br2 /KOH

55. Given below are two statements: (NEET 2024)

Statement I: Aniline does not undergo Friedel-Crafts
alkylation reaction.
Statement II: Aniline cannot be prepared through
Gabriel synthesis
(a) Both statement I and statement II are false
(b) Statement I is correct but statement II is false
(c) Statement I is incorrect but statement II is true
(d) Both statement I and statement II are true
AMINES 93

Exercise – 3: Achiever’s Section

Single Choice Questions
5. The major product obtained in this reaction can be
given as
1. Which of the following reactions does not yield an
amine?
(a) R-X+NH3 
Na 
(b) R-CH=NOH+[H]  
C 2 H5OH

H  +
(c) R-CN+H 2 O 
LiAlH (a) (b)
4
(d) R-CONH 2 +4[H] 
2. What is the end product in the following sequence of
operations?
HNO PCl
5  B 
3C NH (c) (d)
2  A 
C 2 H 5 NH 2 
6. The reaction of primary amine with chloroform and
(a) Ethyl cyanide (b) Methylamine
ethanolic solution of KOH is called
(c) Ethylamine (d) Acetamide
(a) Hofmann’s reaction
3. Which statement is not correct
(b) Reimer-Tiemann’s reaction
(a) Amines form hydrogen bond
(c) Carbylamine reaction
(b) Ethyl amine has higher boiling point than
(d) Kolbe’s reaction
propane
7. Which of the following is more basic than aniline?
(c) Methyl amine is more basic than ammonia
(a) Diphenylamine (b) Triphenylamine
(d) Dimethyl amine is less basic than methyl amine
(c) p-nitroaniline (d) Benzylamine
4. The increasing order of basicity of the following
8. An organic compound (A) on reduction gives
compounds is:
compound (B). (B) on treatment with CHCl3 and
alcoholic KOH gives (C). (C) on catalytic reduction
(A) gives N-methylaniline. The compound A is
(a) Methylamine (b) Nitromethane
(c) Aniline (d) Nitrobenzene
(B) 9. A compound ‘A’ when treated with HNO3 (in presence
of H2SO4) gives compound ‘B’, which is then reduced
with Sn and HCl to aniline. The compound ‘A’ is
(a) Toluene (b) Benzene
(c) Ethane (d) Acetamide
(C) 10. An aliphatic amine on treatment with alcoholic carbon
disulphide and mercuric chloride forms ethyl
isothiocyanate, the reaction is known as
(D) (a) Hofmann’s reaction
(a) (D) < (B) < (A) < (C) (b) (A) < (B) < (C) < (D) (b) Hofmann’s rearrangement
(c) (B) < (A) < (C) < (D) (d) (B) < (A) < (D) < (C) (c) Hofmann’s mustard oil reaction
(d) Hofmann’s bromamide degradation reaction
94 AMINES

11. Aniline react with Acetaldehye to form (c)

(a) Schiff’s base (b) carbylamines
(c) immine (d) None of these
12. The most favourable site of protonation in following
compound is:

(d)

16. When 2, 4-dinitro aniline reacts with NaNO2 + HCl at

(a) 4 (b) 2 5°C followed by reaction with anisole, a coloured

(c) 3 (d) 1 compound is formed which can be given as
13. In the following reaction, (a)
CHCl3 + C6H5NH2→ A + 3B + 3C,
the product A is
(a) Phenyl isocyanide (b) Phenyl cyanide
(c) Ethylene chloride (d) Chlorobenzene
14. In the following reaction, X is (b)
NaNO2  HCl
Bromin ation  Y  Z
X 
Boiling
 
 syn  Tribromobenzene
C H5OH
2
(a) Benzoic acid (b) Salicyclic acid
(c) Phenol (d) Aniline (c)
15. In the reaction

(d)

the product E is:

(a)

17. Primary and secondary amines are distinguished by

(a) Br2/KOH (b) HClO
(c) HNO2 (d) NH3

(b)
AMINES 95

Assertion and Reason Type Questions: (a) A (b) B

(A) If both assertion and reason are correct and reason (c) C (d) D
is the correct explanation of assertion. 24. Assertion: Aniline is a weaker base than benzylamine.
(B) If both assertion and reason are true but reason is Reason: In aniline, mesomeric interaction occurs
not the correct explanation of assertion. between benzene ring and amino group.
(C) If assertion is true but reason is false. (a) A (b) B
(D) If assertion is false but reason is true. (c) C (d) D
18. Assertion: In order to convert R–Cl to pure R–NH2, 25. Assertion: p-Anisidine is weaker base than aniline.
Reason: –OCH3 group in anisidine exerts +R effect.
Gabriel phthalimide synthesis can be used.
Reason: With proper choice of alkyl halides, (a) A (b) B
phthalimide synthesis can be used to prepare 1°, 2° or (c) C (d) D
3° amines. 26. Assertion: Aniline on reaction with NaNO2/HCl at
(a) A (b) B 0°C followed by coupling with β- naphthol gives a
(c) C (d) D dark blue coloured precipitate.
19. Assertion: In Hoffmann bromide reaction, the amine Reason: The colour of the compound formed in the
formed has one carbon atom less than the parent 1° reaction of aniline with NaNO2/HCl at 0°C
amide. followed by coupling with β -naphthol is due to the
Reason: N-methyl acetamide undergoes Hoffmann extended conjugation.
bromamide reaction. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 27. Assertion: On heating aniline hydrogen sulphate form
20. Assertion: Amines are more basic than esters and a mixture of ortho and para aminobenzene sulphonic
ethers. acids.
Reason: Nitrogen is less electronegative than oxygen. Reason: The sulphonic acid group is electron
It is in better position to accommodate the positive withdrawing.
charge on the proton (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 28. Assertion : In strongly acidic solutions, aniline
21. Assertion: n-Propylamine has a higher boiling point becomes more reactive towards electrophilic reagents.
than trimethylamine. Reason: The amino group being completely protonated
Reason: Among n-propylamine molecules there is in strongly acidic solution, the lone pair of electrons on
hydrogen bonding, but there is no hydrogen bonding the nitrogen is no longer available for resonance.
among trimethylamine molecules. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 29. Assertion: Benzene diazonium chloride does not give
22. Assertion: Carbylamine reaction involves the reaction tests for nitrogen.
between 1° amine and chloroform in basic medium. Reason: N2 gas is lost during heating.
Reason: In carbylamine reaction, –NH2 group is
(a) A (b) B
converted into –NC group. (c) C (d) D
(a) A (b) B 30. Assertion: In Sandmeyer reaction, diazonium salt is
(c) C (d) D heated with copper powder.
23. Assertion: Me3N reacts with BF3 whereas Ph3N does Reason: Sandmeyer reaction occurs by a free radical
not. mechanism.
Reason: The electron pair on nitrogen atom in Ph3N is (a) A (b) B
delocalised in the benzene ring and is not available to (c) C (d) D
boron in BF3
96 AMINES

Notes:

Find Answer Key and Detailed Solutions at the end of this book

AMINES
BIOMOLECULES
Chapter 08 98

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 2.1.3 On the basis of Sweetness:

Carbohydrates are primarily produced by plants and form a very
large group of naturally occurring organic compounds. Some
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, NOTE:
C6H12O5 is a carbohydrate but does not fit in this definition.
Saccharide came from a Latin word Saccharum which means
Chemically, the carbohydrates may be defined as optically active
Sugar
polyhydroxy aldehydes or ketones or the compounds which
produce such units on hydrolysis. Some of the carbohydrates, which 2.1.4 On the basis of Number of Carbon atoms:
are sweet in taste, are also called sugars. The most common sugar, Carbon General Aldehyde Ketone
used in our homes is named as sucrose whereas the sugar present Atoms Term
in milk is known as lactose. 3 Triose Aldotriose Ketoriose
4 Tetrose Aldotetrose Ketotetrose
5 Pentose Aldopentose Ketopentose
2.1 Classification of Carbohydrates 6 Hexose Aldohexose Ketohexose
Carbohydrates are classified on the basis of their behaviour on 7 Heptose Aldoheptose Ketoheptose
hydrolysis. They have been broadly divided into following three
groups: 2.1.5 On the basis of Number of Product of Hydrolysis:
2.1.1 On the basis of Functional Group:

SCAN CODE
Biomolecules
BIOMOLECULES 99
[Link] Monosaccharides 3.2 Reactions
A carbohydrate that cannot be hydrolysed further to give simpler
units of polyhydroxy aldehyde or ketone is called a (A) Oxidation
monosaccharide. Some common examples are glucose, fructose,
ribose, etc.
[Link] 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.
[Link] 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)

Fig. 7.1 : 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 O6
Sucrose Glu cos e Fructose

(B) From Starch

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

H 
 C6 H10O5 n  nH2 O 
393K,2-3 atm
 nC6 H12 O6
Starch or Cellulose Glucose

Fig. 7. 2 :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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(C) Oxime Formation 3.3 Configuration in Monosaccharides

Glucose is correctly named as D(+)-glucose. ‘D’ before the name
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 follows. The letters ‘D’ or ‘L’ before the
name of any compound indicate the relative configuration of a
Fig. 7.3: Oxime Formation particular stereoisomer. This refers to their relation with a particular
isomer of glyceraldehyde. Glyceraldehyde contains one
(D) Cyanohydrin Formation
asymmetric carbon atom and exists in two enantiomeric forms as
illustrated.

D-Glyceraldehyde L-Glyceraldehyde

Fig. 7. 4: Cyanohydrin Formation All those compounds which can be chemically correlated to (+)
NOTE: isomer of glyceraldehyde are said to have D-configuration whereas
those which can be correlated to (–) isomer of glyceraldehyde are
Carbonyl C has become chiral so 2 products are obtained which
are diastereomers. said to have L-configuration. For assigning the configuration of
monosaccharides, it is the lowest asymmetric carbon atom (as
(E) Acetylation shown below) which is compared. As in (+) glucose, –OH on the
lowest asymmetric carbon is on the right side which is comparable
to (+) glyceraldehyde, so it is assigned D-configuration. For this
comparison, the structure is written in a way that most oxidised
carbon is at the top.

Fig. 7.5: Acetylation

(F) Reaction with phenylhydrazine (formation of osazone)

3.4 Cyclic Structure of Glucose

Glucose is found to exist in two different crystalline forms which are
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
Fig. 7. 6 : Reaction with phenylhydrazine aqueous solution at 371 K.

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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
from the fact that the specific rotation of a freshly prepared aqueous
solution of -D(+)-glucose falls gradually from +111° to +52.5°
with time and that of -D(+)-glucose increases from +19.2° to
52.5°. Thus,

Fig. 7. 8 : Haworth Structure of Glucose

3.4.1 How to draw a Haworth Projection

This spontaneous change in specific rotation of an optically active A ring of 6 atoms (5 ‘C’ and 1 ‘O’) is drawn in which ‘O’ atom is
compound with time, to an equilibrium value, is called mutarotation. placed at right hand top corner as shown below
It was found that glucose forms a six-membered ring in which –
OH at C-5 is involved in ring formation. This explains the absence
of –CHO group and also existence of glucose in two forms as
shown below. These two cyclic forms exist in equilibrium with
open chain structure.

Carbon atom at the right hand side of oxygen is given number 1.

Then other carbon atoms are given numbers 2, 3 ......... in a clockwise
fashion. Groups attached to a carbon in Fischer projection lying
on the right hand side of that carbon are placed below the ring
and on the left hand side are placed above the ring. But CH2OH
group of carbon 5 is placed above the plane of ring by convention

Fig. 7.7: Cyclic and open chain structure of Glucose

The two cyclic hemiacetal forms of glucose differ only in the
configuration of the hydroxyl group at C1, called anomeric carbon
(the aldehyde carbon before cyclisation). Such isomers, i.e., -
form and -form, are called anomers. The six membered cyclic
structure of glucose is called pyranose structure (– or –), in
analogy with pyran. Pyran is a cyclic organic compound with one
oxygen atom and five carbon atoms in the ring. The cyclic structure
of glucose is more correctly represented by Haworth structure.

Fig. 7. 9: Cyclic and Haworth Projection of a-D-Glucose

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4. Fructose (Ketohexose) The cyclic structures of two anomers of fructose are represented
by Haworth structures as given.
Fructose also has the molecular formula C6H12O6 and on the basis
of its reactions it was found to contain a ketonic functional group
at carbon number 2 and six carbons in straight chain as in the case
of glucose. It belongs to D-series and is a laevorotatory compound.
It is appropriately written as D-(–)-fructose. Its open chain structure
is as shown

Fig. 7.12: Haworth Structure of Fructose

Table 7. 1: Comparison of Glucose and Fructose
[Link]. Property Glucose Fructose
(i) Molecular formula C6H12O6 C6H12O6
(ii) Nature Polyhydroxy Polyhydroxy
aldehyde ketone
(iii) Melting point 146°C 102°C
Fig. 7.10: Fructose (iv) Optical nature Dextro rotatory Laevo rotatory
It also exists in two cyclic forms which are obtained by the addition (v) Tollen’s reagent Silver mirror Silver mirror
 \  (vi) Fehling’s solution Red ppt Red ppt
of –OH at C5 to the  / C  O  group. The ring, thus formed is a
  (vii) Molisch test Violet colour Violet colour
five membered ring and is named as furanose with analogy to the (viii) Phenyl hydrazine Forms osazone Forms osazone
compound furan. Furan is a five membered cyclic compound with (ix) Oxidation by Saccharic acid Mixture of
one oxygen and four carbon atoms. conc. HNO3 glycolic acid,
Tetaric acid and
Trihydroxy
Gluteric acid

5. Disaccharides
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
-D- (–)-Fructofuranose -D- (–)-Fructofuranose
One of the common disaccharides is sucrose which on hydrolysis
Fig. 7.11: Cyclic Structure of Fructose gives equimolar mixture of D-(+)-glucose and
D-(–)-fructose.

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These two monosaccharides are held together by a glycosidic
linkage between C1 of -glucose and C2 of
-fructose. Since the reducing groups of glucose and fructose are
involved in glycosidic bond formation, sucrose is a non reducing
sugar.

 -linkage
Fig. 7.14:Maltose

Fig. 7.13: Sucrose 5.3 Lactose

Sucrose is a dextrorotaty compound and its hydrolysis produces It is more commonly known as milk sugar since this disaccharide
an equimolar solution of glucose and fructose. This solution is is found in milk. It is composed of -D-galactose and -D-glucose.
laevorotaty because laevo rotation of fructose is greater than Fischer projections of -D-Glucose and -D-Galactose are drawn
dextro rotation of glucose. below :
Thus, hydrolysis of sucrose brings about a change in the sign of
rotation, from dextro (+) to laevo (–) and the product is named as invert
sugar and this phenomenon is called as inversion of sugar.

5.2 Maltose
Another disaccharide, maltose is composed of two -D-glucose
units in which C1 of one glucose (I) is linked to C4 of another
glucose unit (II). The free aldehyde group can be produced at C1
of second glucose in solution and it shows reducing properties
so it is a reducing sugar.

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Cyclisation

- linkage
Fig. 7.15: Lactose

6. Polysaccharides
Polysaccharides contain a large number of monosaccharide units
joined together by glycosidic linkages. They mainly act as the
food storage or structural materials.
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
6.1 Starch
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 Starch is the main storage polysaccharide of plants. It is the most
are epimers and C-4 is epimeric carbon atom. In lactose, the linkage is important dietary source for human beings. High content of starch
between C1 of galactose and C4 of glucose. Hence it is also a reducing is found in cereals, roots, tubers and some vegetables. It is a
sugar. polymer of -glucose and consists of two components - Amylose
and Amylopectin. Amylose is water soluble component which
constitutes about 15-20% of starch. Chemically amylose is a long
unbranched chain with 200-1000 -D-(+)-glucose units held by
C1-C4 glycosidic linkage. Amylopectin is insoluble in water and
constitutes about 80-85% of starch. It is a branched chain polymer
of -D-glucose units in which chain is formed by C1-C4 glycosidic
linkage whereas branching occurs by C1-C6 glycosidic linkage.

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Fig. 7.16: Amylose

Fig. 7.17: Amylopectin

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6.2 Cellulose 6.3 Glycogen

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

Fig. 7.18: Cellulose

Table 7. 2: 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

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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 7.3.
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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Table 7. 3: Natural Amino Acids
[Link]. 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

N = Neutral (No. of carboxylic group = [Link] amino group) NOTE:

B = Basic (No. of carboxylic group < [Link] amino group)
A = Acidic (No. of carboxylic group > [Link] amino group) 1. *Essential amino acids.
2. Arginine has highest isoelectric point i.e. 10.8.
3. Cysteine has lowest isoelectric point i.e. 5.1.

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7.3 Classification of Amino Acids number of negatively charged groups equals the number of
positively charged groups.
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. Alanine

7.4 Properties of Amino Acids

Amino acids are usually colourless, crystalline solids. These are
water-soluble, high melting solids and behave like salts rather
than simple amines or carboxylic acids. This behaviour is due to
the presence of both acidic (carboxyl group) and basic (amino If an amino acid has an ionizable side chain, its pI is the average of
group) groups in the same molecule. the pKa values of the similarly ionizing groups (positive ionizing
to uncharged, or uncharged ionizing to negative). For example,
the pI of lysine is the average of the pKa values of the two groups
that are positively charged in their acidic form and uncharged in
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 Lysine
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.
This is because at pH = 2.34, half the molecules have a negatively
charged carboxyl group and half have an uncharged carboxyl
group, and at pH = 9.69, half the molecules have a positively Glutamic acid
charged amino group and half have an uncharged amino 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

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7.5 Structure of Proteins - Peptide Bond (ii) Secondary Structure

The secondary structure of protein refers to the shape in which a
Proteins are the polymers of -amino acids and they are connected
long polypeptide chain can exist. They are found to exist in two
to each other by peptide bond or peptide linkage. Chemically,
different types of structures viz. -helix and -pleated sheet
peptide linkage is an amide formed between –COOH group and –
structure. These structures arise due to the regular folding of the
NH2 group.
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.
Peptide linkage In -structure all peptide chains are stretched out to nearly
maximum extension and then laid side by side which are held
Fig. 7.19: Peptide linkage in proteins together by intermolecular hydrogen bonds.
The reaction between two molecules of similar or different amino
acids, proceeds through the combination of the amino group of
one molecule with the carboxyl group of the other. This results in
the elimination of a water molecule and formation of a peptide
bond –CO–NH–.

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
said to be the primary structure of that protein. Any change in this
primary structure i.e., the sequence of amino acids creates a
different protein.
Fig. 7.20: -Helix structure of proteins

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Fig. 7.22: 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 of
egg white on boiling is a common example of denaturation.
Another example is curdling of milk which is caused due to the
formation of lactic acid by the bacteria present in milk.
Fig. 7.21: - Pleated sheet structure of proteins
(iii) Tertiary Structure 8. Nucleic Acids
The tertiary structure of proteins represents overall folding of the
Every generation of each and every species resembles its ancestors
polypeptide chains i.e., further folding of the secondary structure.
in many ways. How are these characteristics transmitted from one
It gives rise to two major molecular shapes viz. fibrous and
generation to the next ? It has been observed that nucleus of a living
globular. The main forces which stabilise the 2° and 3° structures
cell is responsible for this transmission of inherent characters, also
of proteins are hydrogen bonds, disulphide linkages, van der
called heredity. The particles in nucleus of the cell, responsible for
Waals and electrostatic forces of attraction.
heredity, are called chromosomes which are made up of proteins and
(iv) Quaternary Structure another type of biomolecules called nucleic acids. These are mainly
Some of the proteins are composed of two or more polypeptide of two types, the deoxyribonucleic acid (DNA) and ribonucleic acid
chains referred to as sub-units. Subunits with respect to each (RNA). Since nucleic acids are long chain polymers of nucleotides,
other is known as quaternary structure. so they are also called polynucleotides.

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8.1 Chemical Composition of Nucleic Acids Nucleotides are joined together by phosphodiester linkage
between 5’ and 3’ carbon atoms of the pentose sugar. A simplified
Complete hydrolysis of DNA (or RNA) yields a pentose sugar,
version of nucleic acid chain is as shown below
phosphoric acid and nitrogen containing heterocyclic compounds
(called bases). In DNA molecules, the sugar moiety is -D-2-
deoxyribose whereas in RNA molecule, it is -D-ribose.

Information regarding the sequence of nucleotides in the chain of

a nucleic acid is called its primary structure. Nucleic acids have a
secondary structure also. James Watson and Francis Crick gave a
double strand helix structure for DNA. Two nucleic acid chains
are wound about each other and held together by hydrogen bonds
(a) (b) between pairs of bases. The two strands are complementary to
Fig. 7.23: (a) -D- ribose (b) -D-2deoxyribose each other because the hydrogen bonds are formed between
DNA contains four bases viz. adenine (A), guanine (G), cytosine specific pairs of bases. Adenine forms hydrogen bonds with
(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). thymine whereas cytosine forms hydrogen bonds with guanine.
In secondary structure of RNA, helices are present which are
only single stranded. Sometimes they fold back on themselves to
form a double helix structure. RNA molecules are of three types
and they perform different functions. They are named as
messenger RNA (m-RNA), ribosomal RNA (r-RNA) and transfer
RNA (t-RNA).

Fig. 7.24: Bases in DNA and RNA

8.2 Structure of Nucleic Acids

A unit formed by the attachment of a base to 1’ position of sugar is
known as nucleoside. In nucleosides, the sugar carbons are
numbered as 1’, 2’, 3’, etc. In order to distinguish these from the
bases. When nucleoside is linked to phosphoric acid at 5’-position
of sugar moiety, we get a nucleotide.

Fig. 7.25: Structure of (a) a nucleoside and (b) a nucleotide Fig. 7.26: Double strand helix structure for DNA

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8.3 DNA Vs RNA 9. Enzymes
Table 7. 4: DNA Vs RNA Enzymes are biological catalysts. Chemically all enzymes are
[Link]. Deoxyribonucleic Ribonucleic globular proteins. Some important enzymes and their functions
Acid (DNA) Acid (RNA) are given
(i) DNA occurs in the RNA occurs in the Table 7. 5:Enzymes
nucleus of the cell. cytoplasm of the cell.
[Link]. Enzyme Reaction Catalysed
(ii) The sugar present in The sugar present in
(i) Invertase Sucrose  Glucose +
DNA is RNA is D(-) ribose
or sucrase Fructose
D-(–)-2-deoxyribose.
(ii) Maltase Maltose  2 Glucose
(iii) DNA contains cytosine RNA contains cytosine
(iii) Lactase Lactose  Glucose +
and thymine as pyrimidine and uracil as pyrimidine
Galactose
bases and guanine and bases and guanine and
(iv) -Amylase Starch  n × Glucose
adenine as purine bases. adenine as purine bases.
(v) Emulsin Cellulose  n × Glucose
(iv) DNA has double-stranded RNA has single stranded (vi) Urease NH2CONH2  CO2 + 2NH3
-helix structure. -helix structure. (vii) Carbonic H2CO3  CO2 + H2O
(v) DNA undergoes replication. RNA usually does not anhydrase
undergo replication (viii) Pepsin Proteins   - Amino acids
(vi) DNA controls the RNA controls the (ix) Trypsin Proteins   - Amino acids
transmission of synthesis of proteins. (x) Nucleases DNA or RNA  Nucleotides
hereditary effects. (xi) DNA Deoxynucleotide  DNA
polymerase triphosphates
8.4 Biological Functions of Nucleic Acids (xii) RNA Ribonucleotide  RNA
polymerase triphosphates
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.

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10. Vitamins 10.1 Classification of Vitamins

They are generally regarded as organic compounds required in Vitamins are classified into two groups depending upon their
the diet in small amounts to perform specific biological functions solubility in water or fat.
for normal maintenance of optimum growth and health of the (i)Fat soluble vitamins: Vitamins which are soluble in fat and oils
organism. Vitamins are designated by alphabets A, B, C, D, etc. but insoluble in water are kept in this group. These are vitamins
Some of them are further named as sub-groups e.g. B1, B2 , B6, B12, A, D, E and K. They are stored in liver and adipose (fat storing)
etc. Excess of vitamins is also harmful and vitamin pills should not tissues.
be taken without the advice of doctor. (ii) Water soluble vitamins: B group vitamins and vitamin C are
soluble in water so they are grouped together. Water soluble
vitamins must be supplied regularly in diet because they are
readily excreted in urine and cannot be stored
(except vitamin B12) in our body.

Table 7. 6: Some important Vitamins, their Sources and their Deficiency Diseases
[Link]. 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.

11. Lipids 11.1 Function of Lipids

Biological substances which are insoluble in water are known as The function of lipids are very diverse.
lipids. This characteristic physical property of lipids makes them (i) Some lipids are used to store energy.
very different from other biomolecules like carbohydrates, proteins, (ii) In addition to serving as energy sources, some lipids
and nucleic acids. Lipids have extremely varied structure. accumulate in tissues around to act as insulation and
Lipids play important roles in many cellular processes like energy protection.
storage, structural support, protection, and communication. (iii) Other lipids carry chemical messages and help regulate cell
Common lipid groups are waxes, steroids, triglycerides, and
activity from one part of the body to another.
phospholipids.

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BIOMOLECULES 115
12. Hormones 12.2 Peptide Hormones
Hormones are biomolecules which are produced in the ductless Table 7. 8: Peptide Hormones
(endocrine) glands and are carried to different parts of the body
Organ
by the blood stream where they control various metabolic
Name of Functions
processes. These are required in minute quantites and unlike fats
and carbohydrates these are not stored in the body but are Secretion
continuously produced. (i) Oxytocin Posterior Control the contraction of
pituitary the uterus after child birth
and releases milk from the
12.1 Steroidal Hormones mammary glands
(ii) Vasopressin Posterior Control the reabsorption
Table 7. 7: Steroidal Hormones pituitary of water in the kidney.
gland
Name Organ of Functions
Secretion (iii) Angiotensin II Blood Potent vasoconstrictor i.e.
(i) Adrenaline or Adrenal It is an amine compound and Plasma contracts the blood vessels
Epinephrine medulla was the first hormone to be of with high blood pressure.
isolated. Prepares animals and persons
humans for emergency in (iv) Insulin Pancreas Controls the metabolism of
many ways by raising the glucose, maintains glucose
pulse rate, blood pressure level in the blood.
etc. stimulates the breakdown
of liver glycogen into blood
glucose and fats into fatty 12.3 Amine Hormones
acids during emergency.
These properties make
Table 7. 9:Amine Hormones
adrenaline as one of the most Organ
valuable drugs used in Name of Functions
medicine. Secretion
(ii) Thyroxine Thyroid Controls metabolism of (i) Sex hormones Control the development
gland carbohydrates, lipids and (a) Androgens Testes and normal functioning of
proteins. (Testosterone) Androsterone and male sex
organs.

(b) Estrogens Ovary Control the development

(Estrone, and normal functioning of
Estradiol,Estriol) female sex organs.
(c) Gestogens Corpus Control the development
(Progesterone) luteum and maintenance of
pregnancy

(ii) Adrenal corex Adrenal Regulate the metabolism

hormones or cortex of fats, proteins and
corticoids carbohydrates: control the
(Cortisone, balance of water and
Corticosterone minerals in the body.
Aldosterone
etc.)

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13. Test for Biomolecules The furfural derivatives formed by a sugar with ketonic functional
group condense with resorcinol to form a chromogen having
13.1 Test of Carbohydrates cherry-red color.
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, i.e. solution forms complex blue colour solution. On heating the blue
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 The appearance of blue colour solution confirms the presence of
along the sides of the test tube. A violet ring is formed at the starch.
junction of the two layers.

13.1.2 Benedict’s Test

13.2 Test for Proteins
Benedict’s solution contains copper sulfate that provides cupric
ions, Sodium carbonate that makes solution alkaline, and Sodium 13.2.1 Biuret Test
Citrate that provides citrate ions. An alkaline solution of a protein when treated with a few drops of
It is a test for reducing sugars. Carbohydrates having free 1% CuSO4 solution, produces a violet colouration. The colour is
functional group, that is not involved in a glycosidic bond, give
due to the formation of a coordination complex of Cu+2 with
this test positive. All monosaccharides and reducing disaccharides
give positive Benedict’s test. This test is negative for and –NH– groups of the peptide linkages.
polysaccharides.
In the presence of an alkali, reducing sugars undergo
13.2.2 Xanthoproteic Test
tautomerization to form enediols. These enediols reduce the cupric
ions (Cu+2) to form cuprous ions (Cu+). The cuprous ions from When a protein is treated with conc. HNO3 a yellow colour is
cuprous hydroxide. Upon heating, it is converted to cuprous oxide produced. This test is given by a protein which consists of -
that forms precipitates. The citrate ions present in the reagent amino acids containing a benzene ring such as tyrosine,
release the cuprous ions slowly for reduction and prevent the phenylalanine etc. and the yellow colour is due to the nitration of
formation of Cu(OH)2 until the oxidation-reduction process is the benzene ring. An important example of this test is that when
completed. conc. HNO3 is spilled on your hands, the skin turns yellow due to
nitration of benzene ring of the amino acids of the proteins present
13.1.3 Barfoed’s Test in your skin.
Barfoed’s reagent contains copper acetate in glacial acetic acid. It
is a differentiating test to distinguish between monosaccharides 13.2.3 Millon’s Test
and disaccharides. Barfoed’s test is also based on the reducing Millon’s reagent is a solution of mercurous nitrate and mercuric
ability of sugar. However, sucrose also gives this test positive as nitrate in nitric acid containing little nitrous acid. When Millon’s
it undergoes hydrolysis in the presence of an acid. reagent is added to aqueous solution of protein, a white ppt. is
Monosaccharides give early positive test while the disaccharides formed. This test is given by all proteins containing phenolic -
give late positive test. amino acids i.e. tyrosine. As such gelatin which does not contain
Formation of red precipitates after the initial first 5 minutes phenolic -amino acids does not give this test.
indicates the presence of a monosaccharide. If precipitates are
13.2.4 Ninhydrin Test
formed after 15 minutes, a disaccharide is present in the test
solution. When proteins are boiled with a dilute aqueous solution of
ninhydrin (2, 2-dihydroxyindane-1,3-dione), a blue-violet colour
13.1.4 Seliwanoff’s Test is produced. This test is actually given by all
Seliwanoff’s reagent contains water, resorcinol and concentrated -amino acids. Since proteins on hydrolysis give -amino acids,
HCl This test is used to detect monosaccharides with a ketonic therefore, proteins and peptides also give this test.
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.

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BIOMOLECULES 117
Summary
Reactions of Glucose

Classification of Amino Acids

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118 BIOMOLECULES

Structure of Proteins

Chemical Composition of Nucleic Acids

Classification of Vitamins

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BIOMOLECULES 119

Exercise – 1: Basic Objective Questions

Carbohydrates
1. A disaccharide on hydrolysis gives 10. D-Glucose exists in x different forms. The value of x
(a) Two molecules of the same monosaccharide (stereoisomer) is
(b) One molecule each of two different (a) 2 (b) 3
monosaccharides (c) 4 (d) 5
(c) Three molecules of the same monosaccharide 11. Molisch test is answered by
(d) Two molecules of the same or one molecule each (a) All carbohydrates (b) Sucrose
of the two different monosaccharides. (c) Fructose (d) Glucose
2. What is the structure of L-Glucose? 12. Glucose and mannose are
(a) Optical isomers (b) Anomers
(c) Epimers (d) Chain isomers
13. When amylases catalyse the hydrolysis of starch, the
final product obtained is chiefly
(a) Cellubiose (b) Glucose
(a) (b) (c) Maltose (d) Sucrose
14. Which L-sugar on oxidation gives an optically active
dibasic acid (2 COOH groups)?

(c) (d) None of these

3. Which of the following is a non-reducing sugar?
(a) Sucrose (b) Maltose (a) (b)
(c) Lactose (d) Ribose
4. The commonest disaccharide has the molecular formula
(a) C12H22O11 (b) C10H18O9
(c) C10H20O10 (d) C10H32O11
5. Table sugar is a
(a) Disaccharide of D-glucose and D-fructose (c) (d) None of these
(b) A monosaccharide 15. Glucose and fructose are
(c) A disaccharide containing two glucose units (a) Optical isomers (b) Tautomers
(d) D-glucose (c) Functional isomers (d) Chain isomers
6. A certain compound gives negative test with ninhydrin 16. Number of stereo centers present in linear and cyclic
and positive test with Benedict’s solution. The structures of mannose are respectively:
compound is (a) 4 & 5 (b) 4 & 4
(a) A protein (b) A monosacchride (c) 5 & 5 (d) 5 & 4
(c) A lipid (d) An amino acid 17. Glucose is a/an
7. Which of the following is the sweetest sugar? (a) Aldohexose (b) Aldopentose
(a) Sucrose (b) Glucose (c) Aldotetrose (d) Ketohexose
(c) Fructose (d) Maltose 18. Which of the following is a reducing sugar?
8. D-glucose & D-fructose can be differentiated by (a) Glucose (b) Fructose
(a) Fehling sol (b) Tollens reagent (c) Maltose (d) All of these
(c) Benedict test (d) Br2/H2O 19. α-D-Glucose and β-D-glucose differ from each other due
9. Glucose reduces to difference in one carbon with respect to its?
(a) Tollen’s reagent (b) Fehling’s solution (a) Size of hemiacetal ring (b) Number of OH groups
(c) Benedict’s solution (d) All (c) Configuration (d) Conformation
120 BIOMOLECULES

20. Lactose is a disaccharide of Choose the correct range from the given option.
(a) Glucose only (b) Glucose and fructose (a) 1  10 (b) 2  10
(c) Glucose and galactose (d) Galactose only (c) 4  10 (d) 5  10
21. Rapid interconversion of α-D-glucose and β-D-glucose 32. Choose the appropriate statement(s) about glucose.
in solution is known as (a) It is also called dextrose
(a) racemization (b) asymmetric induction (b) It is monomer of compound containing starch,
(c) fluxional isomerization (d) mutarotation cellulose
22. Assuming sweetness of the cane sugar to be 10, the (c) Its molecular formula is C6H12O6
sweetness of glucose is (d) All of the above
(a) 15 (b) 1.5 33. Name the reagent and condition required for the
(c) 12.5 (d) 7.5 following reaction.
23. Which of the following reduces Tollen’s reagent?
(a) Glucose (b) Fructose
(c) Lactose (d) All
24. Which carbohydrate is an essential constituent of plant n-hexane
cells? (a) HF, (b) HCl, 
(a) Starch (b) Cellulose
(c) HBr, (d) HI,
(c) Sucrose (d) Maltose
25. On hydrolysis of starch, we finally get 34. Fructose is a/an
(a) glucose (b) fructose (a) ketohexose (b) aldohexose
(c) both (a) and (b) (d) sucrose (c) hexoseketo (d) hexosealdo
26. Which one of the following gives positive Fehling’s 35. Sucrose (cane sugar) is a disaccharide. One molecule of
solution test ? sucrose on hydrolysis gives
(a) Sucrose (b) Glucose (a) 2 molecules of glucose
(c) Fats (d) Proteins (b) 2 molecules of glucose +1 molecule of fructose
27. Which of the following is the general formula of (c) 1 molecule of glucose +1 molecule of fructose
Carbohydrates? (d) 2 molecules of fructose
(a) (C4H2O)n (b) (C6H2O)n 36. I. Disaccharides on hydrolysis with dilute acid gives
(c) (CH2O)n (d) (C2H2O)n three molecules of same or different monosaccharides.
28. Select the biomolecule(s) that help during the formation II. Disaccharides are formed by the loss of water with
of the living system an oxide linkage.
(a) Carbohydrates III. The oxide linkage in the disaccharide is called
(b) Nucleic acids glycosidic linkage.
(c) Lipids Choose the incorrect statement about disaccharide and
(d) All of the above select the most appropriate option.
29. Carbohydrates are produced by ...I... and form group of (a) Only I
natural occurring ...II... compounds. (b) Only II
Fill in the blanks I and II with appropriate words. (c) Only III
(a) I  plants; II  inorganic (d) Only II and III
37. Polysaccharides contain a large number of …I… units
(b) I  plants; II  organic
joined by …II… linkage. They act as the food storage
(c) I  animals; II  organic
or structural material.
(d) I  animal; II  inorganic
Fill in the blanks with appropriate words and choose the
30. Select the group in which the cane sugar, glucose and
correct option.
starch are classified.
(a) I Oligosaccharide, II  glycosidic
(a) Carbohydrates (b) Proteins
(b) I Monosaccharide, II  carbon
(c) Nucleic acids (d) Vitamins
31. Carbohydrate that yield …….. monosaccharide unit on (c) I Monosaccharide, II  glycosidic
hydrolysis are called oligosaccharide. (d) I Disaccharide, II  glycosidic
BIOMOLECULES 121

38. Select the evidence for the open chain structure of 44. Which of the following represents the anomer of the
glucose. compound shown?
(a) Reaction with Tollen’s reagent
(b) Reaction with Fehling solution
(c) Pentacetyl derivative of glucose
(d) Cyanohydrin formation with HCN.
39. “Carbohydrate that cannot be hydrolysed further to give
simpler unit of polyhydroxy aldehyde or ketone”. Name
the type of carbohydrate.
(a) Monosaccharide (b) Oligosaccharide
(c) Polysaccharide (d) All of these
40. Select the incorrect statement about the sugar.
(a) It is sweet in taste
(b) Sugar present in milk is called lactose (a) (b)
(c) Greek word ‘sakcharon’ means sugar
(d) None of these
41. Sucrose reacts with acetic anhydride to form
(a) Penta-acetate (b) Hexa-acetate
(c) Tetra-acetate (d) Octa-acetate
(c) (d) None of these
42. Identify the correct set of stereochemical relationships
45. Among the three compounds shown below, two yield the
amongst the following monosaccharides I-IV.
same product on reaction with warm HNO3. The
exception is

(I) (II)
(a) (b)

(III) (IV)
(a) I and II are anomers ; III and IV are epimers (c) (d) None of these
(b) I and III are epimers ; II and IV are anomers 46. Oxidation of glucose with Ag2O gives
(c) I and II are epimers ; III and IV are anomers (a) D-Gluconic acid (b) L-Glucaric acid
(d) I and III are anomers ; I and II are epimers
(c) L-Gluconic acid (d) L-Glucaric acid
43. The optical rotation of the α-form of a pyranose is +
HNO
150.7°, that of the β-form is +52.8°. In solution an 47. D-Glucose 
 
3
(A), Product (A) is
equilibrium mixture of these anomers has an optical
rotation of +80.2°. The percentage of the α form in (a) D-Gluconic acid (b) D-Glucitol
equilibrium mixture is (c) D-Fructose (d) D-Glucaric acid
(a) 28% (b) 32%
(c) 68% (d) 72%
122 BIOMOLECULES

48. Assertion (A) Glucose on acetylation gives pentaacetate. 56. The number of amino acids found in proteins that a
Reason (R) It contains five OH group. human body can synthesize is
(a) Both A and R are correct; R is the correct (a) 20 (b) 10
explanation of A (c) 5 (d) 14
(b) Both A and R are correct; R is not the correct 57. The number of tripeptides formed by three different
explanation of A amino acids are
(c) A is correct; R is incorrect (a) Three (b) Four
(d) R is correct; A is incorrect (c) Five (d) Six
Amino Acids 58. When pieces of human hair are heated strongly with
49. The acid showing salt-like character in aqueous solution soda- lime, smell of ammonia can be detected. Which
is one of the following conclusion can be drawn from this
(a) Acetic acid (b) Benzoic acid observation?
(c) Formic acid (d) α-Aminoacetic acid (a) Ammonia is present in the human hair
50. Which of the following α-amino acids does not contain a (b) Ammonium salt is present in hair
chiral carbon? (c) Hair contains amino acids
(a) Glycine (b) Alanine (d) None of the above
(c) Phenylalanine (d) Valine 59. Which amino acid is achiral?
51. Which statement correctly completes the statement? (a) Alanine (b) Valine
Except for glycine, which is achiral, all the amino acids (c) Proline (d) None of these
present in proteins .......... 60. In aqueous solutions, amino acids mostly exist as
(a) are chiral, but racemic (a) NH2  CHR  COOH
(b) have the L configuration at their α carbon 
(b) NH2  CHR  COO
(c) have the R configuration at their α carbon

(d) have the S configuration at their α carbon (c) H 3 N  CHR  COOH

52. At Iso-electric point (d) H 3 N  CHR  COO 
(a) Conc. of cation is equal to conc. of anion
61. In an amino acid, the carboxyl group ionises at
(b) Net charge is zero.
pKa1  2.34 and ammonium ion at pKa2 = 9.60. The
(c) Maximum conc. of di-polar ion (Zwitter ion) will
be present isoelectric point of the amino acid is at pH
(d) All of the above (a) 5.97 (b) 2.34
53. Find iso-electric point of the given amino acid (c) 9.60 (d) 6.97

62.
Identify the amino acid obtained by hydrolysis of the
(a) 5.5 (b) 6.5 above compound.
(c) 3 (d) 5 (a) Glycine (b) Alanine
54. Lack of essential amino acids in the diet leads to the (c) Both (a) and (b) (d) None of these
disease called 63. Which of following amino acid has lowest iso-electric
(a) Night blindness point?
(b) Pernicious anaemia (a) Glycine (b) Alanine
(c) Kwashiorkor (c) Aspartic acid (d) Lysine
(d) Sickel cell anaemia 64. Which of the following does not exist as a zwitterion?
55. Which one of the following is an essential amino acid? (a) Glycine (b) Alanine
(a) Tyrosine (b) Lysine (c) Sulphanilic acid (d) p-methylbenzoic acid
(c) Proline (d) Glycine
BIOMOLECULES 123

65. Which of the functional group(s) is/are present in the 73. Which one of the following amino acid has phenolic OH
amino acids? group?
(a) –NH2 (b) – COOH (a) Lysine (b) Arginine
(c) –COOR (d) Only (a) and (b) (c) Proline (d) Tyrosine
66. Which of the following statement is false? 74. The relation of the isoelectric point for an amino acid, to
(a) Glycine is named since it has sweet taste solubility is
(b) Tyrosine means cheese (a) the two are not related
(c) Amino acids are generally represented by 3- (b) an amino acid is least soluble at its isoelectric point
letter symbol (c) an amino acid has the maximum solubility at the
(d) None of these isoelectric point
67. How many amino acids (approx) are involved during the (d) solubilities of only some amino acids depend on it.
synthesis of protein? 75. Lysine is least soluble in water in the pH range
(a) 15 (b) 18 (a) 3 to 4 (b) 5 to 6
(c) 20 (d) 91 (c) 6 to 7 (d) 8 to 9
68. How many essential amino acids are present in the living 76. Assertion (A) Amino acids react with acid and base both.
system? Reason (R) In Zwitter ionic form, amino acids show the
(a) 5 (b) 10 amphoteric behavior.
(c) 15 (d) 20 (a) Both A and R are correct; R is the correct
69. I. Histidine II. Proline explanation of A
III. Threonine IV. Aspartic acid (b) Both A and R are correct; R is not the correct
Select the essential amino acid(s) from the above amino explanation of A
acid and choose the appropriate option. (c) A is correct; R is incorrect
(a) II and III only (b) I and IV only (d) R is correct; A is incorrect
(c) I and III only (d) I and II only
70. Consider the following statements of amino acids: Proteins
I. they are colourless, crystalline solids.
II. they are water soluble and are high melting solids. 77. Denaturation of proteins leads to loss of its biological
III. they behave like salts rather than simple amines or activity by
carboxylic acids. (a) Formation of amino acids
Select the correct statement(s) from the above statements (b) Loss of primary structure
and choose the appropriate option. (c) Loss of both primary and secondary structures
(a) I and II (b) II and III (d) Loss of both secondary and tertiary structures
(c) Only III (d) All of these 78. The peptide bond is
71. Name the molecule which is eliminated during the (a) –CONH2 (b) –CONH–
formation of peptide bond. (c) –COONH4 (d) –N = C = O
(a) Acid (b) Amine 79. Proteins are
(c) Water (d) Alcohol (a) Polyamides
H 2 N   CH 2  4  C H  COOH (b) Polyesters
72. Lysine | is…… (c) Polyhydric alcohols
NH 2
(d) Polycarboxylic acids
I.  -amino acid 80. Which one of the following is not a protein?
II. basic amino acid (a) Wool (b) Nail
III. amino acid synthesised in body (c) Hair (d) DNA
IV.  -amino acid
Select the option with correct properties about lysine.
(a) I and II (b) II and III
(c) III and IV (d) IV and I
124 BIOMOLECULES

81. Mark the wrong statement about denaturation of proteins 90. Which of the following statement is incorrect about the
(a) The primary structure of the protein doesn’t change secondary structure of protein?
(b) Globular proteins are converted into fibrous (a) It refers to the shape in which long polypeptide
proteins chain can exist
(c) Fibrous proteins are converted into globular
(b) It exists in two different type of structures, i.e.,  -
proteins
(d) The biological activity of the protein is destroyed helix and  -pleated sheet structure
82. The sequence in which the α-amino acids are linked to (c) Its structure arises due to regular folding of the
one another in a protein molecule is called its backbone of the polypeptide chain
(a) Primary structure (b) Secondary structure (d) There is the covalent bonding between  C  O and
(c) Tertiary structure (d) Quaternary structure NH groups of the peptide bond
83. Which of the following contains nitrogen? 91. The tertiary structure of proteins arises due the further
(a) Fats (b) Proteins folding of the …I… structure. It gives rise to major
(c) Carbohydrates (d) None molecular shapes, i.e., …II…
84. Proteins are condensation polymers of Select appropriate words to complete the above
(a) α-Amino acids (b) β-Amino acids statement from the options given below.
(c) α-Hydroxy acids (d) β-Hydroxy acids (a) I primary; II  fibrous and globular
85. The bond that determines the secondary structure of a (b) I  secondary; II  fibrous and globular
protein is (c) I  primary; II  tertiary
(a) Co-ordinate bond (b) Covalent bond (d) I  secondary; II  tertiary
(c) Hydrogen bond (d) Ionic bond
92. During denaturation, ...I... structures of proteins are
86. Which of the following is not a function of proteins?
destroyed but ...II... structure remains intact. Here I and
(a) nail formation
II refer to
(b) skin formation
(a) I  1o and 2o ; II  3o
(c) muscle formation
(d) providing energy for metabolism (b) I  2o and 3o ; II  1o
87. On what basis, do the fibrous and globular proteins are (c) I  1o and 3o ; II  2o
classified? (d) I  1o and 4o ; II  3o
(a) On the basis of number of the amino acids 93. The spatial arrangement of the two or more polypeptide
(b) On the basis of their molecular shape chains with respect to each other is known as
(c) On the basis of type of the amino acids (a) primary structure (b) secondary structure
(d) All of the above (c) tertiary structure (d) quaternary structure
88. Which of the following statement(s) is/are correct about 94. Proteins can be classified into two types on the basis of
proteins? their molecular shape i.e., fibrous proteins and globular
(a) Proteins form the basis of structure and function of proteins. Examples of fibrous proteins are
life I. insulin II. keratin
(b) They are required for growth and maintenance of III. albumin IV. Myosin
body Select the correct option.
(c) They are polymers of  -amino acids (a) I and II (b) II and IV
(d) All of the above (c) III and I (d) I and III
89. In.....I… proteins, chains of polypeptides coil around
each other to give a spherical shape. Nucleic Acids
They are generally …II… in water. …III… and insulin 95. The pentose sugar in DNA and RNA has the
are the common example of these proteins. (a) Open chain structure
Here I, II and III refer to (choose the correct option). (b) Pyranose structure
(a) I  fibrous; II  soluble; III  keratin (c) Furanose structure
(b) I  fibrous; II  insoluble; III  albumin (d) None of the above
(c) I  globular; II  insoluble; III  keratin
(d) I  globular; II  soluble; III  albumin
BIOMOLECULES 125

96. Chargaff’s rule states that in an organism 105. In DNA, the complementary bases are
(a) amount of adenine (A) is equal to that of guanine (G) (a) Uracil and adenine : cytosine and guanine
and the amount of thymine (T) is equal to that of (b) Adenine and thymine : guanine and cytosine
cytosine (C) (c) Adenine and thymine : guanine and uracil
(b) amount of adenine (A) is equal to that of cytosine (d) Adenine and guanine : thymine and cytosine
(C) and the amount of thymine (T) is equal to that of 106. Which of the following compound is responsible for the
guanine (G) transmission of heredity characters?
(c) amount of all bases are equal (a) RNA
(d) amount of adenine (A) is equal to that of thymine (T) (b) DNA
and the amount of guanine (G) is equal to that of (c) Glucose
cytosine (C) (d) Haemoglobin
97. Which of the following statements about DNA is not 107. If the sequence of bases in DNA is TGAACCCTT then
correct? the sequence of bases in m-RNA is
(a) It has a double helix structure.
(a) ACUUGGGAA
(b) It undergoes replication.
(b) TCUUGGGTT
(c) The two strands in a DNA molecule are exactly
(c) ACUUCCCAA
similar.
(d) None of the above
(d) It contains the pentose sugar, 2-deoxyribose.
108. Which base is found only in the nucleotides of RNA?
98. Which substance is not present in nucleic acids?
(a) Adenine (b) Uracil
(a) Cytosine (b)Adenine
(c) Guanine (d) Cytosine
(c) Thymine (d)Guanidine
109. In the double helix structure of DNA, base pairs are
99. Which of the following sets of bases is present both in
(a) Part of the back bone structure
DNA and RNA?
(b) Inside the helix
(a) Adenine, uracil, thymine
(c) Outside the helix
(b) Adenine, guanine, cytosine
(d) None of these
(c) Adenine, guanine, uracil
110. A nucleotide consists of
(d) Adenine, guanine, thymine
(a) carbon sugar
100. Purine derivative among the following bases is
(b) nitrogen containing base
(a) thymine (b) uracil
(c) phosphoric acid
(c) guanine (d) cytosine
(d) all of these
101. Which of the following statements about RNA is not
111. In DNA, the linkages between different nitrogenous
correct?
bases is?
(a) It has a single strand.
(a) H-Bonding (b) Phosphate linkage
(b) It does not undergo replication.
(c) Glycosidic linkage (d) Peptide linkage
(c) It does not contain any pyrimidine base.
112. What is the composition of nucleoside?
(d) It controls the synthesis of proteins.
(a) a sugar + a phosphate
102. If one strand of DNA has the sequence ATGCTTGA, the
(b) a base + a sugar
sequence in the complimentary strand would be
(c) a base + a phosphate
(a) TACGAACT (b) TCCGAACT
(d) a base + a sugar + phosphate
(c) TACGTACT (d) TACGTAGT
113. DNA molecule takes the shape of…I…helix which are
103. The double helical structure of DNA was proposed by
made up of alternate units of …II…and…III….
(a) Watson and Crick (b) Meichers
(c) Emil Fischer (d) Khorana (a) I  double II  phosphate III  Sugar ribose
(b) I  -pleated II  phosphate III  Sugar
104. In nucleic acids, the nucleotides are linked to one
deoxyribose
another through
(c) I  double II  phosphate III  sugar
(a) Hydrogen bond (b) Peptide bond deoxyribose
(c) Glycosidic linkage (d) Phosphodiester bonds (d) I  -pleated II  phosphate III  sugar ribose
126 BIOMOLECULES

114. Which of the following statement(s) is/are true ? (c) RNA  -D-ribose
(a) Every individual has unique fingerprints and it (d) RNA  -D-3-deoxyribose
occur at the tips of fingers 122. In the …I…structure of RNA, helices are ..II…stranded.
(b) A sequence of bases of DNA is also unique for a They fold back to form…III…structure. Here, I II and III
person and information regarding this is called refers to (Choose the correct option).
fingerprinting (a) I  primary IIdouble IIIhelical
(c) Fingerprints can be altered by the surgery (b) I  secondary IIdouble IIIhelical
(d) All of the above (c) I  primary IIsingle IIIdouble helix
115. DNA fingerprinting is now used (d) Isecondary IIsingle IIIdouble helix
(a) In forensic laboratories for the identification of
123. James Watson and Francis Crick gave a double strand
criminals
helix structure for…I…Two nucleic acid chains are
(b) To identify racial groups to rewrite biological
wound about each other and held together
evolution
by..II…between pair of bases.
(c) To determine paternity of an individual
(a) I  DNA
(d) All of the above
II  hydrogen bond
116. Which of the following are purine bases ?
(b) I  DNA
I. Guanine II. Adenine
III. Thymine IV. Uracil II  covalent bond
(a) I and II (c) I  RNA
(b) II and III II  hydrogen bond
(c) III and IV (d) I  RNA
(d) I and IV II  covalent bond
117. A segment of DNA molecule, which codes or specifies 124. In nucleic acids, the sequence is
for one polypeptide chain is called… (a) Phosphate–Base–sugar
Fill the blank with an appropriate word. (b) Sugar–Base–phosphate
(a) phosphate group (b) amino acid (c) Base–sugar–phosphate
(c) gene (d) adenine (d) Base–phosphate–sugar
118. Which one of the following does not constitute the 125. If one strand of DNA has the sequence ATCGTATG,
nucleic acid? the sequence in the complementary strand would be
(a) Uracil (a) TAGCTTAC (b) TCACATAC
(b) Ribose sugar (c) TAGCATAC (d) TACGATAC
(c) Phosphoric acid 126. Select the correct and simplified version of nucleic acid
(d) Guanidine from the following chains given in the options.
119. Two strands in DNA are…. (a)
Complete the above statement with the best suitable
statement(s) from the options given below.
(a) ot identical (b)
(b) not identical but are complementary
(c) not complementary but are identical
(d) All of the above
120. Complete hydrolysis of DNA/RNA yields (c)
(a) a pentose sugar
(b) phosphoric acid
(c) base (Nitrogen containing heterocyclic compounds) (d)
(d) All of the above
121. Which of the following match is correct?
(a) DNA  ,D-3-deoxyribose
(b) DNA  -D-1-deoxyribose
BIOMOLECULES 127

127. Assertion (A) The two strands of DNA are

complementary to each other.
Reason (R) Adenine forms hydrogen bonds with
guanine and thymine forms hydrogen bonds with
cytosine. (c) (d)
(a) Both A and R are correct; R is the correct
explanation of A 134. Which enzyme converts starch into glucose?
(b) Both A and R are correct; R is not the correct (a) Sucrase (b) -amylase
explanation of A (c) Trypsin (d) Lactase
(c) A is correct; R is incorrect 135. The enzyme which converts glucose and fructose into
(d) R is correct; A is incorrect ethyl alcohol is
(a) Diastase (b) Invertase
Enzymes (c) Zymase (d) Sucrose
136. Name the enzyme that catalyses the reaction given
128. Enzymes in the living systems below.
(a) Provide energy  
 ?
(b) Provide immunity C12 H 22 O11 
 
2C6 H12 O6
(c) Transport oxygen maltose glucose
(d) Catalyse biological processes (a) Talose (b) Lactase
129. Enzymes take part in a reaction and (c) Pepsin (d) Maltase
(a) decrease the rate of a chemical reaction 137. The enzyme which catalyse the oxidation of one
(b) increase the rate of a chemical reaction substrate with simultaneous reduction of another
(c) both (a) and (b) substrate are called as…I…enzyme. The enzyme ends
(d) None of these with the name of …II…Identify. I and II for the above
130. Enzymes are made up of blanks from the options given below.
(a) edible proteins (a) I  reductioxidase II  ase
(b) proteins with specific structure (b) I  oxidoreductase II  ase
(c) nitrogen containing carbohydrates (c) I  oxidoreductase II  ese
(d) carbohydrates (d) I  reductoxidese II  ese
131. Enzyme which breaks down starch to maltose is 138. Enzymes are needed only in ……quantity for the
(a) Maltase progress of reaction.
(b) Zymase Select the appropriate word to fill the blank.
(c) Diastase (a) small
(d) Invertase (b) large
132. Which of the following enzymes is not useful in the (c) Both (a) and (b)
digestion of proteins? (d) None of these
(a) Lipase 139. Assertion (A) In the presence of enzyme, substrate
(b) Pepsin molecule can be attacked by the reagent effectively.
(c) Trypsin Reason (R) Active sites of enzymes hold the substrate
(d) Chymotrypsin molecule in suitable position.
133. Which one of the following chemical units is (a) Both A and R are correct ; R is the correct
certainly to be found in enzyme? explanation of A
(b) Both A and R are correct ; R is not the correct
explanation of A
(c) A is correct ; R is incorrect
(a) (b)
(d) R is correct ; A is incorrect
128 BIOMOLECULES

Vitamins,Lipids & Hormones Assertion Reason & Statement Type Question

140. Which vitamin can be obtained from sunlight ? 151. Consider the following statements.
(a) A (b) H I. Proteins are the polymers of α-amino acids and they
(c) D (d) E are connected to each other by glycosidic linkage.
141. Which one of the following metal is present in vitamin II. In globular proteins, chains of polypeptides coil
B12 ? around each other to give a spherical shape.
(a) Aluminium (b) Iron III. Structure and shape of globular protein can be
(c) Zinc (d) Cobalt studied at three different level.
142. Pyridoxine is also known as Select the correct statement(s) and mark the correct
(a) Vitamin B2 (b) Vitamin B6 option.
(c) Vitamin B12 (d) Vitamin B1 (a) Only I
(b) Only II
143. Which of the following acids is a vitamin ? (c) Both II and III
(a) Aspartic acid (b) Ascorbic acid (d) All statements are correct
(c) Adipic acid (d) Saccharic acid 152. Consider the following statements.
144. Which of the following B groups vitamins can be stored I. Tripeptide contains three amino acids linked by three
in our body ? peptide linkage.
(a) Vitamin B1 (b) Vitamin B2 II. In  -pleated sheet structure all peptide chain after
(c) Vitamin B6 (d) Vitamin B12 maximum extension laid side by side and are held
145. Assertion: (A) The term vitamine is replaced by together by intramolecular H-bonds.
vitamin now days. III. The tertiary structure of proteins arises due to
Reason: Vitamine came vital + amine and it was further folding of the secondary structure.
identified that vitamin did not contain amino groups. Select the correct statements and mark the correct
(a) Both A and R are correct; R is the correct option.
explanation of A (a) Only I (b) Only III
(b) Both A and R are correct; R is not the correct (c) II and III (d) None of these
explanation of A 153. Which of the following are non Reducing in nature-
(c) A is correct ; R is incorrect (A) Cellulose (B) Sucrose
(d) R is correct ; A is incorrect (C) Lactose (D) Starch
146. Which of the vitamins given below is water soluble? (a) A and B are correct
(a) Vitamin E (b) Vitamin D (b) A, B and C are correct
(c) Vitamin C (d) Vitamin K (c) A, B and D are correct
147. The chemical messengers produced in the ductless (d) A, C and D are correct
glands are 154. Read given statements
(a) Vitamins (b) Lipids (A) During denaturation, 2° & 3° structures of proteins
(c) Hormones (d) Antibodies are not destroyed.
148. Which of the following hormones contains iodine? (B) 1° structure of protein is destroyed during
(a) Insulin (b) Thyroxine denaturation.
(c) Adrenaline (d) Testosterone (C) Curdling of milk which is caused due to formation
149. Insulin is a of lactic acid by bacteria present in milk is an example
(a) Steroid hormone (b) Peptide hormone of denaturation.
(c) Amine hormone (d) None of the above Which statement(s) is/are incorrect in given options -
150. Which of the following is not an amine hormone? (a) A, C only (b) A, B only
(a) Norepinephrine (b) Adrenaline (c) A, B, C (d) B, C only
(c) Thyroxine (d) Oxytocin
BIOMOLECULES 129

155. Given below are two statements; one is labeled as (b) Assertion & reason both are true but reason is not a
Assertion (A) and the other is labelled as correct explanation of the assertion.
Reason(R). (c) Both assertion & reason are false.
Assertion: Amino acids are water soluble, high melting (d) Assertion is true but reason is false.
solids & behave like salts rather than simple amines or 159. Statement-I: Enzymes which do not catalyse the
carboxylic acids. oxidation of one substrate with simultaneous reduction
Reason: This behaviour is due to presence of both of another substrate are named as oxido-Reductase
acidic (–COOH) & basic (–NH2) groups in the same enzymes.
molecule. Statement-II: Enzymes are needed in large quantity for
In the light of the above statements, choose the most the progress of a reaction.
appropriate answer from the options given below : (a) Statement I is incorrect but statement II is correct.
(a) Both assertion and reason are false. (b) Statement I is correct but statement II is incorrect
(b) Assertion is true but reason is false. (c) Both statements I and statements II are incorrect.
(c) Both assertion & reason are true but reason is not (d) Both statements I and statements II are correct
the correct explanation of assertion. 160. Given below are two statements:
(d) Both assertion & reason are true and reason is a Statement-I: the pentaacetate of glucose does not react
correct explanation of assertion.
with hydroxylamine indicating the absence of free –
156. Assertion (A) Sucrose is called an invert sugar.
Reason (R) On hydrolysis, sucrose bring the change in CHO group.
the sign of rotation from dextro (+) to laevo (–). Statement-II: Despite having the aldehyde group,
(a) Assertion & reason both are true & reason is a
glucose does not give schiff's test and it does not form
correct explaination of the assertion.
(b) Assertion & reason both are true but reason is not a the hydrogen-sulphite addition product with NaHSO3.
correct explaination of the assertion. In the light of the above statements, choose the most
(c) Both assertion & reason are false.
appropriate answer from the options given below:
(d) Assertion is true but reason is false.
157. Assertion(A) β-glycosidic linkage is present in (a) Statement I is correct and statement II is incorrect
maltose. (b) Statement-I and statement-II both are correct.
Reason (R) Maltose is composed of two glucose units (c) Statement I and statement II both are incorrect
in which C-1 of one glucose unit is linked to C-4 of
another glucose unit. (d) Statement I is incorrect and statement II is correct.
(a) Assertion & reason both are true & reason is a 161. Given below are two statements:
correct explaination of the assertion. Statement-I: All carbohydrates which reduce Fehling's
(b) Assertion & reason both are true but reason is not a
solution and Tollen's reagent are refered to as reducing
correct explaination of the assertion.
(c) Both assertion & reason are false. sugars.
(d) Assertion is false but reason is true.. Statement-II: All disaccharides whether aldose or
158. Given below are two statements; one is labeled as
ketose are reducing sugares.
Assertion and the other is labelled as Reason.
Assertion:- Glucose gets oxidised to six carbon In the light of the above statements, choose the most
carboxylic acid (gluconic acid) on reaction with a mild appropriate answer from the options given below:
oxidising agent like Br2 water.
(a) Statement I is incorrect and statement II is correct.
Reason:- This indicates the presence of a primary
alcoholic (–OH) group in glucose. (b) Statement-I and statement-II both are correct.
In the light of the above statements, choose the most (c) Statement I is correct and statement II is incorrect
appropriate answer from the options given below : (d) Statement I and statement II both are incorrect
(a) Assertion & reason both are true & reason is a
correct explaination of the assertion.
130 BIOMOLECULES

162. Given below are two statements: Column I Column II

Statement-I: Sucrose is laevorotatory but after A. 1. Thymine (T)
hydrolysis gives dextrorotatory glucose and
laevorotatory fructose.
Statement-II: Hydrolysis of sucrose brings about a
change in the sign of rotation, from dextro (+) to laevo
(–) and the product is named as invert sugar. B. 2. Guanine (G)
In the light of the above statements, choose the most
appropriate answer from the options given below:
(a) Statement I is correct and statement II is incorrect
(b) Statement I is incorrect and statement II is correct.
(c) Statement-I and statement-II both are correct. C. 3. Cytosine (C)
(d) Statement I and statement II both are incorrect
163. Given below are two statements:
Statement-I: Amylose is water soluble component
which constitutes about 15 – 20% of starch. Chemically
amylose is a long unbranched chain with 200–1000 α–
D–(+)–glucose units held together by C1–C4 glycosidic
linkage. D. 4. Uracil (U)
Statement-II: Amylopectin is insoluble in water and
constitutes about 80–85% of starch. It is a branched
chain polymer of α–D–glucose units in which chain is
formed by C1–C4 glycosidic linkage whereas branching
occurs by C1–C6 glycosidic linkage.
In the light of the above statements, choose the most
appropriate answer from the options given below:
E. 5. Adenine (A)
(a) Statement-I and statement-II both are correct.
(b) Statement I is correct and statement II is incorrect
(c) Statement I is incorrect and statement II is correct.
(d) Statement I and statement II both are incorrect
164. Given below are two statements:
Statement-I: Only α–Amino acids are obtained on
hydrolysis of proteins.
Codes
Statement-II: The amino acids which can be A B C D E
synthesised in body are known as essential amino acids. (a) 5 3 2 4 1
In the light of the above statements, choose the most (b) 5 1 2 4 3
appropriate answer from the options given below: (c) 2 3 1 5 4
(a) Both statement I & II are correct. (d) 5 3 1 2 4
(b) Both statement I & II are incorrect. 166. Match the column.
(c) Statement I is incorrect but statement II is correct Column-I Column-II
(d) Statement I is correct but statement II is incorrect (Carbohydrates) (Source or name)
(a) Sucrose (p) Animal starch
Match the following Questions (b) Lactose (q) Cereals, roots,
Tubers
165. Match the following structure of base given in Column (c) Glycogen (r) Milk sugar
I with their name given in the Column II and select the (d) Starch (s) Cane sugar
correct option from the codes given below. (a) a – r, b – s, c – q, d - p
(b) a – s, b – r, c – p, d - q
(c) a – s, b – p, c – r, d - q
(d) a – p, b – q, c – r, d - s
BIOMOLECULES 131

167. Match the column. (b) (q) β-D-Fructose

Column-I Column-II
(Reaction of Glucose (Product)
(a) HI,  (p) Osazone
Glucose  
(b) Glucose (q) n-Hexane (c) (r) α-D-Glucose
Br2 ,water


(c) Glucose (r) Gluconic acid
Nitric acid


(d) Glucose (s) Saccharic acid
3Ph  NH  NH 2 (d) (s) α-D-Fructose

 
H
(a) a – q, b – s, c – p, d - r
(b) a – q, b – p, c – r, d - s
(c) a – q, b – s, c – r, d - p
(d) a – q, b – r, c – s, d - p (a) a – p, b – r, c – q, d - s
168. Match the column. (b) a – r, b – p, c – q, d - s
Column-I Column-II (c) a – p, b – r, c – s, d - q
(Carbohydrates) (Monosaccharide unit) (d) a – r, b – p, c – s, d - q
(a) Maltose (p) β-D-Glucose 170. Match the column.
(b) Lactose (q) Two α-D-Glucose Column-I Column-II
(c) Cellulose (r) β-D-Galactose & (Vitamins) (Vitamins)
β-D-Glucose (a) Vitamin-A (p) Exposure to
(d) Sucrose (s) α-D-Glucose & β- sunlight
D Fructose (b) Vitamin-B12 (q) Yeast, milk
(a) a – q, b – s, c – r, d - p (c) Vitamin-B6 (r) Meat
(b) a – q, b – r, c – p, d - s (d) Vitamin-D (s) Fish liver oil
(c) a – r, b – s, c – p, d - q (a) a - s, b - r, c - q, d - p
(d) a – r, b – p, c – q, d - s (b) a - s, b - q, c - p, d - r
169. Match the column. (c) a - q, b - s, c - r, d - p
Column-I Column-II (d) a - r, b - p, c - q, d - s
(Structure) (name)
(a) (p) α-D-Mannose
132 BIOMOLECULES

Exercise – 2: Previous Year Questions

1. Which one of the following structures represents the (a) L-sugar component
peptide chain? (Manipal 2007) (b) chiral bases
(a) (c) chiral phosphate ester units
(d) D-sugar component
7. Which of the following vitamins is water soluble?
(AIPMT 2007)
(a) Vitamin E (b) Vitamin K
(b) (c) Vitamin A (d) Vitamin B
8. Which one of the following is an amine hormone?
(AIPMT 2008)
(a) Thyroxine (b) Oxypurin
(c) Insulin (d) Progesterone
(c) 9. In DNA, the complimentary bases are
(AIPMT 2008)
(a) adenine and guanine; thymine and cytosine
(b) uracil and adenine; cytosine and guanine
(c) adenine and thymine; guanine and cytosine
(d)
(d) adenine and thymine; guanine and uracil.
10. The segment of DNA, which acts as the instrumental
manual for the synthesis of the protein is
(AIPMT 2009)
2. A sequence of how many nucleotides in messenger (a) nucleotide (b) ribose
RNA makes a codon for an amino acid? (c) gene (d) nucleoside
(Manipal 2007) 11. Which one of the following does not exhibit the
(a) Three (b) Four phenomenon of mutarotation? (AIPMT 2010)
(c) One (d) Two (a) (+)–Sucrose (b) (+)–Lactose
3. The hormone that helps in the conversion of glucose (c) (+)–Maltose (d) (–)–Fructose
to glycogen is (Manipal 2007) 12. Fructose reduces Tollens’ reagent due to
(a) cortisone (b) bile acids (Mains 2010)
(c) adrenaline (d) insulin (a) asymmetric carbons
(b) primary alcoholic group
4. Number of chiral carbon atoms in -D(+) glucose is
(c) secondary alcoholic group
(Manipal 2007)
(d) enolisation of fructose followed by conversion to
(a) five (b) six
aldehyde by base.
(c) three (d) four
13. Which of the following is a basic amino acid?
5. The helical structure of protein is stabilised by
(NEET 2020)
(Manipal 2007)
(a) Serine (b) Alanine
(a) dipeptide bonds
(c) Tyrosine (d) Lysine
(b) hydrogen bonds
14. Hyrolysis of sucrose is called (AFMC 2018)
(c) ether bonds
(a) inversion (b) esterification
(d) peptide bonds
(c) hydration (d) saponification
6. RNA and DNA are chiral molecules, their chirality is
due to (AIPMT 2007)
BIOMOLECULES 133

15. The change in optical rotation of freshly prepared (c) two -D glucopyranose units with 1, 4 - glycosidic
solution of cane sugar with time is known as linkage
(Manipal 2010) (d) two -D glucopyranose units with 1, 4 -glycosidic
(a) mutarotation (b) inversion linkage
(c) specific rotation (d) rotatory motion 23. What is the nature of glucose-glucose linkage in starch
16. The monomer units of starch are (RPMT 2010) that makes it so susceptible to acid hydrolysis?
(a) -glucose (b) - glucose (DUMET 2011)
(c) pyranose (d) galactose (a) Starch is a hemiacetal
17. Which one of the following statements is not true (b) Starch is an acetal
regarding (+)–lactose? (AIPMT 2011) (c) Starch is a polymer
(a) On hydrolysis (+)–lactose gives equal amount of (d) Starch contains only few molecules of glucose
D(+)–glucose and D(+)–galactose. 24. How glucose is related with fructose?
(b) (+)–Lactose is a -glucoside formed by the union (Guj CET 2011)
of a molecule of D(+)–glucose and a molecule of (a) Functional isomerism
D(+)–galactose. (b) Rotamers
(c) (+)–Lactose is a reducing sugar and does not (c) Positions isomerism
exhibit mutarotation. (d) Geometrical isomerism
(d) (+)–Lactose, C12H22O11 contains 8– OH groups. 25. How you can say that glucose is cyclic compound?
18. Which of the statements about “Denaturation” given (Guj CET 2011)
below are correct? (AIPMT 2011) (a) Glucose undergoes Tollen’s test
(1) Denaturation of proteins causes loss of secondary (b) Glucose reacts with phenyl hydrazine
and tertiary structures of the protein. (c) Glucose fails to react with sodium hydrogen
(2) Denaturation leads to the conversion of double sulphite
strand of DNA into single strand. (d) Glucose reacts with nitric acid
(3) Denaturation affects primary structure which gets 26. Which of the following hormones contains iodine?
distorted. (JIPMER 2012)
(a) (2) and (3) (b) (1) and (3) (a) Insulin (b) Testosterone
(c) (1) and (2) (d) (1), (2) and (3) (c) Adrenaline (d) Thyroxine
19. Which of the following is not a fat soluble vitamin? 27. Which one of the following sets of monosaccharides
(AIPMT 2011) forms sucrose? (AIPMT 2012)
(a) Vitamin B complex (b) Vitamin D (a) -D-galactopyranose and -D-glucopyranose
(c) Vitamin E (d) Vitamin A (b) -D-glucopyranose and -D-fructofuranose
20. Glucose does not react with (Kerala CEE 2011) (c) -D-glucopyranose and -D-fructofuranose
(a) Br2/H2O (b) H2N—OH (d) -D-glucopyranose and -D-fructopyranose
(c) HI (d) NaHSO3 28. Deficiency of vitamin B1 causes the disease
21. The linkage between the two monosaccharide units in (AIPMT 2012)
lactose is (Kerala CEE 2011) (a) convulsions (b) beri-beri
(a) C-1 of -D glucose and C-4 of -D-galactose (c) cheilosis (d) sterility.
(b) C-1 of -D galoctose and C-4 of -D-glucose 29. Which one of the following is an example of non-
(c) C-1 of -D galoctose and C-4 of -D-glucose reducing sugar? (UP CPMT 2012)
(d) C-1 of -D galoctose and C-4 of -D-glucose (a) Sucrose (b) Lactose
22.  -maltose consists of (KCET 2011) (c) Maltose (d) Cellubiose
(a) one -D glucopyranose unit and one –D 30. In DNA, the linkages between different nitrogenous
glucopyranose unit with 1, 2- glycosidic linage bases are (Karnataka NEET 2013)
(b) two -D glucopyranose unit with 1, 2 - glycosidic (a) phosphate linkage (b) H-bonding
linkage (c) glycosidic linkage (d) peptide linkage.
134 BIOMOLECULES

31. Which of the following is an aldohexose?

(KCET 2013)
(a) Cellulose (b) Sucrose
(c) Glucose (d) Raffinose
32. A certain compound gives negative test with ninhydrin
and positive test with Benedict’s solution, it is
(KCET 2013)
(a) an amino acid (b) a monosaccharide
(c) a lipid (d) a protein
33. Which of the following hormones is produced under the (c)
conditions of stress which stimulate glycogenolysis in
the liver of human beings? (AIPMT 2014)
(a) Thyroxin (b) Insulin
(c) Adrenaline (d) Estradiol
34. One mole of stachyose on hydrolysis yields
(MHT CET 2014)
(a) 1 mole of glucose +1 mole of fructose +2 moles of
galactose
(d)
(b) 2 moles of glucose +1 mole of fructose +1 mole of
36. The correct corresponding order of names of four
galactose
(c) 1 mole of glucose +2 moles of fructose +1 mole of aldoses with configuration given below
galactose (NEET-II 2016)
(d) 2 moles of glucose +2 moles of fructose
35. D(+)-glucose reacts with hydroxyl amine and yields an
oxime. The structure of the oxime would be
(AIPMT 2014)

respectively, is
(a) L-erythrose, L-threose, L-erythrose, D-threose
(b) D-threose, D-erythrose, L-threose, L-erythrose
(c) L-erythrose, L-threose, D-erythrose, D-threose
(a) (d) D-erythrose, D-threose, L-erythrose, L-threose.
37. Which one given below is a non-reducing sugar?
(NEET-I 2016)
(a) Glucose (b) Sucrose
(c) Maltose (d) Lactose
38. In a protein molecule various amino acids are linked
together by (NEET-I 2016)
(a) peptide bond
(b) dative bond
(c) -glycosidic bond
(b) (d) -glycosidic bond.
BIOMOLECULES 135

39. The central dogma of molecular genetics states that the 47. Which structure(s) of proteins remain(s) intact during
genetic information flows from (NEET-II 2016) denaturation process? (Odisha NEET 2019)
(a) Amino acids → Proteins → DNA (a) Both secondary and tertiary structures
(b) DNA → Carbohydrates → Proteins (b) Primary structure only
(c) DNA → RNA → Proteins (c) Secondary structure only
(d) DNA → RNA → Carbohydrates (d) Tertiary structure only
40. The correct statement regarding RNA and DNA, 48. Invert sugar is mixture of (JIPMER 2019)
respectively is (NEET-I 2016) (a) D-glucose + D-fructose
(a) the sugar component in RNA is arabinose and the (b) L-glucose + D-fructose
sugar component in DNA is ribose (c) L-glucose + D-glucose
(b) the sugar component in RNA is 2’ – deoxyribose (d) L-glucose + L-glucose
and the sugar component in DNA is arabinose 49. Sucrose on hydrolysis gives (NEET 2020)
(c) the sugar component in RNA is arabinose and the (a) -D-glucose + -D-fructose
sugar component in DNA is 2’ – deoxyribose. (b) -D-glucose + -D-glucose
(d) the sugar component in RNA is ribose and the (c) -D-glucose + -D-fructose
sugar component in DNA is 2’-deoxyribose. (d) -D-fructose + -D-fructose
41. Which of the following statements is not correct? 50. The RBC deficiency is deficiency of (NEET 2021)
(NEET 2017) (a) Vitamin B1 (b) Vitamin B2
(a) Ovalbumin is a simple food reserve in eggwhite. (c) Vitamin B12 (d) Vitamin B6
(b) Blood proteins thrombin and fibrinogen are 51. The incorrect statement regarding enzymes is :
involved in blood clotting. (NEET 2022)
(c) Denaturation makes the proteins more active. (a) Enzymes are biocatalysts.
(d) Insulin maintains sugar level in the blood of a (b) Like chemical catalysts enzymes reduce the
human body. activation energy of bio processes.
42. On hydrolysis of starch, we finally get (c) Enzymes are polysaccharides.
(JIPMER 2017) (d) Enzymes are very specific for a particular reaction
(a) glucose and substrate.
(b) fructose 52. Given below are two statements:
(c) Both (a) and (b) Statement I: A unit formed by the attachment of a base
(d) sucrose to l' position of sugar is known as nucleoside
43. The difference between amylose and amylopectin is Statement II: When nucleoside is linked to
(NEET 2018) phosphorous acid at 5'-position of sugar moiety, we get
(a) amylopectin have 1 → 4 -linkage and 1 → 6 nucleotide.
-linkage In the light of the above statements, choose the correct
(b) amylose have 1 → 4  -linkage and 1 → 6 answer from the options given below:
-linkage (NEET 2023)
(c) amylopectin have 1 → 4 -linkage and 1 → 6 (a) Both Statement I and Statement II are false
-linkage (b) Statement I is true but Statement II is false
(d) amylose is made up of glucose and galactose. (c) Statement I is false but Statement II is true
44. Which of the following compounds can form a zwitter (d) Both Statement I and Statement II are true
ion? (NEET 2018) 53. The reagents with which glucose does not react to give
(a) Aniline (b) Acetanilide the corresponding test /products are (NEET 2024)
(c) Benzoic acid (d) Glycine A. Tollen’s reagent
45. Which of the following represents the correct structure B. Schiff’s reagent
of cellulose? (AIPMT 2018) C. HCN
(a) Branched,  (1, 4) and  (1, 6) - glucose D. NH2OH
(b) Unbranched,  (1, 6) - glucose E. NaHSO3
(c) Branched,  (1, 4) - glucose Choose the correct options from the given below:
(d) Unbranched,  (1, 4) - glucose (a) A and D (b) B and E
46. The non-essential amino acid among the following is (c) E and D (d) B and C
(NEET 2019)
(a) lysine (b) valine
(c) leucine (d) alanine.
136 BIOMOLECULES

Exercise – 3: Achiever’s Section

Single Choice Questions 8. How many number of water molecules are removed
1. Sucrose in water is dextrorotatory, []D = + 66.4° from the n number of amino acids during the
formation of peptide bond?
when boiled with dil. HCl, the solution becomes
(a) (n + 1) (b) n
laevo-rotatory, []D = – 39.9°. In this process the (c) ( n/2 ) (d) (n-1)
sucrose breaks into 9. Which statement is incorrect about peptide bond?
(a) L-glucose + D-fructose (a) C - N bond length in proteins is longer than usual
(b) L-glucose + L-fructose bond length of C-N bond.
(c) D-glucose + D-fructose (b) Spectroscopic analysis shows planar structure of
(d) D-glucose + L-fructose CONH group
2. The total number of basic groups in the following form (c) C–N bond length in proteins is smaller than usual
of lysine is bond length of C–N bond
(d) None of the above
10. Which functional group participates in disulphide
bond formation in proteins ?
(a) Thiolactone (b) Thiol
(c) Thioether (d) Thioester
11. During the process of digestion, the proteins present
(a) 2 (b) 1
in food materials are hydrolysed to amino acids. The
(c) 3 (d) 4
two enzymes involved in the process
3. Sucrose when boiled with dil. HCl produce
(a) glucose (b) fructose
(c) glucose + fructose (d) laevunilic acid
4. Glucose and galactose are
(a) anomers (b) epimers are respectively
(c) ketohexoses (d) disaccharides (a) amylase and maltase (b) diastase and lipase
5. The beta and alpha glucose have different specific (c) pepsin and trypsin (d) invertase and zymase
rotations. When either is dissolved in water, their 12. Why vitamin-C must be supplied regularly in diet?
rotation changes until the same fixed value results. This (a) It is fat soluble vitamin hence stored in the body and
is called. cannot be used in regular basis
(a) epimerization (b) racemization (b) It is required in a large amount by the body hence
(c) anomerisation (d) mutaratation supplied regularly
6. Methyl –D-glucoside and methyl –D- glucoside are (c) It is water soluble vitamin hence excreted in urine
(a) epimers and cannot be stored in the body
(b) anomers (d) It is a water soluble vitamin hence used by the body
(c) enantiomers on daily basis and is to be supplied regularly
(d) conformational diastereomers 13. The correct statement in respect of protein
7. Amino acids are classified as α, β, γ and δ on the haemoglobin is that it
basis of (a) functions as a catalyst for biological reactions
(a) their relative position of amino group (b) maintains blood sugar level
(b) their relative position of amino group with respect (c) acts as an oxygen carrier in the blood
to carboxyl group (d) forms antibodies and offers resistance to diseases
(c) their relative position of carboxyl group 14. The human body does not produce
(d) the relative position of ester with respect to carboxyl (a) DNA (b) vitamins
group (c) hormones (d) enzymes
BIOMOLECULES 137

15. Which one of the following vitamins is water soluble? (D) If the Reason is correct but Assertion is incorrect.
(a) Vitamin B complex (b) Vitamin E (E) Both Assertion & Reason are incorrect.
(c) Vitamin K (d) Vitamin A 20. Assertion: Sucrose is a non-reducing sugar.
16. What type of bonding helps in stabilising the α-helix Reason: It has glycosidic linkage.
structure of proteins? (a) A (b) B (c) C
(a) Intramolecular hydrogen bonding between >C=O (d) D (e) E
and >N-H groups of specific pair of bases 21. Assertion: Maltose is a reducing sugar which gives
(b) Intramolecular hydrogen bonding between >C =O two moles of D-glucose on hydrolysis.
and >N-H groups Reason: Maltose has a 1, 4’-  -glycosidic linkage.
(c) Intramolecular hydrogen bonding between >C=O (a) A (b) B (c) C
and >N-H groups of any pair of bases (d) D (e) E
(d) None of the above 22. Assertion: Hydrolysis of sucrose is known as
17. What is the basic structural difference between starch inversion of cane sugar.
and cellulose? Reason: Sucrose is a disaccharide.
(a) Starch consist of glucose molecules and cellulose (a) A (b) B (c) C
consists of fructose molecules (d) D (e) E
(b) Both have different nature of fructose molecules 23. Assertion: Glucose does not give 2, 4- DNP test.
(c) Both have different nature of glucose molecules Reason: Glucose exists in cyclic hemiacetal form.
(d) Starch consist of fructose molecules and cellulose (a) A (b) B (c) C
consists of glucose molecules (d) D (e) E
18. Consider the following statements regarding glucose. 24. Assertion: In sucrose two sugar units are joined by 1,
I. Glucose occur freely in nature. 2-glycosidic bond.
II. Glucose occur in the combined form. Reason: It joins C1 of -glucose and C2 of -fructose
III. Glucose present in sweet fruits and honey. by glycosidic bond.
IV. Ripe grapes contain glucose in large amounts. (a) A (b) B (c) C
Select the correct statement(s) and choose the most (d) D (e) E
appropriate option. 25. Assertion: Glucose gives reddish brown precipitate
(a) I, II, III and IV (b) II and III with Fehling solution.
(c) IV and I (d) I and III Reason: Reaction of glucose with Fehling solution
19. Amino acids exist in Zwitter ion form, considering this gives CuO and gluconic acid.
fact what is the structure of glycine at pH 4? (a) A (b) B (c) C

(a) H 3 N  CH 2  COO  (d) D (e) E
26. Assertion: Deoxyribose, C5H10O4 is not a

carbohydrate.
(b) H 3 N  CH 2  COOH
Reason: Carbohydrates are hydrates of carbon so
(c) NH 2  CH 2  COOH compounds which follow Cx(H2O)y formula are
 carbohydrates.
(d) NH 2  CH 2  COO
(a) A (b) B (c) C
(d) D (e) E
Assertion-Reason Type Questions 27. Assertion: Proteins on hydrolysis produce amino
While answering these questions, you are required to acids.
choose any one of the following responses. Reason: Amino acids contain –NH2 and –COOH
(A) If both Assertion and Reason are correct and the groups.
Reason is a correct explanation of the Assertion. (a) A (b) B (c) C
(B) If both Assertion and Reason are correct but (d) D (e) E
Reason is not a correct explanation of the
Assertion.
(C) If the Assertion is correct but Reason is incorrect.
138 BIOMOLECULES

28. Assertion: Alpha    -amino acids exist as internal (a) A (b) B (c) C
(d) D (e) E
salt in solution as they have amino and carboxylic
30. Assertion: Activity of an enzyme is pH-dependent.
acid groups in near vicinity.
Reason: Change in pH affects the solubility of the
Reason: H  ion given by carboxylic group
enzyme in water.
(–COOH) is captured by amino group (–NH2) having
(a) A (b) B (c) C
lone pair of electrons.
(d) D (e) E
(a) A (b) B (c) C
(d) D (e) E
29. Assertion: DNA molecules and all RNA molecules
are found in the nucleus of a cell.
Reason: On heating, the enzymes do not lose their
specific activity.
BIOMOLECULES 139

Notes:

Find Answer Key and Detailed Solutions at the end of this book

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 enthaply 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
ionisation enthalpies, as expected is iH1 < iH2 < iH3
1.1 Electronic Configuration
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
orbitals are half- filled, making their electronic configuration extra
stable.
15 Elements
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.

Table 11.1 : 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 171 a
212 a
222 a
76 b
103b
a=M ,b=M
3– +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 state. The stability of + 5 oxidation state decreases down the
group. The only well characterised Bi (V) compound is BiF5. The
15 Elements stability of + 5 oxidation state decreases and that of +3 state
increases (due to inert pair effect) down the group. Nitrogen
Chemical Properties: Oxidation States and trends in a chemical
exhibits +1, + 2, + 4 oxidation states also when it reacts with
reactivity:
oxygen. Phosphours also shows + 1 and + 4 oxidation states in
The common oxidation states of these elements are – 3 , + 3 and some oxoacids.
+ 5. The tendency to exhibit – 3 oxidation state decreases down
the group, bismuth hardly forms any compound in –3 oxidation

SCAN CODE
p-Block Elements (Group 15-18)
142 p-BLOCK ELEMENTS (GROUP 15-18)

In the case of nitrogen , all oxidation states from +1 to +4 tend to Table 11.2 : Properties of Hydrides of Group 15
disproportionate in acid solution. For example, Elements
3 HNO2  HNO3 + H2O + 2 NO
Property NH3 PH3 AsH 3 SbH 3 BiH3
Similarly , in case of phosphorus nearly all intermediate oxidation
states disproportionate into +5 and –3. Melting point/K 195.2 139.5 156.7 185 –
Nitrogen is restricted to a maximum covalency of 4 since only Boiling point/K 238.5 185.5 210.6 254.6 290
four (one s and three p) orbitals are available for bonding. The (E-H) Distance/ 101.7 141.9 151.9 170.7 –
heavier elements have vacant d orbitals in the outermost shell pm
which can be used for bonding (covalency) and hence , expand
HEH angle 107.8 93.6 91.8 91.3 –
their covalence as in PF6– .
fH–/kJ mol–1 –46.1 13.4 66.4 145.1 278
Anomalous properties of nitrogen: Nitrogen differs from the rest
of the members of this group due to its smaller size, high dissH–(E–H)/ –46.1 13.4 66.4 145.1 278
electronegativity , high ionisation enthalpy and non – availability kJ/mol–1 389 322 297 255 –
of d orbitals. Nitrogen has unique ability to form p – p multiple
bonds with itself and with other elements having small size and 3.2 Reactivity Towards Oxygen
high electronegativity (e.g., C ,O). Heavier elements of this group All these elements form two types of oxides: E2O3 and E2O5. The
do not form p – p bonds as their atomic orbitals are so large oxide in the higher oxidation state of the element is more acidic
and diffuse that they cannot have effective overlapping. Thus, than that of lower oxidation state. Their acidic character decreases
nitrogen exists as a diatomic molecule with a triple bond (one s down the group. The oxides of the type E2O3 of nitrogen and
phosphours are purely acidic, that of arsenic and antimony
and two p) between the two atoms. Consequently , its bond amphoteric and those of bismuth is predominantly basic.
enthalpy (941.1 kJ mol –1) is very high. On the contrary,
phosphorus, arsenic and antimony form single bond (P - P, As- 3.3 Reactivity Towards Halogens
As, Sb-Sb) while Bi forms metallic bonds in elemental state. These elements react to form two series of halides: EX3 and EX5.
However , the single N – N bond is weaker than the single P – P Nitrogen does not form pentahalide due to non– availability of
bond because of high interelectronic repulsion of the non – the d– orbitals in its valence shell. Pentahalides are more covalent
bonding electrons, owing to the small bond length. As a result than trihalides. All the trihalides of these elements except those
of nitrogen are stable. In case of nitrogen , only NF3 is known to
the catenation tendency is weaker in nitrogen. Another factor be stable. Trihalides except BiF3 are predominantly covalent in
which affects the chemistry of nitrogen is the absence of d orbitals nature.
in its valence shell. Besides restricting its covalency to four ,
nitrogen cannot form d – p bonds as the heavier elements can 3.4 Reactivity Towards Metals
e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphours and These elements react with metals to form their binary compounds
arsenic can form d – p bond also with transition metals when exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride)
their compounds like P(C2H5)3 and As(C6H5)3 act as ligands. 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 4. General Properties and
E = N , P, As, Sb or Bi. Some of the properties of these hydrides
are shown in Table. The hydrides show regular gradation in their Componds of Nitrogen
properties. The stability of hydrides decreases from NH3 to BiH3 4.1 Nitrogen (N2)
which can be observed from their bond dissociation enthalpy.
Consequently, the reducing character of the hydrides increases. Preparation:
Ammonia is only a mild reducing agent while BiH3 is the strongest (i) By treating an aqueous solution of ammonium chloride with
reducing agent amongst all the hydrides. Basicity also decreases sodium nitrate. It is laboratory method of preparation.
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

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 143
Uses
(v) 2NO + 2Cu  2CuO + N2
(i) for providing an inert atmosphere during many industrial
(red, overheated) (Black)
processes where presence of air or O2 is to be avoided.
(vi) Cl2 passed into liquor NH3 (ii) for manufacture of NH3 by the Haber’s process.
3Cl2 + 2NH3  N2 + 6HCl (iii) for manufacture of HNO3 by the Birkeland-Eyde process.
(iv) for manufacture of nitrolim.
6NH3 + 6HCl  6NH4Cl

3Cl2 + 8NH3  N2 + 6NH4Cl 4.2 Compounds of Nitrogen

In this method NH3 conc. should not be lowered down 4.2.1 Ammonia:
beyond a particular limit.
Preparation:
3Cl2 + NH3  NCl3 + 3HCl (i) By the action of any base or alkali on any ammonium salt :
(Trimendously explosive) 
NH4Cl + NaOH  NH3 + NaCl + H2O
Industrial Methods of Preparation: 
(NH4)2SO4 + 2NaOH  2NH3 + Na2SO4 + 2H2O
(i) From liquefied air by fractional distillation: The bp of N2 is –
196oC and that of oxygen is –183oC and hence they can be 
NH4NO3 + NaOH  NH3 + NaNO3 + H2O
separated. 
(ii) From producer gas from furnaces: Producer gas is a mixture (NH4)3PO4 + 3NaOH  3NH3 + Na3PO4 + 3H2O
of CO and N2. When the mixture of CO and N2 is passed over 
(NH4)2SO4 + CaO  2NH3 + CaSO4 + H2O
heated CuO, the CO gas is oxidized to CO2 which is absorbed
in alkalies & N2 remains which is collected in gas cylinders. This is a general method and is used as a test for ammonium
Properties: salts.
(i) N2 is a colourless, odourless gas insoluble in water. (ii) By the hydrolsis of metal nitrides like AlN or Mg3N2.
(ii) It is non-polar covalent and neutral molecule. AlN + NaOH + H2O  NaAlO2 + NH3
(iii) It is neither combustible nor a supporter of combustion. (iii) From oxides of nitrogen: When oxides of nitrogen are mixed
(iv) It is absorbed by heated Mg and Al. The nitrides formed with H2 and the mixture is passed over heated platinum
thus react with water to form NH3. catalyst, NH3 gas is evolved.
3Mg + N2  Mg3N2 (+ 6H2O)  3Mg(OH)3 + 2NH3 2NO + 5H2  2NH3 + 2H2O
2Al + N2  2AlN (+ 6H2O)  2Al(OH)3 + 2NH3 2NO2 + 7H2  2NH3 + 4H2O
(v) Reaction with H2: At 200 atm and 500oC, and in the presence (iv) From organic amides: When an organic amide is heated with
of iron catalyst and molybdenum promoter, N2 combines with NaOH solution ammonia is evolved.
H2 reversibly to form ammonia. The process is called Haber’s 
CH3CONH2 + NaOH  CH3COONa + NH3
Process and is the industrial method of manufacturing
ammonia. The reaction is exothermic. (v) From nitrates and nitrites: When a metal nitrate or nitrite is
heated with zinc powder and concentrated NaOH solution
N2 + 3H2  2NH3 ammonia is obtained. The reactions are
(vi) Reaction with oxygen: When air free from CO2 and moisture NaNO3 + 7NaOH + 4Zn  4Na2ZnO2 + NH3 + 2H2O
is passed over an electric arc at about 2000 K, nitric oxide is
formed. This reaction is endothermic. NaNO2 + 3Zn + 5NaOH  3Na2ZnO2 + H2O + NH3
N2 + O2  2NO Industrial Methods of Preparation:
(vii) Reaction with CaC2 and BaC2: At 1100oC, these carbides react (i) Haber’s process:
with N2 forming CaCN2 and Ba(CN)2 respectively. 500 C, 200atm
N2 + 3H2           
 2NH3
 Iron oxide  K O &Al O
CaC2 + N2 +  CaCN2 + C (nitrolim, a fertilizer) 2 2 3
 (ii) From destructive distillation of coal: When coal is heated at
BaC2 + N2 +  Ba(CN)2 a high temperature in an iron retort and the distillate is bubbles
CaCN2 reacts with H2O in the soil to produce NH3 gas. NH3 in water, three substances are obtained:
gas is converted by the nitrating bacteria present in soil into
(a) Tarry black pitch, (b) Liquor ammonia & (c) Coal gas
nitrates. (The nitrates are readily absorbed by the plants and
meet their requirement of the element nitrogen.) The liquor ammonia is a concentrated solution of ammonia and
ammonium salts. When heated it gives out ammonia. When all
the free NH3 is obtained, the residual liquid is heated with Ca(OH)2

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144 p-BLOCK ELEMENTS (GROUP 15-18)
when ammonium salts get decomposed to liberate further quantity MCl 2  2NH 4 OH  M  OH  2  2NH 4 Cl
of ammonia.
 white 
 
 
(iii) Cyanamide process:
(M = Mg, Ca, Sr, Ba, Ra, Sn, Pb)
CaO + 2C + N2 2000ºC CaCN + CO (viii) When NH4OH solution is added to AgNO3 solution, a brown
2
CaCN2 + 3H2O  CaCO3 + 2NH3 ppt. is obtained
Properties: 2AgNO3  2NH 4 OH  Ag 2 O  2NH 4 NO3  H 2 O
(i) Colourless gas lighter than air. Being basic in nature turns  brown 
 
 
red litmus blue. It acts as a Lewis base
Brown ppt of silver oxide formed dissolves in excess ammo-
(ii) Highly soluble in water. The solution is called ammonium nium hydroxide forming a soluble complex
hydroxide solution.
Ag2O + 2NH4OH  [Ag(NH3)2]OH + 2H2O

(iii) Na + NH3  NaNH2 + 1/2 H2
(ix) 2NH3 + CO2 + H2O  (NH4)2CO3
Amides decompose back with water to form NH3 and NaOH.
high pressure
Pt ,550ºC 4NO + 6H O 2NH3 + CO2   NH CONH (urea) + H O
(iv) 4NH3 + 5O2   2  2 2 2

(Ostwald’s process of manufacturing HNO3) Uses:

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

Table 11.3 : 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: On warming, its colour fades due to its dissociation into

(i) N2O is obtained generally by heating NH4NO3 with caution. these two oxides.
NH4NO3  N2O + 2H2O (iii) NO2 can be prepared by reduction of concentrated HNO3
with Cu or by heating heavy metal nitrates.
(ii) N2O3 is obtained as an intense blue liquid or a pale blue solid
on cooling an equimolar mixture of NO and NO2 to 250 K. Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O ;
NO + NO2  N2O3 673 K
2Pb(NO3)2  2PbO + 4NO2 + O2

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p-BLOCK ELEMENTS (GROUP 15-18) 145
(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
oxygen have lone pairs capable of forming coordinate bond
• N2O :
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 : [Link] 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 NaNO3 + H2SO4  NaHSO4 + HNO3
5H2 + 2NO   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.
[Link] Nitrous Acid (HNO2): Properties:
Preparation: (i) Pure nitric acid is colourless liquid (bp 359oC). It is a strong
acid and is almost completely dissociated into ions in
(i) By acidifying an aqueous solution of a nitrite
solution.
Ba(NO3)2 + H2SO4  2HNO2 + BaSO4
(ii) Thermal stability
(ii) By passing an equimolar mixture of NO and NO2 into water:

NO + NO2 + H2O  2HNO2 4HNO3  2H2O + 4NO2 + O2

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146 p-BLOCK ELEMENTS (GROUP 15-18)

(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
(a) Oxidises H2S to sulphur due to the formation of a tenacious layer of insoluble oxide
on the metal surface.
H2S + 2HNO3 (conc.)  2H2O + 2NO2 + S 
• Noble metals such as Au, Pt, Rh, and Ir are not attacked by
3H2S + 2HNO3 (dilute)  4H2O + 2NO + 3S
nitric acid. However a 1:3 mixture of conc.
(b) Oxidises SO2 to H2SO4 HNO3 and conc. HCl known as aqua regia dissolves Au and
Pt as it contains free(atomic) chlorine:
SO2 + 2HNO3 (conc.)  H2SO4 + 2NO2 
HNO3 + 3HCl  2H2O + 2Cl + NOCl
3SO2 + 2H2O + 2HNO3 (dilute)  3H2SO4 + 2NO Au + 3Cl + HCl  HAuCl4
Similarly oxidises ferrous salts to ferric salts, halogen acids Pt + 4Cl + 2HCl  H2PtCl6
to respective halogens. Brown Ring Test:
(iv) Reaction with non-metals. 2HNO3 + 3H2SO4 + 6FeSO4  3Fe2(SO4)3 + 2NO + 4H2O

C + 4HNO3  H2CO3 + H2O + 4NO2 FeSO4 + NO + 5H2O  [Fe(H2O)5 NO]SO4

S + 6HNO3  H2SO4 + 2H2O + 6NO2

2 + 10HNO3  2HO3 + 4H2O + 10NO2 ; 5. General Properties and

P + 5HNO3  H3PO4 + H2O + 5NO2 Compounds of Phosphorus
These reactions are given with conc. HNO3 . It is a very reactive non-metal. It catches fire in air. It occurs in
(v) Reaction with metals: Metals that are more electropositive nature in the form of stable phosphates. (Animal bones also
than hydrogen contain calcium phosphate (58 %)).
(a) Action on zinc or Fe : Allotropic forms of Phosphorus:
(i) White or yellow phosphorus (P4):
Zn + 4HNO3 (conc.)  Zn(NO3)2 + 2H2O + 2NO2
Preparation:
4Zn + 10HNO3 (dil.)  4Zn(NO3)2 + 5H2O + N2O 
2Ca3(PO4)2 + 10C + 6SiO2  6CaSiO3 + 10CO + P4(s)
4Zn + 10HNO3 ([Link].)  4Zn(NO3)2 + NH4NO3 + 3H2O Properties: It is white-to-transparent and soft waxy solid. Its mp
and bp are 44°C and 287°C respectively. It is soluble in CS2 but
4Mg + 10HNO3 ([Link].)  4Mg(NO3)2 + NH4NO3 + 3H2O insoluble in water. It glows in dark due to slow oxidation producing
(b) Action on tin : yellowish-green light.
P4 + 5O2  P4O10
Sn + 4HNO3 (conc.)  H2SnO3 + 4NO2 + H2O
White phosphorus is poisonous. It turns yellow after some time;
4Sn + 10HNO3 (dil.)  4Sn(NO3)2 + NH4NO3 + 3H2O it is called yellow phosphorus. It undergoes oxidation in the
(c) Action on lead : presence of air which slowly raises its temperature and due to its
low ignition temperature (~ 30ºC) after a few moments it catches
Pb + 4HNO3 (conc.)  Pb(NO3)2 + 2NO2 + 2H2O fire spontaneously.
3Pb + 8HNO3 (dil.)  3Pb(NO3)2 + 2NO + 4H2O
Metals which are less electropositive than hydrogen.
(i) Action on copper
Cu + 4HNO3 (conc.)  Cu(NO3)2 + 2NO2 + 2H2O
3Cu + 8HNO3 ([Link])  3Cu(NO3)2 + NO + 4H2O Fig 11.1: Structure of white phosphorus

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p-BLOCK ELEMENTS (GROUP 15-18) 147
(ii) Red phosphorus: P4 + 5O2  2P2O5
Preparation: When white phosphorus is heated in the atmosphere P4 + 3O2  2P2O3
of CO2 or coal gas at 573 K red phosphorus is prodouced. This Red and other forms of phosphorus also burn in air or oxygen
red phosphorus may still contain some white phosphours which but on heating.
is removed by boiling the mixture with NaOH where white
(ii) Action of non-metals: When heated with non-metals
phosphorus is converted into PH3 gas but red phosphorus remains
phosphorus forms compounds PX3, PX5, P2S3 and P2S5.
inert.
2P + 3X2  2PX3
P4 + 3NaOH + 3H2O  PH3(g) + 3NaH2PO2
2P + 5X2  2PX5 (where X = Cl, Br, and I.)
It is also prepared by heating white phosphorus with a few
crystals of iodine catalyst at 250oC under high pressure in (iii) Action with metals: Alkali metals when heated with white
absence of air. phosphorus in vacuum produce alkali metal phosphide, which
react with water to form phosphine gas.
Properties : It is a red crystalline solid. It is less reactive than
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.
Fig 11.2: 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.

2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
insulated 
P(red) 
tube803K P(-black) Conversion of white phosphorus to red phosphorus and red phos-
phorus to white phosphorus.
-black phosphorous structure is not definite and is non
conductor of electricity. Heat in presence of 2 catalyst at 250oC and high pressure in ab-
sence of air
(b) -black phosphorous
White phosphorus  Red phosphorus
473 K

P(white) High  Heat above 250°C in presence of inert gas and condense in water
pressure P(-black)
-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
Fig 11.3: 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
phosphorus trioxide and pentoxide.

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148 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) By the action of alkalies on phosphonium salts: gaseous form whereas P4O10 condenses as a solid which is stopped

by glasswool. On passing the remaining gaseous mixture through
PH4I + NaOH  NaI + PH3 + H2O freezing mixture, it converts into colourless crystals of P4O6.
(iii) By the action of dil. HCl or dil. H2SO4 on metal phosphides. Properties:
Na3P + 3HCl  3NaCl + PH3 (i) It is colourless crystalline solid having mp 23.8oC and bp
178oC.
AlP + 3HCl  AlCl3 + PH3 (ii) It dissolves in cold water to form phosphorus acid. It is thus
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
to litmus paper, It is heavier than air and only slightly soluble 2P2O3 + 6H2O  3H3PO4 + PH3
in water, It is a poisonous gas and acts as a Lewis base. (iv) It slowly gets oxidized in air to form P2O5
(ii) Action of chlorine: It reacts with Cl2 to form PCl5. P2O3 + O2  P2O5
[Link] Phosphorus Pentoxide (P2O5) :
PH3 + 4Cl2  PCl5 + 3HCl
Preparation : It is obtained by burning phosphorus in air.
Similar reaction occurs between heated phosphine and Br2
and I2 vapours. P4 + 5O2  P4O10
(iii) Reaction with hydrogen halides: When PH3 is bubbled in Properties:
solution of HX, phosphonium halides are formed. (i) It is a white powder acidic in nature and is the anhydride of
PH3 + HX  PH4X orthophosphoric acid. Its empirical formula is P2O5 and its
(iv) Action on CuSO4 solution: When PH3 is bubbled in acidic molecular formula is P4O10.
solution of copper sulphate, a black precipitate of copper (ii) It sublimes on heating at 250oC.
phosphide is formed. (iii) Action of water: It dissolves in water with hissing sound
3CuSO4+2PH3 Cu3P2 {black} + 3H2SO4 forming metaphosphoric acid and finally orthophosphoric
(v) Reaction with AgNO3 solution: When PH3 gas is bubbled in acid.
a solution of AgNO3, a yellow precipitate of silver phosphide, P4O10 + 2H2O  4HPO3 , HPO3 + H2O  H3PO4
Ag3P, is first formed which later decomposes to black Ag. (iv) Dehydrating power: It dehydrates conc. H2SO4 and conc.
HNO3 to SO3 and N2O5 respectively.
3AgNO3 + PH3  Ag3P (yellow) + 3HNO3
Ag3P + 3AgNO3 + 3H2O  6Ag + 3HNO3 + H3PO3 distillation  2HPO + N O
2HNO3 + P2O5  3 2 5

(vi) Reaction with mercuric chloride solution: When mercuric

chloride solution is treated with PH3 gas, a brownish black distillation  2HPO + SO
H2SO4 + P2O5  3 3
precipitate of mercuric phosphide is formed.
Uses:
3HgCl2 + 2PH3  Hg3P2(brownish-black) + 6HCl (i) For drying acidic gases
Samples of PH3 can be dried using quick lime, or NaOH sticks. (ii) As a dehydrating agent
It cannot be dried by conc. H2SO4 because of its reaction (iii) For the preparation of SO3 and N2O5
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
screens in battle-fields. [Link] Phosphorus Acid (H3PO3)
Preparation:
5.1.2 Oxides of Phosphorus
(i) By dissolving P2O3 in water:
[Link] Phosphorus Trioxide (P2O3)
Preparation: It is prepared by burning phosphorus in a limited P2O3 + 3H2O  2H3PO3
supply of oxygen when gaseous P4O10 and P4O6 are formed. On (ii) By hydrolysis of PCl3 with water:
lowering the temperature using a condenser, P4O6 remains in

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p-BLOCK ELEMENTS (GROUP 15-18) 149
CaSO4 is insoluble. Solution of H3PO4 is separated from
PCl3 + 3H2O  H3PO3 + 3HCl
CaSO4. It is then concentrated by evaporating it at 180oC
The solution containing H3PO3 and HCl is heated to 180oC
and dehydrated by conc. H 2SO 4 placed in a vacuum
and HCl gas is driven out. The resulting solution on
dessicator cooled by freezing mixture. White crystals of
crystallization gives white crystals of H3PO3.
H3PO4 are thus formed.
Properties:
(ii) By hydrolysis of PCl5:
(i) It is a white crystalline solid, soluble in water and having
melting point of 74oC. PCl5 + 4H2O  H3PO4 + 5HCl
(ii) It is a weak acid and a reducing agent (iii) By heating white phosphorus with conc. HNO3:
(iii) When neutralized with bases or alkalies, it forms neutral salts
called phosphites which are unstable. P + 5HNO3  H3PO4 + 5NO2 + H2O
Properties:
H3PO3 + 3NaOH  Na3PO3 + 3H2O
(i) Pure orthophosphoric acid is a white crystalline solid highly
Its basicity is 2 because it has only two replaceable H atoms. soluble in water having melting point of 42oC. It is a weak
The third H atom is not replaceable because it is not acid. It forms two acid salts and one normal salt.NaH2PO4 is
connected to oxygen. sodium dihydrogen phosphate,Na 2HPO 4 is disodium

(iv) 4H3PO3  3H3PO4 + PH3 (Disproportionation) hydrogen phosphate & Na3PO4 is sodium orthophosphate.
(ii) Action of heat:
(v) H3PO3 + 3PCl5  PCl3 + 3POCl3 + 3HCl
(vi) It is a strong reducing agent: 220ºC H P O (pyrophosphoric acid)
H3PO4  4 2 7

2AgNO3 + H3PO3 + H2O  2Ag + 2HNO3 + H3PO4 316ºC HPO (metaphosphoric acid)
H4P2O7  3

2HgCl2 + H3PO3 + H2O  Hg2Cl2 + 2HCl + H3PO4 (iii) Neutralization with alkalies or bases:
[Link] Orthophosphoric Acid (H3PO4) NaOH  NaOH 
H3PO4  
H O NaH2PO4 (pri. phosphate) H O
Preparation: 2 2
(i) By heating calcium phosphate with conc. H2SO4 NaOH 

NaHPO4 (sec. phosphate) H O Na3PO4
2
Ca3(PO4)2 + 3H2SO4  2CaSO4 + 2H3PO4 (tert. phosphate)

•   NaPO + H O
NaH2PO4  3 2

Table 11.4 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 P2O3 + H2O

(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

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150 p-BLOCK ELEMENTS (GROUP 15-18)

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

Fig 11.4: Oxoacids of Phosphorus

[Link] of Group 15 Elements 7. Introduction of Group 16
(i) The main use of dinitrogen is in the manufacture of ammonia Elements (Oxygen Family)
and other industrial chemicals containing nitrogen, (e.g.,
Oxygen, sulphur, selenium, tellurium and polonium constitute
calcium cyanamide). It also finds use where an inert
group 16 of the periodic table. This is sometimes known as group
atmosphere is required (e.g., in iron and steel industry, inert
of chalcogens. The name is derived from the greek word for brass
diluent for reactive chemicals). Liquid dinitrogen is used as
and points to the association of sulphur and its congeners with
a refrigerant to preserve biological materials, food items and
copper. Most copper minerals contain either oxygen or sulphur
in cryosurgery.
and frequently the other members of the group.
(ii) Ammonia is used to produce various nitrogenous fertilisers
Occurrence :Oxygen is the most abundant of all the elements on
(ammonium nitrate, urea, ammonium phosphate and
the earth. Oxygen forms about 46.6% by mass of earth’s crust .
ammonium sulphate) and in the manufacture of some
Dry air contains 20.946% oxygen by volume.
inorganic nitrogen compounds, the most important one being
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

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p-BLOCK ELEMENTS (GROUP 15-18) 151
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

The elements of group 16 have six electrons in the outermost 7.5 Electronegativity
shell and have ns2 np4 general electronic configuration. Next to fluorine, oxygen has the highest electronegativity value
amongst the elements. Within the group, electronegativity
decrease with an increase in atomic number. This implies that the
7.2 Atomic and Ionic Radii metallic character increase from oxygen to polonium.
Due to increase in the number of shells , atomic and ionic radii
increase from top to bottom in the group. The size of oxygen
atoms is however, exceptionally small.
[Link] Properties of Group 16
Elements
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.

Table 11.5 : 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]2s 2p
2 4
[Ne]3s 3p 2 4
[Ar]3d 4s 4p
10 2 4
[Kr]4d105s25p4
Covalent Radius/pm 74 103 119 142
Ionic Radius X–2/pm 140 184 198 221
Ionization enthalpy (KJ mol–1) I 1314 1000 941 869
Ionization enthalpy (KJ mol ) II
–1
3388 2251 2045 1790
Electronegativity 3.5 2.44 2.48 2.01
Density/[g cm–3 (293 K)] 1.32 2.06 4.19 6.25
Melting point/K 54 393 490 725
Boiling point/K 90 718 958 1260

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152 p-BLOCK ELEMENTS (GROUP 15-18)

9. Chemical Properties of Group 9.1 Reactivity with Hydrogen

16 Elements All the elements of group 16 form hydrides of the type H E (E = S,
Se., Te, Po). Some properties of hydrides are given in Table. Their
2

The elements of group 16 exhibit a number of oxidation states. acidic character increases from H2O to H2Te. The increase in
The stability of -2 oxidation state decreases down the group. acidic character can be explained in terms of decrease in bond (H-
Polonium hardly shows -2 oxidation states. Since electronegativity E) dissociation enthalpy down the group. Owing to the decrease
of oxygen is very high, it shows only negative oxidation states as in bond (H-E) dissociation enthalpy down the group, the thermal
-2 except in the case of OF2 where its oxidation states is + 2. Other stability of hydrides also decreases from H2O to H2Po. All the
elements of the group exhibit + 2 + 4 + 6 oxidation states but + 4 hydrides except water possess reducing property and this
and + 6 are more common. Sulphur, selenium and tellurium usually character increases from H2S to H2Te.
show + 4 oxidation in their compounds with oxygen and +6
oxidations state with fluorine. The stability of +6 oxidation state
decreases down the group and stability of + 4 oxidation state 9.2 Reactivity with Oxygen
increases (inert pair effect). Bonding in + 4 and + 6 oxidation All these elements form oxides of the EO2 and EO3 types where E
states are primarily covalent. = S, Se, Te or Po. Ozone (O3) and sulphur dioxide (SO2) are gases
Anomalous behaviour of oxygen: The anomalous behaviour of while selenium dioxide (SeO2) is solid. Reducing property of dioxide
oxygen, like other member of p-block present in second period is decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an
due to its small size and high electronegativity. One typical example oxidising agent. Besides EO2 type sulphur, selenium and tellurium
of effects of small size and high electronegativity is the presence also form EO3 type oxide (SO3, SeO3, TeO3). Both types of oxides
of strong hydrogen bonding in H2O which is not found in H2S. are acidic in nature.
The absence of d orbitals in oxygen limits its covalency to four
and in practice, rarely exceeds two. On the other hand, in case of
other elements of the group, the valence shell can be expanded
and covalence exceeds four.
Table 11.6 : 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 constant a
1.8×10 –16
1.3×10 –7
1.3×10 –4
2.3×10–3

9.3 Reactivity Toward Halogens Amongst terrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid
These fluorides have sp3d hybridisation and thus, have trigonal
Elements of group 16 form a larger number of halides of the type
bipyramidal structure in which one of the equatorial position is
EX6, EX4 and EX2 where E is an element of the group and X is an
occupied by a lone pair of electrons. This geometry is also regarded
halogen. The stabilities of the halides decrease in the order F > Cl
as see - saw geometry.
> Br > l. Amongst hexahalides, hexafluorides are the only stable
halides. All hexafluorides are gaseous in nature. They have All elements except selenium form dichlorides and dibromides.
octahedral structure. Shulphur hexafluoride SF\6 is exceptionally These dihalides are formed by sp3 hybridisation and thus have
stable for steric reasons. tetrahedral structure. The well known monohalides are dimeric in
nature, Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These
dimeric halides undergo disproportionation as given below:
2Se2Cl2  SeCl4 + 3Se.

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p-BLOCK ELEMENTS (GROUP 15-18) 153
16 17 18
8O , 8O and 8O . Oxygen does not burn but is a strong
10. General Properties and supporter of combustion.
Compounds of Oxygen Uses:
Oxygen mixed with helium or CO2 is used for artificial respiration,
10.1 Dioxygen (O2) Liquid oxygen is used as oxidising agent in rocket fuels and Oxy-
It differs from the remaining elements of the VIth group because of gen is used for production of oxy-hydrogen or oxy-acetylene
the following properties. flames employed for cutting and welding.
(i) small size
(ii) high electronegativity and
10.2 Oxides
(iii) non-availability of d-orbitals. 10.2.1 Acidic Oxides
Preparation: They dissolve in water forming oxyacids , e.g., CO2, SO2 , SO3,
(a) Dioxygen N2O5 , N2O3 , P4O6 , P4O10, Cl2O7, CrO3 , Mn2O7 , V2O5.
(i) By thermal decomposition of oxides of metals. Cl2O7 + H2O  2 HClO4
450 C  2 Hg + O
2 HgO  Mn2O7 + H2O  2 HMnO4
2

350 C  4 Ag + O
2 Ag2O 
10.2.2 Basic Oxides
2

  Mn O + O They either dissolve in water to form alkalies or combine with

3 MnO2  3 4 2 acids to form salts and water or combine with acidic oxides to
2 Pb3O4   6 PbO + O form salts; e.g., Na2O, CaO. CuO, FeO, BaO etc.
2

(ii) By thermal decomposition of oxygen rich compounds. Na2O + H2O  2 NaOH
  2NaNO + O
2 NaNO3  CaO + H2O  Ca(OH)2
2 2

  2 KCl + 3O (laboratory method)

2 KClO3  CuO + H2SO4  CuSO4 + H2O
2

  4 K CrO + 2 Cr O + 3O
4 K2Cr2O7  10.2.3 Neutral Oxides
2 4 2 3 2
They neither combine with acids nor with the bases to form salts
2 KMnO4    K MnO + MnO + O
2 4 2 2 e.g., CO, N2O, NO etc.
(iii) By the action of conc. H2SO4 on MnO2. 10.2.4 Amphoteric Oxides
2 MnO2 + 2H2SO4  2 MnSO4 + 2H2O + O2 These can combine with acids as well as bases e.g., ZnO, Al2O3,
(iv) By the action of water on Na2O2. BeO, Sb2O3, Cr2O3, PbO etc.

2 Na2O2 + 2 H2O  4 NaOH + O2 PbO + 2 NaOH  Na2 PbO2 + H2O
(v) By the action of conc. H2SO4 on KMnO4 or K2Cr2O7. PbO + H2SO4  PbSO4 + H2O
4 KMnO4 + 6 H2SO4  2 K2SO4 + 4MnSO4 + 6H2O + 5O2 Cr2O3 + 2 NaOH  Na2Cr2O4 + H2O
2 K2Cr2O7 + 8H2SO4  2 K2SO4 + 2Cr2(SO4)3 + 8H2O + Cr2O3 + 3 H2SO4  Cr2(SO4)3 + 3 H2O
3O2
(vi) By Brins process:
10.2.4 Mixed Oxides
They behave as mixture of two simple oxides, e.g., Pb3O4
500 C  2BaO
2 BaO + O2(air)  2 (2PbO + PbO2), Fe3O4 (FeO + Fe2O3), Mn3O4 (2 MnO + MnO2)
800 C  2 BaO + O
2 BaO2  10.2.5 Peroxides
2

(vii) From air: Oxygen is obtained by liquification of air and then They react with dilute acids and form H2O2, e.g., Na2O2, K2O2,
its fractional distillation. BaO2 etc.
Properties: Colourless , odourless and tasteless gas. It is para- Na2O2 + H2SO4  Na2SO4 + H2O2
magnetic and exhibits allotropy. Three isotopes of oxygen are

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154 p-BLOCK ELEMENTS (GROUP 15-18)

They react with water forming O2 . (b) It oxidises moist S, P, As into their oxy acids.
Na2O2 + H2O  2NaOH + 1/2O2 O3  O2 + [O] × 3
10.2.6 Dioxides
S + 3 [O]  SO3
Like peroxide, they contain excess of oxygen but do not yield
H2O2 with dil. acids e.g. PbO2, MnO2 etc. SO3  H 2 O  H 2SO 4
They evolve Cl2 with conc. HCl and O2 with conc. H2SO4. S  3O3  H 2 O  H 2SO 4  3O 2
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O; (c) It oxidises H2S to S
2MnO2 + 2H2SO4  2MnSO4 + O2 + 2H2O H2S + O3  H2O + S  (yellow)
10.2.7 Super Oxides (iii) Reaction with Silver:
They contain O2– ion, e.g., KO2 , RbO2 and CsO2. These oxides Silver articles become black in contact with ozone.
react with water forming H2O2 and O2
Ag + O3  Ag2O  (black) + O2
10.2.8 Sub Oxides (iv) Reaction with H2O2 :
They contain less oxygen than expected from the normal valency
O3  H 2 O 2  2O 2  H 2 O
of the elements e.g., C3O2, N2O, Pb2O, Hg2O etc. Oxidising Reducing
agent agent
C3O2  O  Csp  Csp  C
sp
O
It is supported by the fact that SRP of ozone is higher (+2.07)
10.3 Ozone (O3) than SRP of hydrogen peroxide (+1.77). Therefore , ozone is
stronger oxidising agent than hydrogen peroxide.
Preparation:It is prepared by passing silent electric discharge
(v) Bleaching Action:
through pure and dry oxygen
O3 also bleaches coloured substances through oxidation
3O2 2O3 H = + 142 kJ/mole
(vi) Ozonolysis:
Mixture obtained contains 5-10% ozone by volume and this mix-
Alkenes, alkynes react with ozone forming ozonides.
ture is called ozonised oxygen. The apparatus used for this is
called as ozoniser.
Zn  H O
Properties : CH2 = CH2 + O3   2 2HCHO
(i) Pale blue gas which forms a blue liquid on cooling and on  ZnO
solidification forms violet black crystals. It has a strong fish- Tests for Ozone
like smell and is slightly soluble in water but more in turpen- (i) A filter paper soaked in a alcoholic benzidine
tine oil, glacial acetic acid or CCl4. O3 molecule is diamag-
netic but O3– is paramagnetic.
(ii) Oxidising agent :

O3 + 2H+ + 2e-  O2 + H2O ; SRP = + 2.07 v becomes brown when brought in contact with O3 (this is not
(In acidic medium) shown by H2O2)
O3 + H2O + 2e-  O2 + 2OH– ; SRP = + 1.24 v (ii) Tailing of mercury
(In alkaline medium) Pure mercury is a mobile liquid but when brought in contact
Therefore, ozone is a strong oxidising agent in acidic me- with O3 its mobility decreases and it starts sticking to glass
dium. surface forming a type of tail due to the dissolution of Hg2O
(mercury sub-oxide) in Hg.
(a) It oxidises – to I2 (from neutral solution of K)
2 Hg + O3  Hg2O + O2
O3  O2   O
Uses:
2Kl  H 2 O   O   2KOH  l 2 (i) As a germicide and disinfectant for sterilising water and im-
2Kl  H 2 O   2KOH  O 2  l2 proving the atmosphere of crowded places.
• Alkaline K is oxidised to potassium iodate & periodate. (ii) For detecting the position of double bond in the unsatur-
ated organic compounds.
K + 3O3  KO3 + 3O2 (iii) In mfg. of artificial silk, synthetic camphor, KMnO4 etc.
K + 4O3  KO4 + 4O2

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p-BLOCK ELEMENTS (GROUP 15-18) 155
11. General Properties and 11.1 Compounds of Sulphur
Compounds of Sulphur 11.1.1 Sodium Thiosulphate (Na2S2O3 .5H2O)
Preparation:
Sulphur Allotropic Froms: Sulphur forms numerous allotropes
of which the yellow rhombic ( - sulphur) and monoclinic ( - boiled
sulphur) forms are the most important. The stable forms at room (i) Na2SO3 + S in absence of air Na2S2O3
temperature is rhombic sulphur, which transfroms to monoclinic
sulphur when heated above 369 K. (ii) Na2CO3 + 2SO2 (excess) + H2O  2NaHSO3 + CO2
Rhombic Sulphur (- sulphur): This allotrope is yellow in colour 2NaHSO3 + Na2CO3  2Na2S2O3 + H2O + CO2
, m.p. 385.8 K and specific gravity 2.06. Rhombic sulphur crystals (iii) Na2S + Na2SO3 + I2  Na2S2O3 + 2 NaI
are formed on evaporating the solution of roll sulphur in CS2. It is Properties:
insoluble in water but dissolved to some extent in benzene, alcohol
(i) It is a colourless crystalline substance soluble in water which
and ether. It is readily soluble in CS2 .
loses water of crystallisation on strong heating
Monoclinic Sulphur ( - sulphur): Its m.p. is 393 K and specific
(ii) As antichlor: It removes the chlorine from the surface of
gravity 1.98. It is soluble in CS2. This form of sulphur is prepared
fibres (while dyeing) according to following reaction.
by melting rhombic sulphur in a dish and cooling till crust is
formed. Two holes are made in the crust and the remaining liquid Na2S2O3 + Cl2 + H2O  Na2SO4 + 2HCl + S
poured out. On removing the crust, colourless needle shaped Therefore, it is known as antichlor
crystals of  - sulphur are formed. It is stable above 369 K and (iii) Reaction with HCl :
transforms into  - sulphur below it . Conversely, - sulphur is Na2S2O3 + HCl  2NaCl + SO2 + S + H2O
stable below 369 K and transfroms into  - sulphur above this. At
369 K both the forms are stable. This temperature is called transition This test is used for distinction between S2O32- and SO32-
temperature. ions as SO32- ions give only SO2 with HCl.
(iv) Complex formation reactions :
Both rhombic and monoclinic sulphur have S8 molecules these S8
molecules are packed to give different crystal structures. The S8 (a) Reaction with silver salts (AgNO3 , AgCl, AgBr or AgI):
ring in both the forms is puckered and has a crown shape. The Na2S2O3 + 2AgNO3  Ag2S2O3  (white) + 2 NaNO3
molecular dimensions are given in figure.
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
Fig 11.5: (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.

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11.1.2 Hydrogen Sulphide (H2S) Similarly bisulphites also give SO2 with dil. HCl
Preparation: NaHSO3 + HCl  NaCl + SO2 + H2O
(i) FeS + H2SO4  FeSO4 + H2S (v) By heating sulphides in excess of air
It is prepared in kipp’s apparatus 2 ZnS + 3O2  2ZnO + 2SO2
(ii) Preparation of pure H2S gas 
(vi) CaSO4 (gypsum) + C 
1000C 2 CaO + SO2 + CO2
Sb2S3 (pure) + 6 HCl (pure)  2 SbCl3 + 3 H2S
Properties: By this method SO2 is obtained in large scale
(i) Colourless gas with rotten egg smell Properties:
(ii) Moderately soluble in water but solubility decreases with (i) Colourless gas with burning sulphur smell.
increasing temperature. (ii) It is heavier than air and is highly soluble in water
(iii) Reducing Agent: (iii) Neither burns nor helps in burning but burning magnesium
Acts as a strong reducing agent as it decomposes evolv- and potassium continue to burn in its atmosphere.
ing hydrogen. 3Mg + SO2  2 MgO + MgS
(a) H2S + X2  2 HX + S 4K + 3SO2  K2SO3 + K2S2O3
(iv) Acidic Nature : Acidic oxide and thus dissolve in water form-
(b) moisture  H O + S
H2S + SO2  2 ing sulphurous acid.
(c) It also reduces KMnO4  Mn2+ SO2 + H2O  H2SO3
H2SO4  SO2 & K2Cr2O7  Cr3+ (v) Addition Reaction:
(iv) Acidic Nature: Its aquesous solution acts as a weak
Sun light SO Cl (sulphuryl chloride)
SO2 + Cl2 
dibasic acid according to following reaction  2 2

H2S HS + H+ S2- + 2H+ platinised

 SO
SO2 + O2 
Therefore, It forms two series of salts as given below Asbests 3

NaOH + H2S  NaHS + H2O PbO2 + SO2  PbSO4

NaOH + NaHS  Na2S + 2H2O (vi) Reducing Nature :
(v) Formation of Polysulphides: They are obtained by H2O + SO2  H2SO3
passing H2S gas through metal hydroxides.
H2SO3 + H2O  H2SO4 + 2H
Ca(OH)2 + H2S  CaS + 2H2O
Reducing character is due to the liberation of nascent hy-
CaS + 4 H2S  CaS5 + 4H2 drogen
Tests for H2S: (a) Reduces halogens to corresponding halides
(i) Turns acidified lead acetate paper black SO2 + 2H2O  H2SO4 + 2H
(ii) Gives violet or purple colouration with sodium nitropruside
2H + Cl2  2HCl
solution.
––––––––––––––––––––––––––––––––
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 agnet. 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) &
Ferric Sulphate  Ferrous sulphate
(i) Burn
S + O2 or air   SO2 (vii) Oxidising nature: Acts as oxidising agent with strong
  3SO + 2H O reducing agent
(ii) S + 2H2SO4 (conc.)  2 2
moisture  2H O + 3S
(a) 2H2S + SO2 
(iii) By heating Cu or Ag with conc. H2SO4 2

Cu + H2SO4  CuSO4 + 2H2O + SO2 (b) 2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
(iv) By reaction of metal sulphites with [Link] (c) 2Hg2Cl2 + SO2 + 4HCl  2HgCl2 + 2H2O + S
Na2SO3 + 2HCl  2NaCl + SO2 + H2O

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p-BLOCK ELEMENTS (GROUP 15-18) 157
(d) 2CO + SO2  2CO2 + S (iii) Contact process (Industrial method) :
(e) 2 Fe + SO2  2FeO + FeS catalyst
 2SO3
O2 + 2SO2 
(viii) Bleaching Action:
SO2 + 2H2O  H2SO4 + 2H The commonly used catalysts are platinum, ferric oxide or
vanadium pentoxide. V2O5 is preferred as it is cheaper and is
This is due to the reducing nature of SO2 not poisoned by impurities

Coloured matter + H   colourless matter.. H2SO4 (58%) + SO3  H2S2O7 (oleum)
Air oxidation
Sulphuric acid of any desired concentration can be obtained
Therefore, bleaching is temporary
from oleum by dilution with water.
Uses:
H2S2O7 + H2O  2H2SO4
(i) Used in manufacture of H2SO4 & paper from wood pulp.
Oxidation of sulphur dioxide is reversible and exothermic.
(ii) As a bleaching agent for delicate articles like wool, silk and According to Le-chatelier principle, the favourable condi-
straw. tions for the greater yield of sulphur trioxide are.
(iii) Used in refining of petroleum and sugar. (a) An excess of air- SO2 and oxygen are taken in 2:3 molecular
11.1.4 Sulphur Trioxide (SO3) proportion
Preparation: (b) Low tempt-optimum tempt. 450°C
(i) 6H2SO4 + P4O10  6SO3 + 4H3PO4 (c) Higher pressure-one atmosphere
P4O10 is dehydrating agent Properties :
(i) A colourless syrupy liquid (it is H-bonded)
  Fe O + 3SO
(ii) Fe2(SO4)3  2 3 3 (ii) It fumes strongly in moist air and is highly corrosive in
pt nature.
 2SO
(iii) 2SO2 + O2  3 440C H O + SO

(iii) Thermal decomposition : H2SO4 
Properties:  2 3

(i) Acidic Nature: Dissolves in water forming sulphuric acid (iv) Acidic Nature: It is a strong dibasic acid and ionises as
SO3 + H2O  H2SO4 H2SO4 H+ + HSO4– 2H+ + SO42–
(ii) H2SO4 + SO3  H2S2O7 (oleum) (a) Forms two series of salts
(iii) SO3 + HCl  SO2(OH) Cl (chlorosulphuric acid) NaOH + H2SO4  NaHSO4 (sodium bisulphate) + H2O
(iv) Oxidising Nature : NaHSO4 + NaOH  Na2SO4 (sodium sulphate) + H2O
(b) Decomposes carbonates and bicarbonates into carbon
100C
(a) 2SO3 + S  3SO2 dioxide
(b) 5SO3 + 2P  5SO2 + P2O5 Na2CO3 + H2SO4  Na2SO4 + H2O + CO2
(c) SO3 + PCl5  POCl3 + SO2 + Cl2 NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(d) SO3 + 2HBr  H2O + Br2 + SO2 (c) Displaces more volatile acids from their metal salts.
Uses: 2NaCl + H2SO4  Na2SO4 + HCl
(i) Used in manufacture of H2SO4 and oleum. 2NaNO3 + H2SO4  Na2SO4 + 2HNO3
(ii) Used as a drying agent for gases. CaF2 + H2SO4  CaSO4 + 2HF
11.1.5 Sulphuric Acid (H2SO4) (v) Oxidising Nature: H2SO4 acts as a strong oxidising agent
Preparation: H2SO4  H2O + SO2 + [O]
(a) Non-metals (carbon, sulphur etc) are oxidised to their oxides.
(i) dist. Fe O + H SO + SO + 13H O
2FeSO4 . 7H2O  2 3 2 4 2 2
H2SO4  H2O + SO2 + O] × 2
(ii) Lead Chamber Process (Industrial method) :
C + 2[O]  CO2
2SO2 + O2 (air) + 2H2O + [NO] (catalyst)  2H2SO4 +
––––––––––––––––––––––––––––––––––––
[NO] (catalyst)
C + 2H2SO4  CO2 + 2SO2 + 2H2O
Acid obtained is 80% pure and is known as brown oil of
––––––––––––––––––––––––––––––––––––
vitriol
2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O

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158 p-BLOCK ELEMENTS (GROUP 15-18)
(b) Metals (copper, silver, mercury etc.) are oxidised to their (e) H2SO4 + P2O5  2HPO3 + SO3
oxides which then combine with acid to form corresponding Uses :
sulphates. (i) For the manufacture of fertilizer such as ammonium sulphate
H2SO4  H2O + SO2 + [O] and super phosphate of lime.
Cu + [O]  CuO (ii) As an important laboratory reagent.
CuO + H2SO4  CuSO4 + H2O (iii) In storage batteries.
––––––––––––––––––––––––––––––––– (iv) In leather, textile, paper and dyeing industries.
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
(c) Iodine is liberated from KI
12. Uses of Group 16 Elements
2 KI + H2SO4  K2SO4 + 2HI Sulphur dioxide is used (i) in refining petroleum ans sugar (ii) in
bleaching wool and silk and (iii) as an anti-chlor, disinfectant and
H2SO4  H2O + SO2 + [O]
preservative. Sulphuric acid, sodium hydrogen sulphite and
2 HI + [O]  I2 + H2O calcium hydrogen sulphite (industrial chemicals) are manufactured
––––––––––––––––––––––––––––––––––––– from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve
2 KI + 2H2SO4  K2SO4 + SO2 + I2 + 2H2O a number of organic and inorganic chemicals.
Here HI is oxidised to I2. Similarly bromine is liberated from
KBr 13. Introduction of Group 17
(vi) Dehydrating agent: Sulphuric acid acts as a powerful Elements: The Halogen Family
dehydrating agent because it has a great affinity for water
Fluorine, chlorine, bromine, iodine and astatine are members of
H SO Group 17. These are collectively known as the halogens (Greek
2 4
(a) C12H22O11 (cane sugar) 
–11H O 12C
2 halo means salt and genes born i.e., salt producers). The halogens
are highly reactive non-metallic elements.
COOH H SO
(b) | 2 4
 CO + CO2 + H2O
COOH 
(vii) Miscellaneous reactions: 13.1 Electronic Configuration
(a) Sulphonation of aromatic compounds All these elements have seven electrons in their outermost shell
(ns2 np5) which is one electron short of the next noble gas.

13.2 Atomic and Ionic Radii

The halogens have the smallest atomic radii in their respective
Benzene Benzene sulphonic acid periods due to maximum effective nuclear charge . Atomic and
ionic radii increase from fluorine to iodine due to increasing number
(b) Reaction with PCl5:
of quantum shells.

+ POCl3 + HCl 13.3 Ionisation Enthalpy

They have little tendency to lose electron. Thus they have very
Chlorosulphonic acid high ionisation enthalpy. Due to increase in atomic size, ionisation
enthalpy dereases down the group.

+ 2 POCl3 + 2HCl 13.4 Electron Gain Enthalpy

Halogen have maximum negative electrons gain enthalpy in the
Sulphury chloride corresponding period. This is due to the fact that the atoms of
(c) K4[Fe(CN)6] + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + these elements have only one electron less than stable noble gas
3(NH4)2SO4 + 6CO configurations. Electron gain enthalpy of the elements of the group

(d) 3KClO3 + 3H2SO4  3 KHSO4 + HClO4 + 2ClO2 + H2O becomes less negative down the group. However, the negative

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p-BLOCK ELEMENTS (GROUP 15-18) 159
electron gain enthalpy of fluorine is less than that of chlorine. It is
13.5 Electronegativity
due to small size of fluorine atom. As a result, there are strong
interelectronic repulsions in the relatively small 2p orbitals of They have very high electronegativity. The electronegativity
fluorine and thus, the incoming electron does not experience much decreases down the group. Fluorine is the most electronegative
attraction. element in the periodic table.

Table 11.7 : 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
Electronegain 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

14. Physical Properties of Group 15. Chemical Properties of Group

17 Elements 17 Elements
Fluorine and chlorine are gases, bromine is a liquid and iodine is Oxidation states and trends in chemical reactivity: All the halo-
a solid. Their melting and boiling points steadily increase with gens exhibit –1 oxidation state. However, chlorine, bromine and
atomic number. All halogen are coloured. This is due to absorp- iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also. The higher
tion of radiations in visible region which results in the excitation oxidation states of chlorine, bromine and iodine are realised mainly
of outer electrons to higher energy level. By absorbing different when the halogens are in combination with the small and highly
quanta of radiation, they display different colours. For example, electronegative fluorine and oxygen atoms e.g., in interhalogens,
F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour. oxides and oxoacids.
Fluorine and chlorine react with water. Bromine and iodine are The fluorine atom has no d orbitals in its valence shell and there-
only sparingly soluble in water. But are soluble in organic sol-
fore cannot expand its octet. Being the most electronegative, it
vents such as chloroform, carbon tetrachloride, carbon disulphide
exhibits only – 1 oxidation state.
and hydrocarbons to give coloured [Link] the smaller
enthalpy of dissociation of F2 compared to that of Cl2 whereas X- All the halogens are highly reactive. They react with metals and
X bond dissocitation enthalpies from chlorine onwards show the non-metals to form halides. The reactivity of the halogens de-
expected trend: Cl – Cl > Br – Br > I – I . A reason for this anomaly creases down the group.
is the relatively larger electrons- electron repulsion among the The ready acceptance of an electron is the reason for the strong
lone pairs in F2 molecule where they are much closer to each other oxidising nature of halogens. F2 is the strongest oxidising halo-
than in case of Cl2. gen and it oxidises other halide ions in solution or even in the
solid phase. The decreasing oxidising ability of the halogen in
aqueous solution down the group is evident from their standard
electrode potentials. Fluorine oxidises water to oxygen whereas

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160 p-BLOCK ELEMENTS (GROUP 15-18)

chlorine and bromine react with water to form corresponding 15.1 Reactivity Towards Hydrogen
hydrohalic and hypohalous acids. The reactions of iodine with
They all react with hydrogen to give hydrogen halides but affinity
water is non- spontaneous . I– can be oxidised by oxygen in acidic
for hydrogen decreases from fluorine to iodine. They dissolve in
medium; just the reverse of the reaction observed with fluorine. water to form hydrohalic acids. The acidic strength of these acids
2F2(g) + 2H2O()  4H+ (aq) + 4F– (aq) + O2(g) varies in the order : HF < HCl < HBr < HI. The stability of these
X2(g) + H2O ()  HX(aq) + HOX (aq) halides dereases down the group due to decrease in bond (H–X)
dissociation enthalpy in the order :
(where X = Cl or Br)
H – F > H – Cl > H –Br > H – I .
+
4I (aq) + 4H (aq) + O2(g)  2 I2 (s) + 2H2O ()
–

Standard Reduction Potential (SRP)

15.2 Reactivity Towards Oxygen
Halogens form many oxides with oxygen but most of them are
X2 + 2e–  2X–
unstable. Fluorine forms two oxides OF2 and O2F2. However, only
F2 + 2e–  2F– ° = + 2.87 V ; OF2 is the thermally stable at 298 K. These oxide are essentially
oxygen fluorides because of the higher electronegativity of
Cl2 + 2e–  2Cl– ° = + 1.36 V
flurorine than oxygen . Both are strong fluorinating agents. O2F2
Br2 + 2e –  2Br – ° = + 1.09 V;; oxidises plutonium to PuF6 and the reactions is used in removing
2 + 2e  2 ° = + 0.54 V
– – plutonium as PuF6 from spent nuclear fuel.
Chlorine, bromine and iodine form oxides in which the oxidation
 More the value of the SRP, more powerful is the (algebraically)
states of these halogen range from + 1 to + 7. A combination of
oxidising agent. Hence the order of oxidising power is
kinetic and thermodynamic factors lead to the generally decreas-
F2 > Cl2 > Br2 > 2
ing order of stability oxides formed by halogens, I > Cl > Br. The
Since SRP is the highest for F2 (among all elements of P.T.), higher oxides of halogens tend to be more stable than the lower
it is a strogenst oxidising agent. ones.
 F2 is more powerful oxidising agent than O3 [Inspite of 3 ‘O’s Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive
in O3 ] oxidising agents and tend to explode. ClO2 is used as a bleaching
NOTE: agent for paper pulp and textiles and in water treatment.
Electrode potential values would be the monitoring parameter The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen
in solution phase because they are experimental (based on the oxides and exist only at low temperature. They are very powerful
correct situation). oxidising agents.
Hydration energy of X– The iodine oxides, I2O4, I2O5, I2O7 are insoluble solids and de-
Smaller the ion, higher is the hydration energy compose on heating. I2O5 is very good oxidising agent and is
used in the estimation of carbon monoxide.
F– Cl – Br – –
515 kJ/mol 381 347 305 15.3 Reactivity Towards Metals
Anomalous behaviour of fluorine: The anomalous behviour of Halogen react with metals to form metal halides. For e.g., bromine
fluorine is due to its small size, highest electronegativity, low F- F reacts with magnesium to give magnesium bromide.
bond dissociation enthalpy, and non availability of d orbitals in
valence shell. Most of the reactions of fluorine are exothermic
(due to the small and strong bond formed by it with other elements). 15.4 Reactivity of Halogen Towards other
It forms only one oxoacid while other halogen form a number of Halogens
oxoacids. Hydrogen fluoride is liquid (b.p. 293 K) due to strong
Halogens combine amongst themselves to form a number of com-
hydrogen bonding. Other hydrogen halides are gases.
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
halogen.

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p-BLOCK ELEMENTS (GROUP 15-18) 161
16. General Properties and F2 + ClO3– + H2O  2F– + ClO4– + 2H+
(iii) Reaction with NaOH Solution : With dilute alkali forms
Compounds of Halogens oxygen difluoride and with concentrated alkali O2.
16.1 Fluorine (F2) 2F2 + 2 NaOH (dil)  OF2 (g) + 2 NaF + H2O
Preparation
2F2 + 4 NaOH (conc.)  O2 (g) + 4 NaF + 2H2O
(i) Electrolytic method: Electrolyte : Molten KHF2 (1 part) +
HF (5 part) (iv) Reaction with NH3 : (Distinction from other halogens)
Anode : Carbon 2NH3 + 3F2  N2 + 6 HF
Cathode : Steel
Other halogens form explosive NX3. with conc. NH3 (liquor
Vessel : Metal ammonia)
On Electrolysis (v) Reaction with H2S :
Cathode : 2H + 2e  H2(g)
+ –
H2S + F2  SF6 + 2 HF
Anode : 2F–  F2 + 2e– (vi) Reaction with SiO2 : It attacks glass at about 1000C.
The F2 gas thus evolved must be free from HF which is more SiO2 (s) + 2F2 (g)  SiF4 (g) + O2 (g)
corrosive than fluorine.
The reaction is slow with dry F2 .
In order to make flourine free from HF, the gas is passed
through NaF which absorbs HF. (vii) Reaction with H2O :

 Anode of carbon should be free from gaaphite because F2 2H2O + 2F2  4 HF + O2
reacts with graphite easily to form a polymeric susbstance sometime a little amount of O3 also forms
known as graphite fluoride.
3H2O + 3F2  6HF + O3
There should be no moisture present in the vessel otherewise
fluorine will react with water. (viii) Reaction with Xe:

3H2O + 3F2  6HF + O3 , 2F2 + 2H2O  4HF + O2

 It is not possible to prepare fluorine by electrolysis of aq.
solution of NaF or KF. It is because when aq. solution of KF
is subjected to electrolysis, there will be following two
oxidation in competition at anode,
(ix) Reaction with H2 :
H2O  1/2O2 + 2H+ + 2e– SOP = – 1.23 v
and H2 + F2  2 HF or H2 F2
–  – This reactions occurs even in dark
F 1/2F + e 2
SOP = – 2.87v
As a matter of rule that substance will be oxidise whose SOP
16.2 Chlorine (Cl2)
is higher therefore water gets oxidise at anode and not F–.
Preparation:
Properties:
(i) Common Method (Cl2 , Br2 , 2) :
(i) Diatomic, Pale green-yellow gas which appears to be almost
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, )
(a) It can oxidise all other halide ions into halogen molecules
5 7
(b) It can oxidise Cl O 3 into Cl O 4 and IO3– to IO4–

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162 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) Only for Cl2 : (iv) Reaction with NH3 (common for Cl2 & Br2) :

(a) NaCl + HNO3  NaNO3 + HCl × 3 (a) 8 NH3 + 3 Cl2  N2 + 6 NH4 Cl

HNO3 + 3HCl  NOCl + Cl2 + 2H2O (b) NH3 + 3Cl2  NCl3 + 3 HCl
–––––––––––––––––––––––––––––––––––– (excess)
3NaCl + 4 HNO3  3 NaNO3 + NOCl (nitrosyl chloride) (v) Reaction with Alkali Metal Halides (KX) :
2 KBr + Cl2  2KCl + Br2
2NOCl + O2  2NO2 + Cl2 ;
2K + Cl2  2 KCl + 2
NO2 + H2O  HNO3 (to be recycled)
 Cl2 can oxidise both Br– & – but Br2 can oxidise – only.
(b) When Cl2 is used for the chlorination of hydrocarbon the
byproduct is HCl. The HCl is catalytically oxidised into H2O  F2 is not used in aqueous reaction since it itself reacts with
water.
& Cl2 using copper powder mixed with rare earth chlorides.
(vi) Oxidising & Bleaching Properties: Chlorine water on
Cu powder  rare earth standing loses its yellow colour due to the formation of HCl
4 HCl + O2 
Chloride
 2H O + 2Cl
2 2 and HOCl. Hypochlorous acid (HOCl) so formed, gives
nascent oxygen which is responsible for oxidising and
OCl
(c) Ca / + 2HCl  CaCl2 + Cl2 + H2O
bleaching properties of chlorine.
\
Cl (a) It oxidises ferrous to ferric, sulphite to sulphate, sulphur
(iii) Manufacture of Chlorine : dioxide to sulphuric acid and iodine to iodic acid.
(a) Deacon’s Process: By oxidation of hydrogen chloride gas 2 FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2 HCl
by atmoshperic oxygen in the presence of CuCl2 (catalyst) Na2SO3 + Cl2 + H2O  Na2SO4 + 2 HCl
at 723 K. SO2 + 2 H2O + Cl2  H2SO4 + 2 HCl
CuCl
4 HCl + O2  I2 + 6 H2O + 5 Cl2  2 HIO3 + 10 HCl
2  2 Cl2 + 2 H2O
(b) It is a powerful bleaching agent ; Bleaching action is due to
(b) Electrolytic Process : Chlorine is obtained by the electrolysis
oxidation.
of brine (concentrated NaCl solution). Chlorine is liberated
at anode. It is also obtained as a by–product in many Cl2 + H2O  2 HCl + O
chemical industries. Coloured substance + O  Colourless substance
NaX (aq)  Na+ (aq) + X– (aq) It bleaches vegetable or organic matter in the presence of
moisture. Bleaching effect of chloride is permanent.
Anode : 2X–  X2 + 2e–  But the bleching action of SO2 is temporary because it takes
Properties: place through reduction.
(i) It is a greenish–yellow gas with pungent and suffocating SO2 + 2 H2O  H2 SO4 + 2 H
odour. It is about 2–5 times heavier than air. It can be liquefied
SO32– + Coloured material  SO42– + Reduced coloured
into greenish–yellow liquid which boils at 239 K. It is soluble
in water. material (colourless)
(ii) At low temperature it forms a hydrate with water having O of air
Reduced Coloured material (colourless) 
2 
formula Cl2 . 8H2O which is infact a clathrate compound.
Coloured material
(iii) H2 + Cl2 
(a zero order reaction) 2HCl (g) , (vii) Reaction with NaOH:
Common to Br2 , 2 & Cl2 (but with F2 it is different, OF2 or O2
[H2 + Br2  2HBr is not a zero order reaction] is obtained)

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p-BLOCK ELEMENTS (GROUP 15-18) 163
(a) 2 NaOH (cold & dilute) + Cl2  NaCl + NaClO + H2O (ii) From Sea-Water: NaCl is main component but NaBr is also
present in some quantity in sea water. Cl2 gas is passed
(b) 6 NaOH (hot & concentrated) + 3 Cl2  5 NaCl + through sea water when vapours of bromine are evolved.
NaClO3 + 3 H2O
2 Br– (aq) + Cl2  2Cl– (aq.) + Br2
(viii) Reaction with Hypo Solution:
Properties:
This reaction is common with Cl2 & Br2 but with 2 it is
(i) Reddish brown liquid, fairly soluble in water. It also forms
different.
hydrate like Cl2
 0 (Br2 . 8H2O)  Clathrate compound
Na 2S2 O3  H 2 O  Cl2  Na 2SO 4  2HCl   S
 colloidal 
 
  (ii) Rest reactions are same as with Cl2
In this reaction thiosulphate ions undergo 16.4 Iodine (I2)
disproportionation into SO42– and S. Cl2 is reduced to Cl– .
Preparation:
(ix) Reaction with dry Slaked Lime, Ca(OH)2: It gives bleaching
(i) Common Method :
powder.

2Na + 3H2SO4 (conc.) + MnO2  2 + MnSO4 +
2 Ca(OH)2 + 2 Cl2  Ca(OCl)2 + CaCl2 + 2 H2O
2NaHSO4 + 2H2O
(x) Reaction with Metals & non–Metals : Forms corresponding
chlorides. (ii) From Caliche or Crude Chile Salt Petre : The main source
of iodine is NaO3 (sodium iodate) which is found in nature
2 Al + 3 Cl2  2 AlCl3
with NaNO3 (chile saltpetre). NaO3 is present in small
2 Na + Cl2  2 NaCl
amount. After crystallisation of NaNO3 , the mother liquor
P4 + 6 Cl2  4 PCl3
left contains NaO3 (soluble). To this solution NaHSO3 is
S8 + 4 Cl2  4 S2Cl2 added where upon 2 is precipitated.
 It has great affinity for hydrogen. It reacts with compounds (iii) From Sea-Weeds : Sea-weeds are dried and burnt in shallow
containing hydrogen to form HCl. pits, ash left is called kelp. Ash on extraction with hot water
H2 + Cl2  2 HCl dissolves out chlorides, carbonates, sulphates and iodides
H2S + Cl2  2 HCl + S of sodium and potassium. The solution on concentration
seperates out all leaving behind iodide in the solution.
Uses : Cl2 is used
Solution is mixed with MnO2 and concentrated H2SO4 in
(i) for bleaching woodpulp (required for the manufacture of iron retorts. Liberated iodine is condensed in series of
paper and rayon). bleaching cotton and textiles, earthen-ware known as aludels.
(ii) in the manufacture of dyes, drugs and organic compounds
2Na+ MnO2 + 3H2SO4 2NaHSO4 + MnSO4 + 2 + 2H2O
such as CCl4 , CHCl3 , DDT, refrigerants, etc.
(iv) 2K+ Cl2  2KCl + 2
(iii) in the extraction of gold and platinum.
(iv) in sterilising drinking water and (v) 2K+ H2O2  2KOH + 2

(v) preparation of poisonous gases such as phosgene (COCl2), (vi) CuSO4 + 2K  K2SO4 + Cu2 ;
tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl). This 2 gets dissolved into K forming 3 , since 3– ions are
yellow, therefore solution develops yellow colour.
16.3 Bromine (Br2) Properties :
Preparation: (i) It is a dark violet solid, undergoes sublimation, least soluble
(i) Common Method: (among halogens) in water but much more soluble in K(aq.)
 Br + MnSO + due to formation of K3
2 NaBr + 3H2SO4 (conc.) + MnO2  2 4
KF3 cannot be formed similarly since F does not have ‘d’ orbitals. So
2NaHSO4 + 2H2O
sp3d hybridisation is not possible with F.

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164 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) It is soluble in organic solvents like CHCl3, CCl4 etc. to get agents and reduce H2SO4 to SO2 and get themselves oxidised
violet solutions. to bromine and iodine respectively.
(iii) Reaction with Hypo: iodometric titrations KX + H2SO4  KHSO4 + HX
2.5
S2 O32– (thiosulphate ions) + 2  S4 O 62  H2SO4 + 2HX  SO2 + X2 + 2H2O (X = Br or )
(tetrathionate ions) + 2– Hence, HBr and H are prepared by heating bromides and
This reaction is the basis of iodometric (direct 2 titration) iodides respectively with conc. H3PO4 .
titration, which is carried out for the estimation of iodine 3KBr(K) + H3PO4  K3PO4 + 3HBr (H)
using starch indicator.
Properties:
(iv) Reaction with KClO3 or KBrO3:
(i) These are colourless, pungent smelling gases with acidic

2 KClO3 + 2  2 KIO3 + Cl2 tastes.
(ii) It is heavier than air, can be liquified to colourless liquids.

2 KBrO3 + 2  2KIO3 + Br2 (iii) These are neither combustible nor supporter of combustion.
(v) Reaction with Ozone (dry) : (iv) When perfectly dry, they have no action on litmus, but in
22 (s) + 3O3 (g)  4O9 (s) presence of moisture, they turn blue litumus red, showing
acidic nature. Among HX, H is the strongest and HF is the
4O9 is an ionic compound consisting of 3+ & O3–)3 weakest acid.
indicative of metallic character of  (low .E, low E.N.) (v) These are quite soluble in water.
With NaOH there is common reaction as with Cl2 and Br2 . With HCl ionises as below.
H2 there is reversible reaction. HCl(g) + H2O ()  H3O+ (aq) + Cl– (aq) Ka = 107
16.5 Hydra Acids (Halogen Acids) It aqueous solution is called hydrochloric acid. High value
HCl, HBr & HI : of dissociation constant (Ka) indicates that it is a strong acid
Preparation: in water.
(i) By direct combination of elements: When three parts of concentrated HCl and one part of
concentrated HNO3 are mixed, aqua regia is formed which is
H2 + Cl2  2HCl
used for dissolving noble metals, e.g., gold, platinum.
Pt 2HBr
H2 + Br2 
Au + 4 H+ + NO3– + 4 Cl–  AuCl4– + NO + 2 H2O
Pt , 450 C 2H
H2 + 2  3 Pt + 16 H+ + 4 NO3– + 18 Cl–  3 PtCl62– + 4 NO + 8 H2O

(ii) By heating a halide with acid : (v) Reaction with metals oxides, hydroxides and bicarbonates

NaCl + H2SO4  NaHSO4 + HCl Zn + 2HCl  ZnCl2 + H2

NaHSO4 + NaCl  Na2SO4 + HCl MgO + 2HCl  MgCl2 + H2O

For HCl we use H2SO4 as an acid, while for HBr and H we NaOH + HCl  NaCl + H2O
use H3PO4.
CaCO3 + 2HCl  CaCl2 + H2O + CO2
(a) HCl cannot be dried over P2O5 (P4O10) or quick lime since
(vi) Reaction with salts, HCl decomposes salts of weaker acids.
they react with gas chemically.
NaHCO3 + HCl  NaCl + CO2 + H2O
CaO + 2HCl  CaCl2 + H2O
Na2S + 2HCl  2NaCl + H2S
P4O10 + 3HCl  POCl3 + 3HPO3

HCl is, hence dried by passing through conc. H2SO4 . Na2SO3 + 2HCl  2NaCl + SO2 + H2O

(b) HBr (or H) cannot be prepared by heating bromide (iodide) Na2S2O3 + HCl  2NaCl + SO2 + H2O + S
with conc. H2SO4 because HBr and H are strong reducing

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p-BLOCK ELEMENTS (GROUP 15-18) 165
2NaNO2 + 2HCl  2NaCl + NO + NO2 + H2O (ix) Action of Halogens:
(a) Cl2 is liberated from HCl by F2 alone.
(vii) Reducing Property and Stability of Hydracids:
HCl: It is quite stable and hence is oxidised by strong F2 + HCl  2HF + Cl2
oxidising agents like MnO2, KMnO4, K2Cr2O7, PbO2, Pb3O4. (b) Br2 is liberated from HBr by F2 and Cl2 (not by 2)
(i) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2 2HBr + F2 / Cl2  2HF (2HCl) + Br2
(ii) 2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2 (c) 2 is liberated from H by F2, Cl2 and Br2

(iii) K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2 2H + F2 (Cl2, Br2)  2HF (HCl, HBr) + 2

(iv) PbO2 + 4HCl  PbCl2 + 2H2O + Cl2 ; (v) Pb3 O4 (x) Detection of Cation:
HCl : AgNO3 + HCl  AgCl (white) + HNO3
+ 8HCl  3PbCl2 + 4H2O + Cl2
Therefore, HCl is a weak reducing agent. (CH3COO)2 Pb + 2HCl  PbCl2(white) + 2CH3COOH
HBr : It is not very stable and hence more easily oxidised or
HBr : AgNO3 + HBr  AgBr (pale yellow) + HNO3
acts as a strong reducing agents. In addition to above
reducing properties of HCl, it also reduces H2SO4 to SO2 (CH3COO)2 Pb + 2HBr  PbBr2  (white) + 2CH3COOH
which is not done by HCl.
H: AgNO3 + H  Ag (bright yellow) + HNO3
H2SO4 + HBr  SO2 + Br2 + 2H2O
(CH3COO)2 Pb + 2H  Pb2 (yellow) + 2CH3COOH
Aqueous HBr on exposure to atmospheric oxygen is oxidised
to bromine (yellow) (xi) Formation of Aqua-regia : 3 parts of conc. HCl and 1 part of
4HBr + O2  2 Br2 + 2H2O conc. HNO3 is known as aqua-regia. This is used for
dissolving noble metals like Au (Gold) and Pt (Platinum).
H : It is least stable hydrogen halide. It is readily oxidised
and thus acts as a powerful reducing agent. 3HCl + HNO3  NOCl + 2H2O + 2Cl (reactive) ;
In addition to reaction shown by HCl, it shows following Au + 3Cl  AuCl3
reactions also.
(a) H2SO4 + 2H  SO2 + 2 + H2O ; Uses:
H2SO4 + 6H  S + 32 + 4H2O; (i) HCl is used in preparation of Cl2, chlorides, aqua regia,
H SO + 8H  H S + 4 + 4H O ;
2 4 2 2 2
glucose, (from corn starch), medicines, laboratory reagents,
cleaning metal surfaces before soldering or electroplating. It
(b) 2HNO3 + 2H  2NO2 + 2 + 2H2O
is also used for extracting glue from bones and purifying
(c) 2HNO2 + 2H  2NO + 2 + 2H2O bone black.
(d) HO3 + 5H  32 + 2H2O (ii) HBr is used as laboratory reagent for preparing bromo
derivatives like sodium bromides and potassium bromide.
(e) K2S2O8 + 2H  K2SO4 + 2 + H2SO4
These are used in medicines as sedatives.
(f) 2FeCl3 + 2H  2FeCl2 + 2 + 2HCl (iii) H is used as reducing agent in organic chemistry.
(g) Aqueous solution of acid, if exposed to O2 is oxidised to
iodine. 16.6 Hydrofluoric Acid [H2 F2, HF]
Preparation : H2 and F2 combine with each other very violently
4H + O2  22 + 2H2O
(even in dark) to form HF. So simple reaction cannot be used for
(viii) Reaction with Ammonia: its preparation, special methods are employed for its preparation.
NH3 + HX  NH4X (white fumes) (where X = Cl, Br, ) (i) Laboratory Method: Anhydrous HF is obtained by heating
dry potassium hydrogen fluoride in a copper retort con-
nected with copper condenser.

KHF2  KF + HF

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166 p-BLOCK ELEMENTS (GROUP 15-18)
(ii) Industrial Method : HF is prepared by heating fluorspar due to release of nascent oxygen easily.
(CaF2) with conc H2SO4. HClO  HCl + O
CaF2 + H2SO4  CaSO4 + 2HF 16.7.2 Chlorous Acid [HClO2]
 Aqueous HF being corrosive to glass, is stored in wax lined Preparation:It is obtained in aqueous solution when barium
bottles or vessel made of copper or monel. chlorite suspension in water is treated with H2SO4 . The insoluble
In glass or silica bottles, it attacks them as follows: barium sulphate is filtered off.
Na2SiO3 + 6HF  Na2 SiF6 + 3H2O; Ba(ClO2)2 + H2SO4  BaSO4 + 2HClO2

CaSiO3 + 6HF  CaSiF6 + 3H2O Properties:

(i) The freshly prepared solution is colourless but it soon
SiO2 + 4HF  SiF4 + 2H2O
decomposes to ClO2 which makes the solution yellow.
SiF4 + 2HF  H2 SiF6
5 HClO2  4 ClO2 + HCl + 2H2O
This action of HF on silica (silicates) is used for etching
(ii) The acid undergoes auto-oxidation.
glass. The glass surface to be etched is coated with wax, the
design, is scratched on glass through wax coating this is 2HClO2  HClO + HClO3
then treated with 40% solution. (iii) The acid liberates iodine from K
Properties:
4K + HClO2 + 2H2O  4KOH + HCl + 22
(i) It is colourless, corrosive liquid with pungent smell with
high boiling point due to hydrogen bonding. 16.7.3 Chloric Acid [HClO3]
(ii) Dry HF does not attack metals under ordinary conditions Preparation: This acid is only known in solutuion. The acid is
(except K), but in presence of water, it dissolves metals with preapred by the action of the dilute H2SO4 on barium chlorate.
liberation of hydrogen gas.
Ba (ClO3)2 + H2SO4  BaSO4+ 2HClO3.
16.7 Oxy-Acids of Chlorine Properties: Concentrated acid is colourless and pungent smelling
16.7.1 Hypo-Chlorous Acid [HClO] liquid. It decomposes in light. However, it is stable in dark. It acts
Preparation: as a strong oxidising and bleaching agent in light. Organic
substances like paper, cotton, wool, etc., catch fire in contact with
(i) The acid is known only in solution, It is obtained by shaking
precipitate of HgO with chlorine water. the acid.

2HgO + 2Cl2 + H2O  Hg2OCl2 + 2HClO 16.7.4 Per-Chloric Acid [HCIO4]

(ii) Commercially, it is obtained by passing CO 2 through Preparation: It is the most stable oxy-acid of chlorine. Anhydrous
suspension of bleaching powder and then distilling. HClO4 is obtained by doing distillation of KCIO4 (potassium
perchlorate), with 96-97.5% H2SO4 under low pressure at 90-160°C.
2CaOCl2 + H2O + CO2  CaCl2 + CaCO3 + 2HClO
KCIO4 + H2SO4  KHSO4 + HCIO4
Properties:
An aqueous solution of the acid is obtained by reacting barium
(i) It is a weak acid. Its concentrated solution is yellow in colour
perchlorate with calculated quantity of dilute H 2SO 4. The
while dilute solution is colourless. It is unstable and
insoluble barium sulphate is removed by filtration.
decomposes.
Ba(CIO4)2 + H2SO4  BaSO4  + 2HClO4
2HClO  2HCl + O2
(ii) It dissolves magnesium with evolution of hydrogen. Properties:

Mg + 3HClO  Mg(ClO)2 + H2 (i) Anhydrous HClO4 is a colourless liquid which turns dark on
keeping. It fumes in moist air.
(iii) With alkalies, it forms salts called hypochlorites.
(ii) It is one of the strongest acid and ionises as follows :
(iv) It acts as a powerful oxidising and bleaching agent. This is
HClO4  H+ + ClO4–

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p-BLOCK ELEMENTS (GROUP 15-18) 167
(iii) It dissolves most of the metals.
CaOCl2 + CO2  CaCO3 + Cl2
Zn + 2HClO4  Zn(ClO4)2 + H2
 HNO3 is a strong oxidising acid to be avoided, here.
(iv) It is an oxidising agent and explodes in contact with organic
matter.
Some Important order
(a) Acid strength:
(v) 2HClO4 + P2O5  2HPO3 + Cl2O7
(i) H > HBr > HCl > HF
16.8 Bleaching Powder (CaOCl2.H2O) (ii) HOCl > HOBr > HO
Bleaching powder is also called calcium chlorohypochlorite (iii) HClO4 > HClO3 >HClO2 > HClO
because it is considered as a mixed salt of hydrochloric acid and (b) Oxidising power :
hypochlorous acid. (i) F2 > Cl2 > Br2 > 2 (According to electrode potential)
Ca(OCl)Cl (ii) BrO4– > IO4– > ClO4–
Preparation: (iii) HClO4 < HClO3 < HClO2  HClO
(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
to the presence of impurities.
17. Interhalogen Compounds
(ii) On long standing, it undergoes auto–oxidation into calcium We know that halogen atoms have different electronegativity.
chlorate and calcium chloride. Due to this difference in electronegativity the halogen atoms
combine with each other and give rise to the formation of binary
6 CaOCl2  Ca(CIO3)2 + 5 CaCl2
covalent compounds, which are called interhalogen
CoCl [Link] are of four types.
(iii) 2 CaOCl2  2  2 CaCl + O
2 2
AB AB3 AB5 AB7
(iv) In presence of a little amount of a dilute acid, it loses oxygen.
ClF ClF3 ClF5 lF7
2 CaOCl2 + H2SO4  CaCl2 + CaSO4 + 2 HClO BrF BrF3 BrF5
ICl ICl3 IF5
HClO  HCl + O
IF IF3
On account of the liberation of nascent oxygen, it shows
Preparation:
oxidising and bleaching properties.
(i) By the direct combination of halogens :
(a) Oxidising properties
473 K
Cl2 + F2 (equal volumes)   2ClF
CaOCl2 + H2S  CaCl2 + H2O + S
573K
CaOCl2 + 2 KI + 2 HCl  CaCl2 + 2 KCl + H2O + I2 Cl2 + 3F2 (excess)   2ClF3

3 CaOCl2 + 2 NH3  3 CaCl2 + 3 H2O + N2 I2 + Cl2  2ICl

It oxidises NO to NO , AsO
2
–
3
–
3
3–
to AsO 4
3–
and Fe to Fe
2+ 3+
(equimolar)
(in acidic medium) (ii) Diluted with water.
(b) Bleaching action
Br2 (g) + 3F2  2BrF3
Coloured matter + [O]  colourless product. (iii) F2 is diluted with N2
(v) When bleaching powder reacts with dilute acids or CO2 it
78ºC 2IF
I2 + 3F2 
liberates chlorine which is known as available chlorine. 3

(iv) F2 is taken in excess.

CaOCl2 + 2 HCl  CaCl2 + H2O + Cl2
Br2 + 5F2 (excess)  2BrF5
CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
IF7 can not be prepared by direct combination of I2 & F2 .

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168 p-BLOCK ELEMENTS (GROUP 15-18)
(ii) From lower Interhalogens: IF7 + 6H2O  7HF + H5IO6
ClF + F2  ClF3
BrF5 + 3H2O  5HF + HBrO3
350ºC ClF
ClF3 + F2 (excess)  5  Hydrolysis products are halogen acid and oxy-halogen acid.
Oxy-halogen acid is of larger central halogen atom.
200ºC BrF
BrF3 + F2 (excess)  5
 Oxidation state of A atom does not change during hydrolysis.
270ºC IF (viii) Reaction with non-metallic and metallic oxides :
IF5 + F2  7

This method is generally applied for the preparation of halogen 4BrF3 + 3SiO2  3SiF4 + 2Br2 + 3O2
fluorides. 4BrF3 + 3WO3  2WF6 + 2Br2 + 3O2
Properties:
(ix) Addition reaction (of AB type compounds):
(i) These compounds may be gases, liquids or solids.
Gases : ClF, BrF, ClF3 , IF7 – CH = CH – + ICI  – CHI – CHCl –
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
halogens consisting of heavier halogens are coloured. The IBr + NaBr  NaIBr2 ICl3 + KCl  KICl4
intensity of colour increases with increase in the molecular Uses
weight of the compounds.
These compounds can be used as non aqueous solvents.
(iii) All interhalogens are covalent molecules and are diamagnetic Interhalogen compounds are very useful fluorinating agents. ClF3
in nature since all the valence electrons present as bonding and BrF3 are used for the production of UF6 in the enrichment of
or non-bonding electrons are paired. 235
U.
(iv) The boiling points increases with the increase in the
electronegativity difference between A and B atoms. U(s) + 3 ClF3 (l)  UF6 (g) + 3 ClF (g)
(v) Thermal stability of AB type interhalogen compounds 18. Pseudo Halogens & Pseudo
decreases with the decrease in electronegativity difference
between A and B atoms. IF > BrF > ClF > ICl > IBr > BrCl. Halides
More polar is the A – B bond more is the stability of interhalogen. Some inorganic compounds like (CN) 2 cyanogen, (SCN) 2
(vi) Interhalogen compounds are more reactive than the parent thiocyanogen, (SeCN) 2 selenocyanogen, (SCSN 3 ) 2
halogens but less reactive than F2. azidocarbondisulphide have been found to behave like halogens
& they are known as pseudo halogen solids. Similarly few ions
ICl + 2Na  NaI + NaCl
are known, consisting of two or more atoms of which at least one
The order of reactivity of some interhalogens is as follows : is N, that have properties similar to those of the halide ions. They
ClF3 > BrF3 > IF7 > BrF5 > BrF. are therefore called pseudohalide ions, e.g. (CN–) cyanide ion,
(vii) Hydrolysis : All these undergo hydrolysis giving halide ion (SCN–) thiocyanate ion, (SeCN–) selenocyanate ion, (OCN–)
derived from the smaller halogen and a hypohalite (when cyanate ion, (NCN2–) cyanamide ion, (N3–) azide ion etc.
AB), halite (when AB3), halate (when AB5), and perhalate
(when AB7) anion derived from the larger halogen.
AB + H2O  HB + HOA
19. Uses of Group 17 Element (Cl2)
It is used (i) for bleaching woodpulp (required) for the manufacture
BrCl + H2O  HCl + HOBr of paper and rayon), bleaching cotton and textiles, (ii) in the
extraction of gold and platinum (iii) in the manufacture of dyes,
ICl + H2O  HCl + HIO
drugs and organic compounds such as CCl4, CHCl3, DDT,
ICl3 + 2H2O  3HCl + HIO2 refrigerants, etc. (iv) in sterilising drinking water and (v) preparation
of poisonous gases such as phosge (COCl2), tear gas (CCl3NO2),
IF5 + 3H2O  5HF + HIO3 mustard gas (ClCH2CH2SCH2CH2Cl).

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p-BLOCK ELEMENTS (GROUP 15-18) 169
[Link] of Group 18 20.1 Electronic Configuration
Elements: (The Zero Group All noble gases have general electronic configuration ns np ex- 2 6

cept helium which has 1s . Many of the properties of noble gases 2

Family) including their inactive nature are ascribed to their closed shell
structures.
Group 18 Consists of six elements: helium, neon, argon, krypton,
xenon and radon . All these are gases and chemically unreactive. 20.2 Ionisation Enthalpy
They form very few compounds . Because of this they are termed Due to stable electronic configuration these gases exhibit very
noble gases. high ionisation enthalpy . However, it decreases down the group
Occurrence: All the noble gases except radon occur in the atmo- with increases in atomic size.
sphere. Their atmospheric abundabce in dry air is ~ 1% by
volume of which argon is the major constituent. Helium and some-
20.3 Atomic Radii
times neon are found in minerals of radioactive origin e.g., pitch- Atomic radii increase down the group with increase in atomic
blende, monazite, cleveite. The main commercial source of helium number.
is natural gas. Xenon and radon are the rarest elements of the 20.4 Electron Gain Enthalpy
group. Radon is obtained as a decay product of 226Ra.
Since noble gases have stable electronic configurations, they
226 Ra  222 Rn  4 He have no tendency to accept the electron and therefore, have larger
88 86 2
positive values of electron gain enthalpy.
Most abundant element in air is Ar. Order of abundance in the air
is Ar > Ne > Kr > He > Xe.
Table 11.8 : 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

21. Physical Properties of Group (i) The noble gases expect helium (1S2) have completely filled
ns2 np6 electronic configuration in their valence shell.
18 Elements (ii) They have high ionisation enthalpy and more positive elec-
All the noble gases are monoatomic. They are colourless, and tron gain enthalpy.
tasteless. They are sparingly soluble in water. They have very The reactivity of noble gases has been investigated occa-
low melting and boiling points because the only type of inter- sionally ever since their discovery, but all attempt to force
atomic interaction in these elements is weak dispersion forces,. them to react to form the compounds were unsuccessful for
Helium has the lowest boiling point (4.2K) of any known sub- quite a few years. In March 1962, Neil Bartlett, then at the
stance. It has a unusual property of diffusing through most com- University of British Columbia, observed the reaction of a
monly used laboratory materials such as rubber, glass or plastics. noble gas. First , he prepared a red compound which is
formulated as O2+ PtF6–. He , then realised that the first
22. Chemical Properties of Group ionisation enthalpy of molecular oxygen (1175 kj mol –1) was
18 Elements almost identical with that xenon (1170 kJ mol –1). He made
efforts to prepare same type of compound with Xe+ PtF6 – by
In general, noble gases are least reactive. Their inertness to chemi- mixing Pt F6 and Xenon. After this discovery, a number of
cal reactivity is attributed to the following reasons:

SCAN CODE
p-Block Elements (Group 15-18)
170 p-BLOCK ELEMENTS (GROUP 15-18)

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. (iv) Reaction with H2: It reacts with hydrogen gas at 400°C
Clatherate compounds : Inert gas molecules get trapped in
XeF2 + H2  Xe + 2HF
the cages formed by the crystal structure of water.
During the formation of ice Xe atoms will be trapped in the (v) Hydrolysis:
cavities (or cages) formed by the water molecules in the (a) 2XeF2 + 2H2O  2Xe + 4HF + O2 (slow)
crystal structure of ice. Compounds thus obtained are called
The above is neither a cationic hydrolysis nor an anionic
clatherate compounds.
hydrolysis as seen in ionic equilibrium. It is a covalent
There are no chemical bonds. They do not possess an exact
compound and hydrolysis is like that of PCl5 .
chemical formula but approx it is 6 water molecules : 1 inert
(b) Hydrolysis is more rapid with alkali.
gas molecule. The cavity size is just smaller than the atom of
the noble gas. Such compounds are also formed by the other 1
XeF2 + 2 NaOH  Xe + O + 2NaF + H2O (fast)
organic liquids like dihydroxybenzene (for example quinol). 2 2
The reaction (a) is slower probably due to dissolution of
XeF2 in HF.
(vi) Oxidising Properties: Higher the value of SRP better is the
oxidising property of the species.
The standard reduction potential for XeF2 is measured to be
+ 2.64 V. Therfore it acts as a strong oxidising agent.
Fig 11.6: Clatherate compound 2e– + 2H+ + XeF2  Xe + 2HF SRP = + 2.64 V
(ii) True chemical compounds (posses proper bonding). This oxidises halides to their respective halogens.
XeF2 + 2 HCl  Xe + 2 HF + Cl2
23. Compounds of Xenon It oxidises 2Br –  Br2 + 2e– & 2–  2 + 2e–
23.1 Xenon Difluoride (XeF2) In this manner XeF2 will oxidise halide ions (except F–) into
free halogens.
Preparation:
Similarly it can oxidise BrO3– (bromate) which are themselves
873K ,1bar good oxidising agents to BrO4– (perbromate ions) and Ce+3
(i) Xe + F2 Ni 
Tube or monel metal (alloy of Ni) XeF2 to Ce+4 ion.
Volume ratio should be 2:1 otherwise other higher fluorides (vii) Oxidising as well as Fluorinating Properties: It can act as
tend to form. strong oxidising agent as well as fluorinating agent.

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 171
C6 H5  + XeF2  C6 H5 F2 + Xe 23.2 Xenon Tetrafluoride (XeF4)
CH3+XeF2  CH3 F2 + Xe Preparation:

 CH3 F2 exists as CH3+F2– ,F2– is analogous to 3– 873K,  XeF

Xe  2F 
2 7bar 4
1 : 5 Ni tube

Properties:
(i) It is a colorless crystalline solid and sublimes at 298 K.
Hybridisation = sp3d (ii) It undergoes sublimation, soluble in CF3 COOH.
It undergoes hydrolysis violently hence no moisture
must be present during it’s preparation.
Fig 11.7 Structure of IF2- (iii) Reaction with H2O :
 F cannot be formed as it has no d-orbitals to attain sp d
3
– 3
6 XeF4 + 12 H2O  4 Xe + 2XeO3 + 24 HF + 3O2
hybridisation.
XeO3 is white solid and explosive compound (dry), soluble in
(viii) Reactions of XeF2 + HF (anhydrous):
water (well behaved in water)
HF
Pt + 3XeF2  PtF6 + 3Xe XeO3 reacts with NaOH forming sodium xenate
S8 + 24 XeF2  8SF6 + 24 Xe XeO3 + NaOH  Na+ [HXeO4]– (sodium xenate)
2CrF2 + XeF2  2CrF3 + Xe  It disproportionates into perxenate ion in basic medium.
2MoO3 + 6XeF2  2MoF6 + 6Xe + 3O2 2 [HXeO4]– + 2OH– [XeO6]4– + Xe + O2 + 2H2O
Xenic acid (H2XeO4) is a very weak acid.
Mo (CO)6 + 3 XeF2  Mo F6 + 3 Xe + 6CO
HF H 
 XeO6 
4–
2 C6H6 + XeF2  2 C6H5F + Xe water  XeO3  O 2
(i)
8 NH3 + 3 XeF2  N2 + 6 NH4 F + 3 Xe
 slow decomposition 

 XeO6 
4–
2NO2 + XeF2  2 NO2 F + Xe (ii)  Mn 2  MnO 4–  XeO3
(nitronium fluoride) [XeO6]4– is obtainable as Na4 XeO6.8H2O
(ix) Formation of Addition Compounds: XeF2 reacts with fluoride (sodium perxenate)
ion acceptors to form cataionic species and fluoride ion (iv) Oxidising properties of XeF4
donors to form fluoroanions.
XeF4 + 2 H2  Xe + 4HF
XeF2 + PF5  [XeF]+ [PF6]–
F5 (lewis acid) + XeF2  [XeF]+ [F6]– XeF4 + 2 Hg  Xe + 2HgF2

2SbF5 (lewis acid) + XeF2  [XeF]+ [SbF6]– (v) Addition Reactions: XeF4 reacts with fluoride ion acceptors
to form cataionic species and fluoride ion donors to form
Similar behaviour is shown by PF5 and AsF5
fluoroanions.
Structure: Shape linear and geometry trigonal bipyramidal.
XeF4 + SbF5  [XeF3]+ [SbF6]–
(vi) Fluorinating Agents:
XeF4 + Pt  PtF4 + Xe

Hybridisation = sp3d XeF4 + 4NO  Xe + 4NOF (nitrosyl Fluoride)

XeF4 + 4 NO2  Xe + 4 NO2 F (nitronium fluoride)

Fig 11.8 Structure of XeF2 XeF4 + 2C6 H6  C6H5F + 2HF + Xe

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p-Block Elements (Group 15-18)
172 p-BLOCK ELEMENTS (GROUP 15-18)
Structure : Shape square planar & geometry octahedral XeF6 + MF  M+ [XeF7]– (M = Na, K, Rb or Cs)

donation { XeF6 + PtF5  (XeF5+) (PtF6–)

 CsF  XeF6  CsXeF7

  alkali metal   caesium heptafluoroxenate 
 

acceptance   fluride
  

2CsXeF7 XeF6  Cs2 XeF8
  caesium octafluoraxenate 
 
  
Fig 11.8: Structure of XeF4
Order of Oxidising Power:
23.3 Xenon Hexafluoride (XeF6) XeF2 > XeF4 > XeF6
Preparation: Structure: Shape caped octahedral (distorted oactahedral)
Xe  3F2 573K, 60–70 bar
  XeF
23.4 Xenon–Oxygen Compounds
(i) 1 : 20 Ni  tube 6
Hydrolysis of XeF4 and XeF6 with water gives XeO3.

6 XeF4 + 12 H2O  4 Xe + 2 XeO3 + 24 HF + 3 O2

(ii) XeF4 + O2 F2  XeF6 + O2
Properties: XeF6 + 3 H2O  XeO3 + 6 HF
(i) Colourless crystalline solid and sublimes at 298 K. Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2
(ii) It gives yellow liquid on melting where as other form white XeF6 + H2O  XeOF4 + 2 HF
liquids on melting (a point of difference)
XeF6 + 2 H2O  XeO2F2 + 4 HF
(iii) HF is a good solvent for all three fluorides.
XeO3 is a colourless explosive solid and has a pyramidal molecu-
(iv) Hydrolysis: lar structure. XeOF4 is a colourless volatile liquid and has a square
(a) Complete hydrolysis: pyramidal molecular structure.
XeF6  3H 2 O  XeO3  2HF

 whitesolid 
[Link] of Group 18 Elements


XeF6  H 2 O  XeOF4  2HF

(b) Partial hydrolysis:  colourless  Helium is a non–inflammable and light gas. Hence, it is used in
 
 
filling ballons for meterological observations. It is also used in
(v) Reaction with Silica (SiO2): gas–cooled nuclear reactors. Liquid helium (b.p.4.2 K) finds use
as cryogenic agent for carrying out various experiments at low
2XeF6 + SiO2  2XeOF4 + SiF4
temperatures. It is used to produce and sustain powerful
(vi) Thermal Decomposition (effect of heat): superconducting magnets which form an essential part of modern
 NMR spectrometers and Magnetic Resonance Imaging (MRI)
2XeF6  XeF2 + XeF4 + 3 F2
systems for clinical diagnosis. It is used as a diluent for oxygen in
XeF2 & XeF4 do not undergo decomposition modern diving apparatus because of its very low solubility in
(vii) Formation of Addition Compounds: blood.
XeF6 + SbF5  [XeF5]+ [SbF6] Neon is used in discharge tubes and fluorescent bulbs for
advertisement display purposes. Neon bulbs are used in botanical
XeF6 + BF3  [XeF5]+ [BF4]– gardens and in green houses.
(viii) Reaction with H2 : Argon is used mainly to provide an inert atmosphere in high
XeF6 + 3H2  6HF + Xe temperature metallurgical process (arc welding of metals or alloys)
and for filling electric bulbs. It is also used in the laboratory for
(ix) Reaction of XeF6 with XeO3 : handing substances that are air–sensitive.
XeO3 + 2 XeF6  3 XeOF4 Xenon and Krypton are used in light bulbs designed for special
purposes.
(x) F donating/F accepting properties: XeF6 reacts with fluoride
–

ion acceptors to form cataionic species and fluoride ion

donors to form fluoroanions.

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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 173
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 p-BLOCK ELEMENTS (GROUP 15-18)

EXERCISE – 1: Basic Objective Questions

Questions marked with asterisk (*) are
deleted from NEET
Introduction and Physical Properties of Group 10. An aqueous solution of ammonia consists of
15 Elements (a) H+ (b) OH–
(c) NH3 and OH– (d) NH4+ and OH–
3+ 3+ 3+
1. Ionic radii (Å) of Sb , Bi and As follow the order 11. Which of the following gases is the least reactive?
(a) Bi3+ >Sb3+ >As3 (b) Bi3+ > As3+ >Sb3+ (a) O2 (b) N2
3+ 3+ 3+
(c) Sb > Bi > As (d) As3+ >Sb3+ >Bi3+
(c) H2 (d) O3
2. Covalent and ionic radii of group-15 elements
(a) increase down the group 12. Which of the following forms strong p - p bonding
(b) increase down the group upto P and then decrease (a) P4 (b) As4
(c) decrease upto P and then increase down the group (c) N2 (d) Sb4
(d) decrease down the group
3. Among the following, the element that does not show 13. *N2 is commercially prepared by
allotropy is (a) fractional distillation of liquefied air
(a) N (b) P (b) heating sodium nitrite
(c) As (d) Bi (c) heating sodium azide
4. Which of the following halides of nitrogen is stable? (d) heating a mixture of ammonium chloride
(a) NF3 (b) NCl3 sodium nitrite
(c) NBr3 (d) NI3
Chemical Properties of Group 15 Elements
5. The tendency of nitrogen halides to act as Lewis bases
decreases in the order 14. *Which of the following reactions is used in the
(a) NF3> NCl3> NBr3> NI3 preparation of N2?
(b) NI3> NBr3> NCl3> NF3 heat 
(a) NH4Cl + NaNO2 
(c) NF3 NCl3> NBr3> NI3 heat 
(b) Ca(OCl)2 + NH3 
(d) NF3> NCl3> NBr3 NI3 heat
(c) (NH4)2 Cr2O7 
6. Which one of the following compounds is most
(d) All of these
explosive?
(a) NCl3 (b) PCl3 15. *Small quantities of very pure N2 is obtained by
(c) AsCl3 (d) NF3 carefully warming
(a) sodium azide (NaN3)
7. Which of the following is the increasing order of
(b) a mixture of CuO and NH3
enthalpy of vaporization?
(a) NH3< PH3 < AsH3 (b) AsH3 < PH3 < NH3 (c) a mixture of NH3 and Br2
(c) NH3 < AsH3 < PH3 (d) PH3 < AsH3 < NH3 (d) a mixture of Zn, NaNO3 and NaOH
8. Among the following compounds of nitrogen and 16. *Which of the following compounds does not give N2
hydrogen, the most acidic compound is
on heating?
(a) NH3 (b) N2H4
(a) KNO3 (b) NH4NO2
(c) N2H2 (d) HN3
(c) (NH4)2 Cr2O7 (d) NaN3
9. Which of the following oxides is the most acidic?
(a) N2O5 (b) P2O5 17. *The reaction between urea and nitrous acid produces
(c) As2O5 (d) Sb2O5 (a) NH3 (b) NO2
(c) N2O (d) N2
p-BLOCK ELEMENTS (GROUP 15-18) 175

Questions marked with asterisk (*) are 27. *FeSO4 is a very good absorber for NO. The number
deleted from NEET of unpaired electrons in the new compound formed by
18. Which of the following fertilizers on repeated this process is.
application would increase the acidity of the soil? (a) 4 (b) 5
(a) Urea (b) Potassium nitrate (c) 3 (d) 6
(c) Superphosphate of lime (d) Ammonium sulphate 28. The most stable oxidation states of nitrogen are
(a) –3, +3 and -5 (b) –3, 0 and –1
19. *Mg(NH4)PO4 and Na(NH4) HPO4 are heated (c) –3, +3 and 0 (d) –3, +3 and +5
separately. Which of the following statements is/are
completely incorrect regarding the product obtained in
29. *N2O3 is
the above process? (a) an acidic oxide and the anhydride of HNO2
(I) Same gas is evolved (b) an acidic oxide and the anhydride of H2N2O2
(II) Same type of phosphate is formed (c) a neutral oxide and the anhydride of HNO3
(III) Different types of gases are formed
(d) a basic oxide and the anhydride of HNO2
(IV) Different types of phosphates are formed
(a) I and II (b) II and IV 30. *Which of the following oxides of nitrogen is a mixed
(c) I and IV (d) II and III anhydride of two acids?
20. *Ammonia gas can be dried by (a) N2O3 (b) N2O4
(a) conc. H2SO4 (b) P4O10 (c) N2O5 (d) NO2
(c) anhydrous CaCl2 (d) none of these
31. *Liquid N2O4 self-ionizes as
21. *Ammonia, on reaction with excess of chlorine, gives: (a) N2O4 (l) ⇌ 𝑁𝑂 + 𝑁𝑂
(a) NCl3 and HCl (b) N4 and NH4Cl (b) 2N2O4 (l) ⇌ 𝑁𝑂 + 2𝑁𝑂 + 𝑁𝑂
(c) NCl3 and NH4Cl (d) N2 and HCl (c) N2O4 (l)⇌ 𝑁𝑂 + 2𝑁𝑂
22. *A solution of sodium in liquid ammonia is blue due (d) N2O4 (l) ⇌2NO2
to the presence of 32. *Which of the following reactions gives reasonably
(a) solvated electrons (b) ammonium ions pure NO?
(c) solvated sodium ions (d) sodium atoms (a) 2NaNO2 + 2NaI + 4H2SO4
23. The bond order in the NO molecule is
(a) 3 (b) 1.5  I2+ 4NaHSO4+ 2H2O +2NO
(c) 2.5 (d) 2.0 (b) 2NaNO2 + 2FeSO4 + 3H2SO4
24. In NO3  ion, the number of bond pairs and lone pair  Fe2(SO4)3+ 2NaHSO4+ 2H2O +2NO
of electrons on nitrogen atom are (c) 3KNO2(1) + KNO3(1) + Cr2O3(s)
(a) 2, 2 (b) 3, 1  2K2CrO4 +4NO
(c) 1, 3 (d) 4, 0
(d) All of these
25. *Which of the following oxides of nitrogen is solid?
33. *At present, HNO3 is industrially prepared by the
(a) NO2 (b) N2O
(a) contact process
(c) N2O3 (d) N2O5 (b) Birkeland-Eyde process
(c) Ostwald process
26. *Which statement is wrong for NO?
(d) Haber process
(a) It is anhydride of nitrous acid
(b) It dipole moment is 0.22 D
(c) It form dimer
(d) It is paramagnetic
176 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are (c) scarlet P (d) black P

deleted from NEET 43. *Red phosphorus is less reactive than white
phosphorus because
34. *Phosphorus reacts with concentrated HNO3 to (a)the P—P bond length is greater in red phosphorus
produce (b) red P has a polymeric structure
(a) hypophosphoric acid (c) red P is held by weak van der Waals forces
(b)orthophosphorus acid (d) red P has greater tendency to act as a donor
(c) pyrophosphoric acid
44. *Which of the following statements is correct
(d) orthophosphoric acid
regarding the behaviour of white phosphorus?
35. *Iodine reacts with concentrated HNO3 to produce (a) It is soft, waxy and reactive
(a) H5IO6 (b) HIO4 (b) It reacts with moist air to emit a light called
(c) HIO3 (d) HIO chemiluminescence.
(c) It exists as tetrahedral P4 molecules both in the
36. *Gold reacts with aqua regia forming liquid and gaseous states.
(a) auric chloride (AuCl3) (d) All the above
(b) chloroauric acid (HAuCl4) 45. The percentage of p-character in the orbitals forming
P–P bonds in P4 is:
(c) chloroaurous acid (HAuCl3)
(a) 25 (b) 33
(d) purple of Cassius
(c) 50 (d) 75
37. *Platinum reacts with aqua regia to produce
46. *The reaction of P4 with X leads selectively to P4O6.
chloroplatinic acid represented by the formula
(a) H4 [PtCl6] (b) H [PtCl4] The X is:
(a) a dry O2
(c) H2 [PtCl6] (d) H2 [PtCl4]
(b) a mixture of O2 and N2
38. Which one of the following is not an ore of
phosphorus? (c) moist O2
(a) Malachite (b) Fluorapatite (d) O2 in presence of aqueous NaOH
(c) Chlorapatite (d) Phosphorite
39. Which of the following statements is correct? 47. *On boiling phosphorus with KOH solution, product
(a) Phosphorus does not form p-p multiple bonds in formed is
its compounds. (a) Potassium sulphate (b) Phosphorus pentoxide
(b) Phosphorus forms weak to moderate d- (c) Phosphorus hydroxide (d) Phosphine
pmultiple bonds in some of its compounds. 48. *White phosphorus reacts with NaOH to give PH3 and
(c) Phosphorus can expand its valence shell by NaH2PO2. This reaction involves
utilizing inner 3d orbitals.
(a) oxidation (b) reduction
(d) All of these
(c) disproportionation (d) neutralization
40. *White phosphorus is kept under
49. *PCl5 on hydrolysis gives
(a) kerosene oil
(b) water (a) H3PO2 (b) H3PO3
(c) concentrated HNO3 (c) H3PO4 (d) H5P3O10
(d) ethanol 50. *PH3 and NH3 on separate reaction with bleaching
41. Phosphorus is more reactive than N2 because
powder produce respectively
(a) electronegativity of phosphorus is low
(a) P and N2 (b) PCl3 and NCl3
(b) ionization energy of phosphorus is low
(c) P—P bond is weaker than N—N bond (c) PCl3 and N2 (d) PCl5 and NCl3
(d) P—P bond is polymeric
42. *The most stable allotropic form of phosphorus is
(a) yellow P (b) red P
p-BLOCK ELEMENTS (GROUP 15-18) 177

Questions marked with asterisk (*) are (a) The order of their acidity is
H3PO4> H3PO3> H3PO2
deleted from NEET (b) All of them are reducing in nature
51. Solid PCl5 exists as (c) All of them are tribasic acids
(a) [PCl4]+ and [PCl6]- ions (d) The geometry of phosphorus is tetrahedral in all
the three
(b) [PCl4]- and [PCl6]+ ions
(c) covalent PCl5 molecules only
58. *Which of the following oxoacids of phosphorus is a
reducing agent and a monobasic acid as well?
(d) [PCl4]2+ and [PCl6]2- ions (a) Orthophosphorus acid (H3PO3)
52. *White phosphorus reacts with concentrated HNO3 to (b) Hypophosphorus acid (H3PO2)
give (c) Pyrophosphorus acid (H4P2O5)
(a) orthophosphoric acid (b) pyrophosphoric acid (d) Metaphosphorus acid (HPO3)
(c) phosphorus acid (d) metaphosphoric acid
59. Which of the following compounds consists of a P–P
53. *Syrupy H3PO4 is viscous due to linkage?
(a) intermolecular hydrogen bonding (a) hypophosphoric acid
(b) van der Waals forces among the H3PO4 molecules (b) pyrophosphorous acid
(c) dipolyphosphoric acid
(c) covalent bonding in P—O linkage
(d) metaphosphoric acid
(d) low activation energy in H3PO4
60. *The number of P–O–P bonds in the structure of
54. *The reaction of white phosphorus with aqueous NaOH
phosphorus pentoxide and phosphorus trioxide are
gives phosphine and another phosphorus containing respectively
compound. The reaction type, the oxidation states of (a) 6, 6 (b) 5, 5
phosphorus in phosphine and other product are (c) 5, 6 (d) 6, 5
respectively:
(a) redox reaction, -3 and -5 61. *The number of P—O—P bonds in cyclic
(b) redox reaction, +3 and +5 metaphosphoric acid is
(c) disproportionation reaction, -3 and +1 (a) zero (b) two
(d) disproportionation reaction, -3 and +3 (c) three (d) four
55. Which of the following statements is true for the
H3PO3 molecule? Physical Properties of Group 16 Elements
(a) It contains two acidic H atoms
(b) It contains one reducing H atom 62. Group 16 elements (except polonium) are called
(c) It can form two series of salts chalcogens because
(d) All of these (a) these elements, particularly sulphur and oxygen,
56. Which of the following structures represents are present in many metallic ores mainly as oxides
hypophosphoric acid? and sulphides
H H H (b) a large number of acids contain these elements,
(a) (b) particularly sulphur and oxygen
H P OH HO P O P OH (c) these elements mainly form anions
(d) these elements exist in different allotropic forms
O O O 63. In which of the following species, S-atom assumes sp3
OH OH OH
hybrid state?
O P P O H O P O (I) SO3 (II) SO2
(III) H2S (IV) S8
(c) OH OH (d) OH
(a) I, II (b) II, III
57. *The true statement for the acids of phosphorus, (c) II, IV (d) III, IV
H3PO2, H3PO3 and H3PO4 is
178 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are Chemical Properties of Group 16 Elements
deleted from NEET
64. Oxygen is more electronegative than sulphur, yet H2S is 71. *Ozone is prepared by the action of silent electric
acidic in nature while H2O is neutral because: discharge upon oxygen in an apparatus called ozonizer.
(a) water molecules are associated due to inter- The reaction
molecular hydrogen bonding (a) is exothermic
(b) water has higher boiling point than H2S (b) is endothermic
(c) H—S is weaker than O—H bond (c) leads to the dissociation of the O2 molecule
(d) H2S is a gas at ordinary temperature while H2O is a (d) leads to the formation of O 2
liquid
65. The stability of the hydrides of oxygen, sulphur, 72. *Ozonized oxygen is a mixture of
selenium and tellurium decreases in the order (a) O3 and N2 (b) O3 and O
(a) H2Te > H2Se >H2S > H2O (c) O3 and O2 (d) O3 and Cl2
(b) H2O > H2S >H2Se > H2Te
73. *Which of the following statements is correct?
(c) H2O > H2S < H2Se > H2Te (a) Ozone decomposes to give oxygen
(d) H2O > H2S > H2Te > H2Se (b) Ozone is thermodynamically unstable.
(c) The decomposition of ozone is exothermic.
66. *Which of the following statements regarding sulphur
(d) All of these
is incorrect?
(a) S2 molecule is paramagnetic 74. *Ozone is an extremely powerful oxidizing agent. It is
(b) The vapour at 200°C consists mostly S8 rings (a) second only to F2 in oxidizing power
(c) At 600°C, the gas mainly consists of S2 molecules (b) second only to O2 in oxidizing power
(d) The oxidation state of sulphur is never less than +4 (c) second only to Cl2 in oxidizing power
in its compounds
67. The number of lone pairs and the number of S—S (d) second only to MnO4 in oxidizing power
bonds in S8 molecules are respectively: 75. *At room temperature, O3 is absorbed by
(a) 8, 8 (b) 16, 8
(c) 8, 16 (d) 8, 4 (a) water (b) palladium
68. Which of the following has pπ – dπ bonding? (c) acetic acid (d) turpentine oil
(a) NO3– (b) SO32– 76. *The gases absorbed by alkaline pyrogallol and oil of
(c) BO3– (d) CO32– cinnamon are respectively
3
(a) O3 and CH4 (b) O2 and O3
69. O3 is
(c) SO2 and CH4 (d) N2O and O3
(a) an allotrope of oxygen
(b) an isomer of oxygen 77. *In the presence of water, sulphur is oxidized by ozone
(c) an isotone of oxygen to give
(d) isostructuralwith O2 (a) H2SO3 (b) SO2
70. In ozone, the central oxygen atom uses
(c) H2SO4 (d) SO3
(a) roughly sp2 orbitals for  bonding
(b) sp orbitals for  bonding only 78. *A green coloured solution of a salt changes its colour
(c) sp3 orbitals for  bonding to light pink on passing ozone through it. Which of the
(d) pπ-dπ bonding for both  and  bonding following species represent pink and green colour
respectively ?
(a) Mn2+ and MnO2 (b) MnO-4 and MnO2-4
(c) Co2+ and Co3+ (d) MnO2- and MnO-
4 4
p-BLOCK ELEMENTS (GROUP 15-18) 179

Questions marked with asterisk (*) are (b) the bonding orbitals of sulphur are smaller and more
diffuse than those of oxygen, and hence they overlap
deleted from NEET less effectively with the 1s orbital of the hydrogen
79. *O3 cannot oxidise: atom
(c) the bonding orbitals of sulphur are smaller and less
(a) KI (b) FeSO4
diffuse than those of oxygen, and hence they overlap
(c) KMnO4 (d) K2MnO4 less effectively with the 1s orbital of the hydrogen
atom
80. *Which of the following is/are correct?
(d) H2O molecules form H bonds but H2S molecules
(a) O3 + moist iodine  HIO3
do not
(b) FeCl3 + H2S  colloidal sulphur
87. *Sulphur dioxide reacts with chlorine in the presence
(c) O3 + Ag  black silver of charcoal (which acts as a catalyst) to give
(d) All (a) sulphuryl chloride
81. *In the cyclo-S8 molecule of rhombic sulphur, all the (b) thionyl chloride
(c) sulphur dichloride and oxygen
S—S bond lengths and all the S—S—S bond angles are
(d) chlorine monoxide and sulphur
respectively (approximate values)
(a) 204 pm and 107° (b) 102 pm and 120°
88. *Which of the following gases may act both as an
oxidizing and a reducing agent?
(c) 204 pm and 180° (d) 102 pm and 60°
(a) H2S (b) SO3
82. Which of the following statements is correct for
(c) SO2 (d) O2
sulphur?
(a) In sulphur, stronger p-d overlap takes place 89. *Dehydration of concentrated H2SO4 in the presence
because the size of the d orbitals is similar to that of P4O10 produces
of the p orbitals. (a) SO2 (b) H2S
(b) The size of the atom and the size of the 3d orbitals (c) O2 (d) SO3
decrease from S to Cl because on crossing a period
in the periodic table, the nuclear charge is 90. *H2SO4 is manufactured from SO2(g) by the
increased and s and p electrons shield the nuclear (a) Hall process (b) contact process
charge incompletely (c) Raschig process (d) Haber process
(c) Due to stronger p-d overlap, only a few sulphur
compounds polymerize.
91. *Which of the following ions does not have an S—S
(d) All of these linkage?
83. *H2S turns an acidified K2Cr2O7 solution (a) S2O 82  (b) S2O 62 
2 2
(a) violet (b) orange (c) S2O 5 (d) S2O 3
(c) green (d) colourless
92. *When SO2 gas is passed into an acidified solution of
84. *H2S turns an acidified KMnO4 solution K2Cr2O7, the oxidation state of chromium changes
(a) green (b) pink (a) from +12 to +6 (b) from +3 to +6
(c) blue-black (d) colourless (c) from +6 to +3 (d) from +6 to +4
85. Which of the following compounds is thermo- 93. *Standard sodium thiosulphate solution is used in the
dynamically unstable? estimation of iodine present in a solution. The
(a) H2O (b) H2Se equivalent weight of sodium thiosulphate which is
(c) H2S (d) NH3 required to make the standard solution is
86. H2S is less stable than H2O because (a) (molecular weight)/2
(b) (molecular weight)/3
(a) the bonding orbitals of sulphur are larger and more
(c) the same as the molecular weight
diffuse than those of oxygen, and hence they overlap
(d) (molecular weight)/4
less effectively with the 1s orbital of the hydrogen
atom
180 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are (a) F– (b) Cl–

deleted from NEET (c) Br– (d) I–
103. One of the reasons why the F—F bond is weak is that
94. *A gas that cannot be collected over water is (a) the repulsion between the nonbonding pairs of
(a) N2 (b) O2 electrons of the two fluorine atoms is high
(c) SO2 (d) PH3 (b) the ionization energy of the fluorine atom is very
high
Physical and chemical Properties of Group 17 (c) the F—F bond distance is large
Elements (d) the F—F bond distance is small and hence
95. Which of the following elements can have both positive internuclear repulsion is small
and negative oxidation states? 104. In spite of having lower dissociation energies, bromine
(a) Fluorine (b) Iodine and iodine are weaker oxidizing agents than chlorine
(c) Lithium (d) Helium due to their
96. Which of the following halogens has only one oxidation (a) smaller electron affinities and greater hydration
state of –1 in an aqueous solution? energies
(a) Iodine (b) Chlorine (b) smaller electron affinities and smaller hydration
(c) Bromine (d) Fluorine energies
97. Which one among the following is the most powerful (c) greater electron affinities and greater hydration
oxidizing agent? energies
(a) Cl2 (b) Br2 (d) greater electron affinities and smaller hydration
(c) F2 (d) I2 energies
98. All the halogens are coloured. The colours arise due to 105. *Which of the following statements is not appropriate
(a) weak van der Waals forces between the halogen regarding the characteristics of interhalogen
molecules compounds?
(b) strong oxidizing power of the halogens (a) They are usually less reactive than halogens (except
(c) absorption of light which causes an electron to fluorine).
jump from the ground state to a higher state (b) They are not so stable, but none of them is explosive
(d) emission of light due to transfer of an electron from (c) They are covalent in nature
a higher state to the ground state (d) They have low boiling points and are highly volatile
99. Which of the following statements is correct for the 106. Which one of the following molecules will form a
iodine molecule? linear polymeric structure due to hydrogen bonding?
(a) In molten state it conducts electricity, though very (a) HCl (b) HF
slightly, due to self-ionization: 3I2  I3  I3 (c) H2O (d) NH3
(b) Its conductivity increases with the rise in 107. Which of the following is not true?
temperature. (a) Among halide ions, iodide ion is the most powerful
(c) It behaves like an intrinsic semiconductor reducing agent
(d) All the above (b) Fluorine is the only halogen which does not show a
100. Which of the following is arranged in order of variable oxidation state
increasing bond energy? (c) HOCl is a stronger acid than HOBr
(a) I2< Br2< Cl2< F2 (b) I2< F2< Br2< Cl2 (d) HF is a stronger acid than HCl
(c) I2< Br2< F2< Cl2 (d) Cl2< Br2< F2 < I2 108. *Which of the following halides forms salt like KHX2
101. Which of the following are not correctly matched? (where X is a halogen atom)?
(a) A halogen which is a liquid at room temperature  (a) HF (b) HCl
bromine (c) HBr (d) HI
(b) The most electronegative element  fluorine 109. The correct order of thermal stability of hydrogen
(c) The strongest oxidizing halogen  iodine halides (H—X) is:
(d) The most reactive halogen  fluorine (a) HI > HBr > HCl > HF (b) HF > HCl > HBr > HI
102. Which of the following halide ions the most basic? (c) HCl > HF > HBr > HI (d) HI > HCl > HF > HBr
p-BLOCK ELEMENTS (GROUP 15-18) 181

Questions marked with asterisk (*) are 118. *Chlorine is manufactured by oxidizing HCl (g) with
deleted from NEET O2 at 400°C in the presence of CuCl catalyst. This
110. The halogen which has zero standard enthalpy of process is known as
formation is (a) Leblanc process (b) Solvay process
(a) Cl2(l) (b) Br2(g) (c) Dennis process (d) Deacon process
(c) Br2(l) (d) F2(s) 119. *PtF6 converts O2 to
   
111. The property of halogen acids, that indicated incorrect (a) O 2 PtF 6 (b) O 2 PtF 6
is: (c) F2+PtO2 (d) F2O + Pt
(a) HF > HCl > HBr > HI ....... acidic strength
(b) HI > HBr > HCl > HF ........ reducing strength 120. *Which of the following reactions may be used for the
(c) HI > HBr > HCl > HF ......... bond length preparation of chlorine?
(d) HF > HCl > HBr > HI ........ thermal stability (a) KMnO4+HCl (conc.) →
112. Which has maximum pH in aqueous solution?
(b) NaCl + MnO2 + H2SO4 (conc.) →
(a) NaClO (b) NaClO2
(c) NaClO3 (d) NaClO4 (c) Ca(OCl)Cl + H2O → (d) All of these

113. *What products are expected from disproportionation 121. *Fluorine react with water to produce
reaction of hypochlorous acid? (a) HF, O2 and O3 (b) HF and O2
(a) HClO3 and Cl2O (b) HClO2 and HClO4 (c) HF and OF2 (d) HF and O3
(c) HCl and Cl2O (d) HCl and HClO3 122. *Which one of the following represents the reaction
114. Which one of the following oxides is expected to between fluorine and cold NaOH (dil.)?
exhibit paramagnetic behaviour? (a) 2F2 + 4 NaOH  4NaF + 2H2O + O2
(a) CO2 (b) ClO2
(b) 3F2 + 6 NaOH  5NaF + NaFO3 + 3H2O
(c) SO2 (d) SiO2
(c) F2 + 2NaOH  NaF + NaOF + H2O
115. In the following statements which combination of true
(T) and false (F)options is correct? (d) 2F2 + 2NaOH  2NaF + OF2 + H2O

(I) Ionic mobility is the highest for I– in water as 123. *Chlorine reacts with dilute NaOH under ordinary
compared to other halides. conditions to give
(II) Stability order is: Cl3- > Br3- > I3- (a) NaCl and NaClO3 (b) NaCl and ClO2
(III) Reactivity order is F < Cl < Br < I (c) NaCl and NaClO (d) NaCl and Cl2O
(IV) Oxidizing power order is : F2< Cl2< Br2< I2
124. *Chlorine on reaction with hot and concentrated NaOH
(a) TFTF (b) TFFF
produces
(c) TFFT (d) FTFT
(a) NaClO3 and NaClO (b) NaCl and NaClO3
116. *Fluorine was first prepared by (c) NaCl and NaClO4 (d)NaClO3and NaClO4
(a) electrolysis of hydrogen fluoride
(b) electrolysis of fused KF 125. *Dry SO2 reacts with Cl2 to produce
(c) electrolysis of a solution of KHF2 in HF (a) S2Cl2 (b) SOCl2
(d) electrolysis of molten cryolite (c) S(OCl)2 (d) SO2Cl2
117. *Pyrolusite on heating with concentrated HCl produces
126. *When SO2 gas is passed into chlorine water, the
Cl2 (g). This process is known as
products formed are
(a) Weldon process
(a) SCl2 and S2Cl2 (b) H2SO4 and HCl
(b) Deacon process
(c) Beckmann process (c) SO2Cl2 (d) SOCl2 and HCl
(d) Mond process
182 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are 135. Tincture iodine is:
(a) aqueous solution of I2
deleted from NEET (b) solution of iodine in aqueous KI
127. *Chlorine shows bleaching action in: (c) alcoholic solution of I2
(d) aqueous solution of KI
(a) dry conditions
136. The shape of O2F2 is similar to that of :
(b) presence of HCl only
(c) moist conditions (a) C2F2 (b) H2O2
(d) none of these (c) H2F2 (d) C2H2
128. *The products of the chemical reaction between 137. *SiO2 reacts with HF to produce
Na2S2O3, Cl2 and H2O are:
(a) SiF4 and H2O (b) Si and HFO2
(a) S, HCl, Na2SO4 (b) S, HCl, Na2S
(c) SiF6 and H2O (d) H2[SiF6] and H2O
(c) S, HCl, Na2SO3 (d) S, NaClO3
138. *The etching action of HF does not involve
129. In BrF3 molecule, the lone pairs occupy equatorial
positions to minimise (a) formation of SiF4
(a) lone pair-bond pair repulsions only (b) corrosion of vessel wall
(b) bond pair-bond pair repulsion only (c) formation of H2SiF6
(c) lone pair-lone pair and lone pair-bond pair (d) white marking on laboratory ware.
repulsions Physical Properties and Compounds of Xenon of
(d) lone pair-lone pair repulsions only Group 18 Elements
130. *Bromine can be liberated from KBr by the action of
139. The element which has the highest first ionization
(a) iodine solution (b) chlorine water
energy is
(c) sodium chloride (d) potassium iodide
(a) hydrogen (b) xenon
131. *Which of the following products is formed when a (c) fluorine (d) helium
mixture of solid NaCl and solid K2Cr2O7 (in excess) is 140. Which of the following forms the least number of
heated with concentrated H2SO4? compounds?
(a) Helium (b) Argon
(a) H2CrO4 (b) Cr2(SO4)3
(c) Krypton (d) Xenon
(c) CrCl3 (d) CrO2Cl2 141. Which of the following noble gases is used for
132. *Sodium thiosulphate reacts with iodine to give cryogenic works?
(a) Neon (b) Krypton
(a) SO 2-
4 (b) SO 32- (c) Helium (d) Argon
(c) S4 O62- (d) S2 O32 142. Noble gases are difficult to liquefy because their
(a) dispersion forces are large
133. *Concentrated HNO3 reacts with iodine to give (b) dispersion forces are small
(a) HI (b) HOIO2 (c) ionization energies are low
(c) HOI (d) HOIO3 (d) electron affinities are high
143. Xenon trioxide (XeO3) has a shape of a
134. *Which of the following processes is not feasible (a) trigonal bipyramid (b) octahedral
spontaneously? (c) pyramid (d) tetrahedral
(a) H2O + F2  HF + HOF 144. Which of the following noble gases is the least
(b) H2O + Cl2  HCl + HOCl polarizable?
(c) H2O + Br2  2HBr + [O] (a) He (b) Ar
(c) Ne (d) Xe
(d) H2O + I2  2HI + [O] 145. What is the correct order of occurrence (% by weight)
in air of Ne, Ar and Kr?
(a) Ne > Ar > Kr (b) Ne > Kr > Ar
(c) Ar > Kr > Ne (d) Ar > Ne > Kr
p-BLOCK ELEMENTS (GROUP 15-18) 183

Questions marked with asterisk (*) are 149. Among the following molecules, (i) XeO3 (ii) XeOF4
(iii) XeF6 those having same number of lone pairs on
deleted from NEET Xe are
146. The structure of XeO3F2 is (a) (i) and (ii) only (b) (i) and (iii) only
(a) square pyramidal (b) pentagonal bipyramidal (c) (ii) and (iii) only (d) (i), (ii) and (iii)
(c) trigonal bipyramidal (d) octahedral
150. *Which of the following reactions of xenon compounds
147. Which of the following is planar?
(a) XeO4 (b) XeO3F is not feasible?
(a) XeO3 + 6HF → XeF6 + 3H2O
(c) XeO2F2 (d) XeF4
(b) 3XeF4 + 6H2O → 2Xe + XeO3+12HF + 1.5 O2
148. *Which of the following compounds is explosive? (c) 2XeF2 + 2H2O → 2Xe + 4HF + O2
(a) XeF2 (b) XeF4
(d) XeF6 + RbF → Rb [XeF7]
(c) XeO3 (d) XeF3
184 p-BLOCK ELEMENTS (GROUP 15-18)

EXERCISE – 2: Previous Years Questions

Questions marked with asterisk (*) are
deleted from NEET
1. *When conc. H2SO4 is heated with P2O5 the acid is 9. *Aqueous solutions of hydrogen sulphide and sulphur-
converted to (UP CPMT 2012) dioxide when mixed together, yield (KCET 2013)
(a) sulphur trioxide (a) Sulphur trioxide and water
(b) sulphur dioxide (b) hydrogen and sulphurous acid
(c) sulphur (c) sulphur and water
(d) a mixture of sulphur dioxide and sulphur trioxide (d) hydrogen peroxide and sulphur
2. Which one of the following statements is not valid for 10. The increasing order of reducing power of halogen acid
oxoacids of phosphorous? (Manipal 2012) is (Manipal 2013)
(a) Orthophosphoric acid is used in the manufacture of (a) HCl < HBr < HF < HI (b) HF < HCl < HBr < HI
triple super phosphate (c) HI < HBr < HCl < HF (d) HBr < HCl < HF < HI
(b) Hypophosphorous acid is a diprotic acid 11. The compound represents phosgene is
(c) All oxoacids contain tetrahedral four coordinated (Manipal 2013)
phosphorus (a) phosphine (b) phosphorus trichloride
(d) All oxo-acids contain at least one P = O unit and (c) carbonyl chloride (d)phosphorus oxychloride
one P–OH group 12. *Bleaching powder loses its power on keeping for a
3. *When Cl2 gas reacts with hot and concentrated long time because (KCET 2013)
sodium hydroxide solution, the oxidation number of (a) it changes into calcium hypochlorate
chlorine changes from (CBSE AIPMT 2012) (b) it changes into calcium chloride and calcium
(a) zero to +1 and zero to –5 hydroxide
(b) zero to –1 and zero to +5 (c) it absorbs moisture
(c) zero to –1 and zero to +3 (d) it changes into calcium chloride and calcium
(d) zero to +1 and zero to –3 chlorate
4. *When a colorless gas is passed through bromine 13. *The statement that is not correct is (KCET 2014)
water, only decolourisation takes places. The gas is (a) hypophosphorus acid reduces silver nitrate to silver
(AFMC 2012) (b) in solid state PCl5 exists as [PCl4]+ [PCl6]–
(a) SO2 (b) HBr (c) pure phosphine in non-inflammable
(c) HCl (d) H2S (d) phosphorous acid on heating disproportionates to
5. Which of the following is not a peroxyl acid? give metaphosphoric acid and phosphine
(Manipal 2012) 14. The species that is not hydrolysed in water is
(a) Per phosphoric acid (b) Per nitric acid (KCET 2014)
(c) Persulphuric acid (d) Perchloric acid (a) P4O10 (b) BaO2
6. *The mixture of concentrated HCl and HNO3 made in (c) CaC2 (d) Mg3N2
15. The correct arrangement of following acids of
3 : 1 ratio contains (AIIMS 2013)
phosphorus in the increasing order of oxidation state of
(a) ClO2 (b) NOCl
phosphorus is (Guj CET 2014)
(c) NCl3 (d) N2O4
(a) hypophosphorus acid < orthophosphorus acid <
7. In pyrophosphoric acid the number of hydroxyl groups pyrophosphoric acid
are (UP CMT 2013) (b) hypophosphorus acid < pyrophosphoric acid =
(a) 2 (b) 3 orthophosphorus acid
(c) 4 (d) 5
(c) pyrophosphoric acid < hypophosphorus acid <
8. The correct order of relative acidity is
orthophosphorus acid
(UP CPMT 2013)
(d) pyrophosphoric acid < orthophosphorus acid <
(a) HClO > HClO2 > HClO3 > HClO4
hypophosphorus acid
(b) HClO4 > HClO3 > HClO2 > HClO
(c) HClO > HClO4 > HClO2 > HClO3
(d) HClO3 > HClO2 > HClO4 > HClO
p-BLOCK ELEMENTS (GROUP 15-18) 185

Questions marked with asterisk (*) are 24. *A gas ‘X’ is used in filling balloons for
deleted from NEET meteorological observations. It is also used in gas-
16. Acidity of diprotic acids in aqueous solutions increases cooled nuclear reactors. Here, the gas X is
in the order (CBSE AIPMT 2014) (AIIMS 2018)
(a) H2S < H2Se < H2Te (b) H2Se < H2S < H2Te (a) neon (b) argon
(c) H2Te < H2S < H2Se (d) H2Se < H2Te < H2S (c) krypton (d) helium
17. *Which among the following group 16 elements exists 25. *Xenon hexafluoride reacts with silica to form a xenon
in more than two allotropic states? (JCECE 2014) compound X. The oxidation state of xenon in X is
(a) Polonium (b) Tellurium (JIPMER 2018)
(c) Selenium (d) Oxygen (a) +2 (b) +4
(c) +6 (d) 0
18. *The gaseous product formed when HOCl reacts with
26. In which of the following arrangements, the order is not
H2O2 in acidic medium is (Kerala CEE 2014) strictly according to the property written against it?
(a) H2 (b) Cl2 (AIIMS 2018)
(c) O2 (d) HCIO2 (a) CO2 < SiO2 < SnO2 < PbO2 (oxidising power)
19. *Nitrogen dioxide and sulphur dioxide have some (b) HF < HCl < HBr < Hl (acidic strength)
properties in common. Which property is shown by one (c) NH3 > PH3 < AsH3 < SbH3 (basic strength)
of these compounds, but not by the other? (d) B < C < O < N (first ionization enthalpy)
(CBSE AIPMT 2015) 27. *Which of the following products will be obtained
(a) Forms acid-rain when copper metal is reacted with HNO3? (AIIMS
(b) Is a reducing agent 2018)
(c) Is soluble in water (a) NO and N2O5 (b) NO and NO2
(d) Is used as a food-preservative (c) NO2 and N2O5 (d) HNO2 and N2
20. Which of the following oxide is most acidic? 28. Which of the following oxyacid does not contain P–O–
(JIPMER 2017) P bond? (AIIMS 2018)
(a) As2O3 (b) P2O5 (a) Isohypophosphoric acid
(c) Sb2O3 (d) Bi2O3 (b) Pyrophosphorus acid
21. *Among the following compounds, which will produce (c) Diphosphoric acid
POCl3 with PCl5? (JIPMER 2017) (d) Hypophosphoric acid
(a) Only O2 29. The correct order of N-compounds in its decreasing
order of oxidation states is (NEET 2018)
(b) O2 and CO2
(a) HNO3, NH4Cl, NO, N2 (b) HNO3, NO, NH4Cl, N2
(c) CO2, O2 and P4O10 (c) HNO3, NO, N2, NH4Cl (d) NH4Cl, N2, NO, HNO3
(d) SO2, H2O, H2SO4,P4O10 30. Which of the following chemicals are used to
22. In which of the following compounds, sulphur show manufacture methyl isocyanate that caused “Bhopal
maximum oxidation number? (JIPMER 2017) Gas Tragedy” ? (JIPMER 2018)
(a) H2SO4 (i) Methylamine (ii) Phosgene
(iii) Phosphine (iv) Dimethylamine
(b) SO3
(a) (i) and (ii) (b) (iii) and (iv)
(c) H2S2O7 (c) (i) and (iii) (d) (ii) and (iv)
(d) All have same oxidation number for sulphur 31. Which of the following pair behaves as strong and
23. *Name the gas that can readily decolourise acidified weak base hydride respectively? (JIPMER 2018)
(a) NH3, PH3 (b) NH3, BiH3
KMnO4 solution. (NEET 2017) (c) PH3, BiH3 (d) BiH3, AsH3
(a) CO2 (b) SO2
(c) NO2 (d) P2O5
186 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are 8NH3  3Cl2 X

(Excess)
deleted from NEET NH3 3Cl2  Y
32. *Conversion of oxygen into ozone is non-spontaneous (Excess)
at (AIIPMT 2018) (a) X = 6NH4 Cl + N 2 ; Y = NCl3 + 3HCl
(a) low temperature (b) X = NCl3+ 3HCL; Y = 6NH4 Cl + N2
(b) all temperature (c) X = NCl3 + N2 ; Y 6 NH4 Cl + 3HCL
(c) high temperature (d) X = 6NH4 Cl + 3HCl; Y = NCl3 + N2
(d) room temperature
33. Among the following, the correct formula of Marshall’s 40. *A green yellow gas reacts with an alkali metal
acid is (JIPMER 2018) hydroxide to form a halite which can be used in
(a) H2S2O6 (b) H2S2O8 fireworks and safety matches. The gas and halite are,
(c) H2SO4 (d) H2SO5 respectively (AIIMS 2019)
34. Which is the correct order of thermal stability for H2E (a) Br2 , KBrO3
(E = O, S, Se, Te and Po)? (NEET 2019) (b) Cl2, KClO3
(a) H2 O  H2S  H2Se  H2 Te  H2 Po (c) I2 , NaIO3
(b) H2 Po  H2 Te  H2Se  H2S  H2O (d) Cl2 , NaClO3
41. Which of the following statements is not true for
(c) H2Se  H2Te  H2 Po  H2O  H2S
halogens? (NEET 2019)
(d) H2S  H2 O  H2Se  H 2Te  H2 Po (a) All except fluorine show positive oxidation states
(b) All are oxidizing agents
35. *Which of the following statement is correct for
(c) All form monobasic oxyacids
oleum? (AIIMS 2019) (d) Chlorine has the highest electron-gain enthalpy
(a) It is prepared by absorption of SO3 in conc. H2SO4 42. Which of the following inert gas participate in
(b) It contains O–O groups chemicals reaction? (AIIMS 2019)
(c) It has six OH groups (a) Xe (b) He
(d) None of the above (c) Ne (d) None of the above
36. Correct order of bond dissociation energy is 43. In how many of the following number of lone pair at
(AIIMS 2019) central atom is zero
(a) Br2 > Cl2 (b) F2 > Cl2 XeO3, XeO2F2, XeO4, XeO3F2, XeO3F6 ?
(c) l2 > F2 (d) F2 > l2 (AIIMS2019)
37. *Yellow colour of chlorine water fades because of (a) 2 (b) 3
(AIIMS 2019) (c) 4 (d) Zero
(a) Form action of chlorine HCl and HOCl 44. Which of the following rare gas is the abundant in air?
(b) Chlorine gas escapes (JIPMER 2019)
(c) ClO2 + H2 (a) He (b) Ne
(d) Cl2O (c) Ar (d) Kr
38. Affinity for hydrogen decreases in the group from 45. Identify the incorrect statement related to PCl5 from the
fluorine to iodine. Which of the halogen acids should following: (NEET 2019)
have highest bond dissociation enthalpy? (a) Two axial P-Cl bonds make an angle of 180º with
(AIIMS 2019) each other
(a) HF (b) HCl (b) Axial P-Cl bonds are longer than equatorial P-Cl
(c) HBr (d) HI bonds.
(c) PCl5 molecule is non-reactive.
39. *What is X and Y in the below reaction?(AIIMS 2019) (d) Three equatorial P-Cl bonds make an angle of 120º
with each other.
p-BLOCK ELEMENTS (GROUP 15-18) 187

Questions marked with asterisk (*) are In the light of the above statements, choose the most
appropriate answer from the options given below:
deleted from NEET (NEET 2022)
46. *A compound ‘X’ upon reaction with H2O produced a (a) Both Statement I and Statement II are correct.
colourless gas ‘Y’ with rotten fish smell. Gas ‘Y’ is (b) Both Statement I and Statement II are incorrect.
absorbed in a solution of CuSO4 to give Cu3P2 as one of (c) Statement I is correct but Statement II is incorrect.
the products. Predict the compound ‘X’ (d) Statement I is incorrect but Statement II is correct.
(NEET (Odisha)2019) 53. Given below are two statements: one is labelled as
Assertion A and the other is labelled as Reason R.
(a) Ca3P2 (b) NH4Cl
Assertion A: Helium is used to dilute oxygen in diving
(c) As2O3 (d) Ca3(PO4)2 apparatus.
47. *Which of the following oxoacids of phosphorus has Reason R: Helium has high solubility in O2.
In the light of the above statements, choose the correct
strongest reducing property? (NEET Odisha2019) answer from the options given below :
(a) H4P2O7 (b) H3PO3 (NEET 2023)
(c) H3PO2 (d) H3PO4 (a) Both A and R are true, but R is NOT the correct
48. In which of the following, oxidation state of explanation of A
phosphorus is +3? (JIPMER 2019) (b) A is true but R is false
(a) Orthophosphoric acid (b) Pyrophosphoric acid (c) A is false but R is true
(d) Both A and R are true and R is the correct
(c) Orthophosphrous acid (d) Meta Phosphoric acid
explanation of A
49. *Urea reacts with water to form A which will 54. Match List-I with List-II : (NEET 2023)
2+
decomposes to form B. B when passed through Cu
(aq), deep blue color solution C is formed. What is the List-I List-II
formula of C from the following. (NEET 2020) (Oxoacids of Sulphur) (Bonds)
A. Peroxodisulphuric acid I. Two S-OH, Four S=O,
(a) Cu(OH)2 (b) CuCO3. Cu(OH)2
One S-O-S
(c) CuSO4 (d) [Cu(NH3)4]+2 B. Sulphuric acid II. Two S-OH, One S=O
50. In which on of the following arrangements the given C. Pyrosulphuric acid III. Two S-OH, Four
sequence is not strictly according to the properties S=O, One S-O-O-S
Indicated against it? (NEET 2021) D. Sulphurous acid IV. Two S-OH, Two
(a) CO2<SiO2<SnO2<PbO2 : Increasing oxidizing power S=O
(b) HF < HCl < HBr < HI : Increasing acidic strength Choose the correct answer from the options given
(c) H2O < H2S < H2Se < H2Te : Increasing pKa values below:
(d) NH3 < PH3 < AsH3 < SbH3: Increasing acidic character (a) A-III, B-IV, C-I, D-II (b) A-I, B-III, C-IV, D-II
51*. Assertion (A): ICl is more reactive than I2 (c) A-III, B-IV, C-II, D-I (d) A-I, B-III, C-II, D-IV
Reason(R): I-Cl bond is weak than I-I bond 55. Which of the following oxoacids of phosphorus has
Choose the most appropriate answer from the options strongest reducing property? (NEET 2024)
given below: (NEET 2022) (a) Se (b) Te
(a) Both (A) and (R) are correct and (R) is the correct (c) Po (d) O
explanation of (A) 56. Given below are two statements:
(b) Both (A) and (R) are correct but (R) is not the Statement I: The boiling point of hydrides of Group
correct explanation of (A) 16 elements follow the order H2O > H2Te > H2Se > H2S
(c) (A) is correct but (R) is not correct Statement II: On the basis of molecules mass, H2O is
(d) (A) is not correct but (R) is correct expected to have lower boiling point than the other
52. Statement I: The boiling points of the following members of the group but due to the presence of
extensive H-bonding in H2O. It has higher boiling
hydrides of group 16 elements increases in the order-
point. (NEET 2024)
H2O < H2S < H2Se < H2Te (a) Both statement I and statement II are false
Statement II: The boiling points of these hydrides (b) Statement I is true but statement II is false
increases with increase in molar mass. (c) Statement I is false but statement II is true
(d) Both statement I and statement II are true.
188 p-BLOCK ELEMENTS (GROUP 15-18)

EXERCISE – 3: Achiever’s Section

Questions marked with asterisk (*) are
deleted from NEET
Single Answer Type Questions
1. The best reducing agent among the following is 7. In the cationic parts of solid N2O5 and solid N2O4, the
(a) NH3 (b) SbH3 bond order of N–O are, respectively,
(c) PH3 (d) AsH3 (a) 3.0 and 2 (b) 2 and 3
2. Which of the following compounds does not form (c) 2.5 and 3.0 (d) 3 in both
ammonia on heating? 8. *NH4NO2 on heating gives
(a) (NH4)2 SO4 (b) NH4Cl
(a) N2O (b) HNO3
(c) (NH4)2 CO3 (d) NH4NO2
(c) N2 (d) N2H4
3. *N2 is passed through overheated CaC2. Which of the
9. Phosphorus is obtained by
following options is correct for the product formed?
(I) State of hybridization of C is sp. (a) reducing phosphate rock with coke at a high
(II) Urea is an intermediate formed during hydrolysis temperature in the presence of silica in an electric
of the above product. furnace
(III) Anion present in the product is not a pseudo (b) reducing phosphate rock with sulphur and alumina
halide ion. (c) reducing phosphate rock with silica and iron oxide
(IV) Hydrolysis of the product gives rise to NH3 gas in an electric furnace
slowly.
(d) reducing phosphatic fertilizers with boron and
(a) I, II and III (b) III and IV
(c) I, II and IV (d) None of the above alumina in an electric furnace
4. *Which of the following compounds give NH3 on 10. *White phosphorus on reaction with limewater gives
heating? calcium salt of an acid (A) along with a gas (X). Which
(I) NH4NO3 (II) NH4NO2 of the following is correct?
(III) (NH4)2 Cr2O7 (IV)(NH4)2CO3 (a) (A) on heating gives (X) and O2
(V) Mg (NH4) PO4
(b) The bond angle in (X) is less than that in case of
(a) I, IV (b) II, V ammonia
(c) IV only (d) IV, V (c) (A) is a dibasic acid
5. *Pure nitric acid is a colourless liquid, but on exposure (d) (X) is more basic than ammonia

to light it turns brownish due to 11. *White phosphorus reacts with calcium to give a
(a) slight decomposition of HNO3 into O2 certain compound. This compound on hydrolysis
produces
(b) slight decomposition of HNO3 into NO2 and O2
(a) P2H4 (b) PH3
(c) the formation of N2O
(c) P2 (d) P4O10
(d) the formation of H3O+ and NO
6. *When AgNO3 is heated strongly above 800°C, it 12. *Which is not correct regarding the Holme’s signal?
(a) PH3 catches fire in contact of air spontaneously.
produces (b) P2H4 catches fire in contact of air spontaneously.
(a) Ag2O, NO and NO2 (c) PH3, C2H2 and P2H4 are formed together
(b) Ag, NO2 and O2 (d) All the gases burn together
13. The p-block element that forms predominantly basic
(c) Ag2O, NO2 and O2
oxide is
(d) Ag, NO and O2 (a) Bi (b) P
(c) As (d) N
p-BLOCK ELEMENTS (GROUP 15-18) 189

Questions marked with asterisk (*) are (c) Br2

(d) no reaction
deleted from NEET
14. The number of S—S bonds in sulphur trioxide trimer 21. *HClO4 + P2O5  (A) + (B)
S3O9 is: (A) and (B) are:
(a) three (b) two (a) HClO3, H3PO4 (b) Cl2O6, HPO3
(c) one (d) zero (c) ClO2, H3PO4 (d) Cl2O7 , HPO3
15. *Na2SO3 on being heated with sulphur produces 22. *Which of the following oxides of chlorine is obtained
(a) Na2S2O3 (b) Na2S4O6
by passing dry chlorine over silver chlorate at 900C?
(c) Na2SO4 (d) Na2S5 (a) Cl2O (b) ClO3
16. *When H2S gas is passed into aqueous sulphur dioxide (c) ClO2 (d) ClO4
(a) a clear solution of H2SO4 is formed
23. *Dry Cl2 reacts with dry SO2 to form:
(b) SO2 is converted into a yellow precipitate of
sulphur (a) thionyl chloride
(c) H2S is converted into a yellow precipitate of (b) sulphuryl chloride
sulphur (c) sulphur dichloride
(d) both SO2 and H2S are converted into a yellow (d) sulphur monochloride
precipitate of sulphur 24. *When F2 reacts with hot and conc. alkali, then
17. *NH4Cl is preferred to NaCl for the preparation of HCl following will be obtained:
by the action of concentrated H2SO4 because (i) OF2 (ii) O2
(a) NH4Cl is not expensive (iii) H2O (iv) NaF
(b) NH4Cl is very volatile (a) (i), (iii) and (iv)
(c) NH4HSO4 formed during the reaction is insoluble (b) (ii) and (iii) only
but NaHSO4 is soluble (c) (ii), (iii) and (iv)
(d) NH4HSO4 formed during the reaction is soluble but (d) all of these
NaHSO4 is insoluble
25. The oxidation state of xenon atom in XeF4, HXeO4
18. The property of halogens, that indicated incorrect is:
(a) F > Cl > Br > I ........ ionisation energy and Na4XeO6 are respectively:
(b) F > Cl > Br > I ......... electron affinity (a) + 4, + 6, + 6 (b) + 4, + 6, + 7
(c) F > Cl > Br > I ........ electronegativity (c) + 4, + 6, + 8 (d) + 4, + 5, + 8
(d) I > Br > Cl > F ........ density in liquid state 26. The shape of XeO2F2 molecule is:
19. Liquid I2 Cl6 has the structure (a) trigonal bipyramidal
(b) square planar
(c) tetrahedral
(a)
(d) see-saw
Assertion and Reason Types questions
(b) [ICl2]+[ICl4]– (A) If both assertion and reason are true and
(c) monomeric reason is the correct explanation of the assertion.
(d) None of these (B) If both assertion and reason are true but reason is not the
correct explanation of the assertion.
20. *When iodine is treated with a mixture of NaF, NaBr
(C) If assertion is true but reason is false.
and NaCl in water, it gives (D) If assertion is false but reason is true.
(a) a mixture of F2, Cl2 and Br2
(b) Cl2
190 p-BLOCK ELEMENTS (GROUP 15-18)

Questions marked with asterisk (*) are 29. *Assertion: O3 has a fishy smell.
deleted from NEET Reason: It absorbs red part of the visible light.
27. Assertion: HNO3 is a stronger acid than HNO2. (a) A (b) B
Reason: In HNO3 there are two nitrogen to oxygen (c) C (d) D
bonds whereas in HNO2 there is only one. 30. *Assertion: The electronic structure of O3 is
(a) A (b) B
(c) C (d) D
28. Assertion: Although PF5, PCl5 and PBr5 are known, the
pentahalides of nitrogen have not been observed.
Reason: Phosphorous has a lower electronegativity Reason: The following structure is not allowed because
than nitrogen. the octet around O cannot be expanded.
(a) A (b) B
(c) C (d) D

(a) A (b) B
(c) C (d) D
p-BLOCK ELEMENTS (GROUP 15-18) 191

Notes:

Find Answer Key and Detailed Solutions at the end of this book
:

p-BLOCK ELEMENTS (GROUP 15-18)

d AND f BLOCK ELEMENTS
Chapter 10 193

d and f Block Elements

1. The d-Block Elements Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9 (Cupric ion)
1.1 Introduction
1.2 Position of d-Block Elements in
“The elements in which the last differentiating electron enters into
the d-orbitals of the penultimate shell are called d-block elements”. Periodic Table
The properties of these elements are intermediate between the In modern periodic table, d-block elements are placed in between
properties of s-block and p-block elements. s-block and p-block elements. There are total 10 groups of d-
These elements represent a change or transition in properties block elements placed in the middle of periodic table. These are
from more electropositive elements (s-block) to less electropositive from group-3 to group-12. d-block elements are further classified
elements (p-block). Therefore these elements are called transition into four series.
elements. 4th period (21Sc to 30Zn, 10 elements) 1st Transition series.
A transition element may also be defined as the element which 5th period (39Y to 48Cd, 10 elements) 2nd Transition series.
has partially filled d-orbital in their ground state or most stable 6th period (51La, 72Hf to 80Hg, 10 elements) 3rd Transition series.
oxidation state. 7th period (89Ac, 104Rf to 112Cn, 10 elements) 4th Transition series.

Fig. 13.1: Blocks in periodic table

SCAN CODE
d and f Block Elements
194 d AND f BLOCK ELEMENTS
Thus, the electronic configuration of chromium (Z = 24) and copper
1.3 Electronic Configuration (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 2p6 3s6 3p6 3d10 4s1
In d-block elements with increase in atomic number, the d-orbitals respectively.
of penultimate shell i.e. (n-1) d are gradually filled by electrons.
The general electronic configuration of d-block element is, (n-1)
d1-10, ns0-2. 1.4 General Properties of Transition
Depending upon the d-orbitals of which penultimate shell (i.e. n = Elements
4, 5, 6, 7) are filled, four rows (called series) of ten elements each
1.4.1 Physical Properties
obtained. They correspond to 3d, 4d, 5d and 6d subshells.
All the transition elements show typical metallic properties like
Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’ subshell,
high tensile strength, ductility, malleability, high thermal and
hence ns orbital is filled first then (n – 1) d orbitals.
electrical conductivity and metallic lustre. With the exceptions of
The electronic configuration of d-block elements of four series is
Zn, Cd, Hg and Mn, they have one or more typical metallic
shown as follows : structures at normal temperatures.
Table 13.1 : First (3d) Transition Series (Sc–Zn)
At. No. 21 22 23 24 25 26 27 28 29 30 Table 13.5 : Lattice Structures of d-Block Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
4s 2 2 2 1 2 2 2 2 1 2 Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d 1 2 3 5 5 6 7 8 10 10 hcp hcp bcc bcc X bcc ccp ccp ccp X
(bcc) (bcc) (bcc, (hcp) (hcp) (hcp)
ccp)
Table 13.2 : Second (4d) Transition Series (Y-Cd) Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
At. No. 39 40 41 42 43 44 45 46 47 48
(bcc) (bcc) (hcp)
Element Y Zr Nb Mo Tc Ru Rh Pd Au Cd
5s 2 2 1 1 1 1 1 0 1 2 La Hf Ta W Re Os Ir Pt Au Hg
4d 1 2 4 5 6 7 8 10 10 10 hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(ccp, (bcc)
bcc)
Table 13.3 : Third (5d) Transition Series (La-Hg)
At. No. 57 72 73 74 75 76 77 78 79 80 The melting and boiling points of transition metals are very high.
Element La Hf Ta W Re Os Ir Pt Au Hg The high melting points of these metals are attributed to the
6s 2 2 2 2 2 2 2 1 1 2 involvement of greater number of electrons from (n-1)d in addition
5d 1 2 3 4 5 6 7 9 10 10
to the ns electrons.

Table 13.4 : Fourth (6d) Transition Series (Ac-Cn)

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 additonal
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 excatly half-filled with
configuration 3d5 4s1 and that in case of copper, it gets completely
filled with configuration 3d10 4s1. This can be explained on the Fig 13.2 : Melting points of transition elements
basis of exchange energy.

SCAN CODE
d and f Block Elements
d AND f BLOCK ELEMENTS 195
In any series of transition elements the melting points rise to a (iii) At the end of the period, there is a slight increase in the
maximum at d5 except for anomalous values of Mn and Tc and fall atomic radii.
regularly as the atomic number increases. Mn has stable electronic Explanation
configuration (3d5 half filled, 4s2 fully filled). As a result 3d electrons Near the end of series, the increased electron-electron
are more tightly held by the nucleus and this reduces the repulsions between added electrons in the same orbitals are
delocalisation of electrons resulting in weaker metallic bonding. greater than the attractive forces due to the increased nuclear
Transition elements have high enthalpies of atomisation. The charge. This results in the expansion of the electron cloud
maxima at about the middle of each series indicate that one and thus the atomic radius increases.
unpaired electron per d orbital is particularly favourable for strong (iv) The atomic radii increase down the group. This means that
interatomic interaction. In general, greater the number of valence the atomic radii of second series are larger than those of first
electrons, stronger is the resultant bonding. Metals with very transition series. But the atomic radii of the second and third
high enthalpy of atomisation tend to be noble in their reactions. transition series are almost the same.
The transition metals of the second and third series have greater The atomic radii of the elements of the second and third
enthalpies of atomisation than the corresponding elements of the transition metals are nearly same due to lanthanide contraction
first series. (or also called lanthanoid contraction) discussed later.)

Fig 13.3 : Enthalpies of atomisation of transition elements

1.4.2 Atomic Radii
(i) The atomic radii of the transition metals lie in-between those Fig 13.4 : Atomic radii of transition elements
of s- and p-block elements. 1.4.3 Ionic Radii
(ii) Generally the atomic radii of d-block elements in a series (i) The trend followed by the ionic radii is the same as that
decrease with increase in atomic number but the decrease in followed by atomic radii.
atomic size is small after midway.
(ii) Ionic radii of transition metals are different in different
Explanation oxidation states.
The atomic radius decreases with the increase in atomic (iii) The ionic radii of the transition metals are smaller than those
number as the nuclear charge increases whereas the shielding of the representative elements belonging to the same period.
effect of d-electron is small. After midway, as the electrons
enter the last but one (penultimate) shell, the added d-electron
1.4.4 Ionisation Enthalpies
shields (screens) the outermost electron. Hence, with the (i) The first ionisation enthalpies of d-block elements lie between s-
increase in the d-electrons, screening effect increases. This block and p-block elements. They are higher than those of s-
counterbalances the increased nuclear charge due to increase block elements and are lesser than those of p-block elements.
in atomic number. As a result, the atomic radii remain practically The ionisation enthalpy gradually increases with increase in
same after chromium. For example in Fe, the two opposing atomic number along a given transition series though some
tendencies almost counterbalance and there is no change in irregularities are observed.
the size from Mn to Fe.

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196 d AND f BLOCK ELEMENTS
Table 13.6 : Ionisation Enthalpies of 3d Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Δi H o in kJ mol-1
IE1 I 631 656 650 653 717 762 758 736 745 906
IE 2 II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
IE 3 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 M3+/M2+  -0.37 -0.26 -0.41 +1.57 +0.77 +1.97   

Explanation 1.4.5 Oxidation State

The increasing ionization enthalpies are due to increased nuclear (i) With the exception of few elements, most of the d-block
charge with increase in atomic number which reduces the size of elements show more than one oxidation state.
the atom making the removal of outer electron difficult.
(ii) The elements show variable oxidation state because ‘(n-1) d’
(ii) In a given series, the difference in the ionisation enthalpies and ‘ns’ orbitals in the atoms of d-block elements have almost
between any two successive d-block elements is very much same energies and therefore electron can be removed from
less than the difference in case of successive s-block or p- ‘(n-1)d’ orbitals as easily as ‘ns’ orbitals electrons.
block elements.
(iii) Minimum oxidation state = Total number of 4s electrons lost.
Explanation Maximum oxidation state = (Total number of 4s electrons lost
The addition of d electrons in penultimate shell with increase + 3d electrons lost).
in atomic number provides a screening effect and thus shields (iv) The elements which give the greatest number of oxidation
the outer s electrons from inward nuclear pull. Thus, the states occur near the middle of the series. For example, Mn
effects of increased nuclear charge and addition of d electrons exhibits all the oxidation states from +2 to +7.
tend to oppose each other.
(v) The extreme ends of a series show less number of oxidation
(iii) The first ionization enthalpy of Zn, Cd and Hg are, however, states. For example, Sc shows only +3 and Zn shows only +2.
very high because of the fully filled (n-1) d10 ns2 configuration.
(vi) Transition metals also show zero oxidation states in metal
(iv) Although second and third ionization enthalpies also, in carbonyl complex. For example : Ni in [Ni(CO)4] (Nickel
general, increase along a period, but the magnitude of increase tetracarbonyl) has zero oxidation state.
for the successive elements is much higher.
(vii) In groups 4 to 10, the lower oxidation states are more stable in
(v) The high values of 3rd ionization enthalpies for Cu, Ni and 3d series. For example, in group 6, Mo(VI) and W(VI) are
Zn explain why they show a maximum oxidation state of +2. more stable than Cr(VI). Thus Cr(VI) in dichromate is a stronger
oxidising agent then MoO3 and WO3 in acidic medium.

Table 13.7 : 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

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1.4.6 Standard Electrode Potentials (E o) Table 13.8 : Eo ( M 2+  M o ) Values for Ti to Zn
In solution, the stability of the compounds of transition metals
depends upon electrode potentials. Electrode potential values M a Ho  i H1o  i H o2  Hyd H o  M 2   Eo/V
depend upon factors such as enthalpy of sublimation (or
Ti 469 656 1309 –1866 –1.63
atomisation) of the metal, the ionisation enthalpy and the hydration
V 515 650 1414 –1895 –1.18
enthalpy, i.e.,
Cr 398 653 1592 –1925 –0.90
 sub H
M  s   M  g  , (  sub H is enthalpy of sublimation) Mn 279 717 1509 –1862 –1.18
Fe 418 762 1561 –1998 –0.44
 iH
M  g    M  g   e , (  i H is ionisation enthalpy)
 
Co 427 758 1644 –2079 –0.28
Cu 339 745 1958 –2121 0.34
 H
M   g   aq 
hyd
M   aq  , (  hyd H is enthalpy of hydration) Zn 130 906 1734 –2059 –0.76

The total energy, T H , for the process involving sublimation,

(iv) The values of Eo for Mn, Ni and Zn are more negative than
ionisation and hydration simultaneously, i.e., for the process, expected from the general trend. This is due to greater stability
M  s  
 M   aq   e  , will be the sum of the three types of of half-filled d-subshell (d5) in Mn2+, and completely filled d-
subshell (d10) in Zn2+. The exceptional behaviour of Ni towards
enthalpies, i.e.,
Eo value from the regular trend is due to its high negative
 T H  sub H   i H   hyd H enthalpy of hydration.

Thus, T H , is the total enthalpy change when solid metal, M is

brought in the aqueous medium in the form of monovalent ion,
M+ (aq).

Trends in the M2+/M Standard Electrode Potentials:

(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.
(ii) The general trend towards less negative Eo values along the
series is due to the general increase in the sum of first and 2
Fig 13.5 : Eo ( M  Mo ) values for Ti to Zn
second ionization enthalpies.
(iii) Copper shows a unique behaviour in the series as it is the
only metal having positive value for Eo. This explains why is Trends in the M3+/M2+ Standard Electrode Potentials:
does not liberate H2 gas from acids. It reacts only with the (i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
oxidizing acids (HNO3 and H2SO4) which are reduced. The Sc3+ ion which has a noble gas configuration.
reason for positive Eo value for copper is that the sum of (ii) The highest value for Zn is on account of very high stability
enthalpies of sublimation and ionization is not balanced by of Zn2+ ion with d10 configuration. It is difficult to remove an
hydration enthalpy. electron from it to change it into +3 state.
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows that
Mn 2+ is very stable which is on account of stable d 5
configuration of Mn2+.

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(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account Diamagnetic substances are repelled by the applied field while
of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy the paramagnetic substances are attracted. Most of the transition
of Fe. metal ions are paramagnetic due to the presence of unpaired
Chemical Reactivity and Eo Values: electrons. Each such electron having a magnetic moment
The transition metals vary widely in their chemical reactivity. Some associated with its spin angular momentum and orbital angular
of them are highly electropositive and dissolve in mineral acids momentum.
whereas a few of them are ‘noble’, i.e., they do not react with simple In first transition elements series the orbital angular magnetic
acids. Some results of chemical reactivity of transition metals as moment is insignificant the orbital contribution is quenched by
related to their Eo values are given below : the electric fields of the surrounding atoms so magnetic moment
is equal to the spin magnetic moment only.
(i) The metals of the first transition series (except copper) are
It can be calculated by using the formula:
relatively more reactive than the other series. Thus, they are
oxidized by H+ ions though the actual rate is slow, e.g., Ti and  eff  n (n  2) BM
V are passive to dilute non-oxidizing acids at room
n  no. of unpaired electron.
temperature.
The magnetic moment increases with the increasing number of
(ii) As already explained, less negative Eo values for M2+/M along unpaired electrons. Thus, the observed magnetic moment is
the series indicate a decreasing tendency to form divalent directly related to the number of unpaired electrons present in the
cations. atom, molecule or ion.
(iii) More negative Eo values than expected for Mn, Ni and Zn
show greater stability for Mn2+, Ni2+ and Zn2+. 1.4.8 Catalytic Properties
(iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+ Most transition elements and their compounds have good catalytic
and Co3+ ions ar the strongest oxidizing agents in aqueous properties because
solution whereas Ti2+, V2+ and Cr2+ are strongest reducing (a) They possess variable oxidation state.
agents and can liberate hydrogen from a dilute acid, e.g.,
(b) They provide a large surface area for the reactant to be
2 Cr2+ (aq) + 2 H+ (aq) 
 2 Cr3+ (aq) + H2 (g) absorbed.

Table 13.10 : Some Common Catalysts

1.4.7 Magnetic Behaviour
When a magnetic field is applied to substances, mainly two types
Catalysts Uses
of magnetic behaviour are observed: diamagnetism and
paramagnetism. TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in
polymerisation of ethylene
Table 13.9 : Magnetic Moments of 3d Series Ions V2O5 Contact process SO2  SO3
Fe Haber Bosch process
Ion Unpaired Magnetic moment PdCl2 Wacker’s process for CH3CHO
electron(s) Calculated Observed
manufacturing
Sc3+ 3d0 0 0 0
Ti3+ 3d1 1 1.73 1.75 Pd Hydrogenation of alkene, alkyne
Tl2+ 3d2 2 2.84 2.76 Pt/PtO Adam’s catalyst for selective
V2+ 3d3 3 3.87 3.86 reduction
Cr2+ 3d4 4 4.90 4.80
Pt Catalytic convertor, for
Mn2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3 – 5.5 cleaning car exhaust fumes
Co2+ 3d7 3 3.87 4.4 – 5.2 Pt/Rh Ostwald’s process :
Ni2+ 3d8 2 2.84 2.9 – 3, 4 NH3  NO
Cu2+ 3d9 1 1.73 1.8 – 2.2
Zn2+ 3d10 0 0 Cu Oxidation of alcohols

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1.4.9 Complex Formation 1.4.11 Interstitital 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
lone pairs of electrons. These ions or molecules are called ligands. lattices.
They donate lone pairs of electrons to the central transition metal They are represented by formulae like TiC, TiH2, Mn4N, Fe3H,
ion forming coordinate bonds. Fe3C etc. However, actually they are non-stoichiometric materials,
A few examples are given below : e.g., TiH1.7, VH0.56 etc. and the bonds present in them are neither
[Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH3)4]2+, [Ni(CN)4]2– typically ionic nor covalent. Some of their important characteristics
and [PtCl4]2– are as follows:
Such complex compounds are not formed by s - and p - block (i) They are very hard and rigid, e.g., steel which is an interstitial
elements. compound of Fe and C is quite hard. Similarly, some borides
Explanation. The transition elements form complexes because of are as hard as diamond.
the following reasons : (ii) They have high melting points which are higher than those
(i) Comparatively smaller size of their metal ions. of the pure metals.
(ii) Their high ionic charges and high charge/size ratio. (iii) They show conductivity like that of the pure metal.
(iii) Availability of vacant d-orbitals so that these orbitals can (iv) They acquire chemical inertness.
accept lone pairs of electrons donated by the ligands.
1.4.10 Formation of Coloured Compounds 1.4.12 Alloy Formation
Transition elements form coloured ions due to presence of Alloys are homogeneous solid solutions of two or more metals
incompletely filled d-orbitals and unpaired electrons. They can obtained by melting the components and then cooling the melt.
undergo d-d transition by absorbing colour from visible region These are formed by metals whose atomic radii differ by not more
and radiating complementary colour, e.g. Cu2+ (blue), V2+(violet), than 15% so that the atoms of one metal can easily take up the
Cr3+(green). Cu+(3d10), Zn2+(3d10), Cd2+(4d10), Sc3+(3d0 ) are white positions in the crystal lattice of the other.
due to presence of no unpaired electrons and cannot undergo d- As transition metals have similar atomic radii and other
d transition. characteristics, hence they form alloys very readily.
Alloys are generally harder, have higher melting points and more
Table 13.11 : Colour of Ions of 3d Series
resistant to corrosion than the individiual metals.
The most commonly used are the ferrous alloys the metals
Configuration Example Colour chromium, vanadium, molybdenum, tungsten and manganese are
3d0 Sc3+ colourless used in the formation of alloy steels and stainless steels. Some
3d0 Ti4+ colourless alloys of transition metals with non-transition metals are also very
common. e.g., brass (Cu + Zn) and bronze (Cu + Sn)
3d1 Ti3+ purple
3d1 V4+ blue
3d2 V3+ green
3d3 V2+ violet
3d3 Cr3+ violet
3d4 Mn3+ violet
3d4 Cr2+ blue
3d5 Mn2+ pink
3d5 Fe3+ yellow
3d6 Fe2+ green
Fig 13.6 : Alloy Formation
3d63d7 Co3+Co2+ bluepink
3d8 Ni2+ green
3d9 Cu2+ blue
3d10 Zn2+ colourless

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2. Important Compounds of After the reaction, the roasted mass is extracted with water
when sodium chromate is completely dissolved while ferric
Transition Elements oxide is left behind. Ferric oxide is separated out by filtration.
(ii) Conversion of Sodium Chromate into Sodium Dichromate:
2.1 Oxides and Oxocations The filtrate containing sodium chromate solution is treated
(i) The metals of the first transition series form oxides with oxygen with concentrated sulphuric acid when sodium chromate is
at high temperature. converted into sodium dichromate.
(ii) The oxides are formed in the oxidation, states +1 to +7.
(iii) The highest oxidation state in the oxides of any transition 2Na 2 CrO4  H 2SO4  Na 2 Cr2 O7  Na 2SO 4  H 2 O
[Link]  Conc. Sod. dichromate
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond
group 7, no higher oxides of iron above Fe2O are known. Sodium sulphate being less soluble crystallizes out as
Some metals in higher oxidation state stabilize by forming decahydrate, Na2SO4. 10H2O and is removed. The clear
solution is then evaporated in iron pans to a specific gravity
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+.
of 1.7 when a further crop of sodium sulphate is formed. It is
(iv) All the metals except scandium form the oxides with the removed and the solution is cooled when orange crystals of
formula MO which are ionic in nature. As the oxidation number sodium dichromate, Na2Cr2O7. 2H2O separate on standing.
of the metal increases, ionic character decreases, e.g., Mn2O7 (iii) Conversion of Na2Cr2O7 into K2Cr2O7 :
is a covalent green oil. Even CrO3 and V2O5 have low melting Hot concentrated solution of sodium dichromate is treated
points. with calculated amount of potassium chloride when potassium
2 8/3 3 4 7 dichromate, being much less soluble than sodium salt,
MnO Mn 3O4 Mn 2 O3 MnO2 Mn 2 O7 crystallizes out on cooling as orange crystals.
(v) In general, the oxides in the lower oxidation states of the
Na 2 Cr2 O7  2KCl 
 K 2 Cr2 O7  2NaCl
metals are basic and in their higher oxidation states, they are
Sodium dichromate Potassium dichromate
acidic whereas in the intermediate oxidation state, the oxides
are amphoteric. 2.2.2 Structures of Chromate and Dichromate Ions
For example, the behaviour of the oxides of manganese may The chromate ion, CrO42– is tetrahedral and the dichromate ion,
be represented as follows : Cr2O72– is made up of two tetrahedra sharing one corner with Cr–
2 8/3 3 4 7
O–Cr bond angle of 126°.
MnO Mn 3O 4 Mn 2 O3 MnO2 Mn 2 O7
Basic Amphoteric Amphoteric Amphoteric Acidic

Thus, Mn2O7 dissolves in water to give the acid HMnO4.

2.2 Potassium Dichromate, K2Cr2O7

2.2.1 Preparation Process Fig 13.7 : Structure of chromate and dichromate ions
It is prepared from the ore called chromite or ferrochrome or chrome
iron, FeO.Cr2O3. The various steps involved are as follows :
2.2.3 Properties of Potassium Dichromate
(i) Preparation of Sodium Chromate:
(a) Colour and Melting Point: It forms orange crystals which
The ore is finely powdered, mixed with sodium carbonate and
melt at 669 K.
quick lime and then roasted, i.e., heated to redness in a
reverberatory furnace with free exposure to air when sodium (b) Solubility: It is moderately soluble in cold water but freely
chromate (yellow in colour) is formed and carbon dioxide is soluble in hot water.
evolved. Quick lime keeps the mass porous and thus facilitates (c) Action of Heat: When heated to a white heat, it
oxidation. decomposes with the evolution of oxygen.

4FeCr2O4 + 8Na2CO3+ 7O2 

 8Na2CrO4 + 2Fe2O3 + 8CO2 4K 2 Cr2 O7 
 4K 2 CrO4  2Cr2 O3  3O2
Chromite ore Sod. chromate Ferric oxide

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(d) Action of Alkalies: When an alkali is added to an orange (ii) It oxidises ferrous salts to ferric salts
red solution of dichromate, a yellow solution results due to  K 2SO 4  Cr2  SO4 3
K 2 Cr2 O7  7H 2SO 4  6FeSO 4 
the formation of chromate.
3Fe2  SO4 3  2H 2 O
K 2 Cr2 O7  KOH 
 2K 2 CrO 4  H 2 O
Pot. dichromate [Link] (iii) It oxidises H2S to sulphur

or Cr2 O72   2OH  

 2CrO24   H 2 O  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3H 2S 

On acidifying, the colour again changes to orange red due to + 7H2O + 3S

the reformation of dichromate. (iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur
2 K 2 CrO4  H 2SO4 
 K 2 Cr2 O7  K 2SO4  H 2 O
 K 2SO4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3Na 2SO3 
or 2 CrO 24   2 H  
 Cr2 O72   H 2 O
+ 4H2O + 3Na2SO4
This interconversion is explained by the fact that in dichromate (v) It oxidises nitrites to nitrates
2
solution, the Cr2 O 7
ions are invariably in equilibrium with  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4 H 2SO 4  3NaNO 2 
2
CrO 4
ions at pH = 4, i.e., + 3 NaNO3 + 4 H2O
(vi) It oxidises halogen acids to halogen
pH  4

Cr2 O72   H 2 O  2CrO 24   2H 
Orange red Yellow K 2 Cr2 O7  14 HCl 
 2KCl  2CrCl3  7H 2 O  3Cl2
 dichromate   chromate 
(vii) It oxidises SO2 to sulphuric acid
(e) Action of Concentrated Sulphuric Acid :
K 2 Cr2 O7  H 2SO4  3SO2  K 2SO4 Cr2  SO4 3 3H 2 O
(i) In cold, red crystals of chromic anhydride (chromium trioxide)
are formed. (viii) It oxidises stannous salts to stannic salts

K 2 Cr2 O7  2H 2SO 4 
 2CrO3  2KHSO4  H 2 O Cr2 O72   14 H   3Sn 2  
 2 Cr3  3 Sn 4   7 H 2 O

(ii) On heating the mixture, oxygen is evolved. (ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

K 2 Cr2 O7  4H 2SO4  K 2SO4  Cr2  SO4 3  4H 2 O  3  O

2K 2 Cr2 O7 8H 2SO4 2K 2SO4 2Cr2  SO4 3  8H 2 O  3O2
(f) Oxidising Properties: It is a powerful oxidising agent. In CH2 CH2 OH O 
 CH3CHO  H2 O
the presence of dilute sulphuric acid, one molecule of Ethyl alcohol
potassium dichromate furnishes 3 atoms of available oxygen
as indicated by the equation : CH3CHO   O 
 CH3COOH
Acetaldehyde Acetic acid
K 2 Cr2 O7 4H 2SO4  K 2SO4 Cr2  SO 4 3 4H2 O  3 O
Test for a drunken driver : The above reaction helps to test
2   3 whether a driver has consumed alcohol or not. He is asked to
or Cr2 O 7  14H  6e 
 2Cr  7H 2 O
breathe into the acidified K2Cr2O7 solution taken in a test tube. If
Mol. wt. 294 the orange colour of the solution changes into green colour (due
 Eq. wt. of K 2 Cr2 O 7    49
6 6 to Cr2(SO4)3 formed in the reaction), the driver is drunk, otherwise
not.
(i) It liberates I2 from KI
(g) Chromyl Chloride test : (Reaction with a chloride and
 4K 2SO 4  Cr2  SO4 3
K 2 Cr2 O7  7H 2SO 4  6KI  conc. sulphuric acid). When heated with concentrated
hydrochloric acid or with a chloride and strong sulphuric
3I2  7H 2 O
acid, reddish brown vapours of chromyl chloride are obtained.

K 2 Cr2 O7  4KCl  6H 2SO 4 

 2CrO 2 Cl 2  6KHSO 4
Chromyl chloride
 Re d vapour   3H 2 O

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(h) Reaction with Hydrogen Peroxide : Acidified K2Cr2O7 MnO2 + 2KOH + KNO3 
 K2MnO4 + KNO2 + H2O
solution reacts with H2O2 to give a deep blue solution due to
the formation of peroxo compound, CrO (O2)2. 3MnO2 +6KOH+KClO3 
 3K2MnO4 +KCl+2H2O
(ii) Oxidation of Potassium Manganate to Potassium
Cr2 O72   2 H   4 H 2 O2 
 2 CrO5  5 H 2 O
Permanganate:
The blue colour fades away gradually due to the Potassium manganate thus formed undergoes
decomposition of CrO5 into Cr3+ ions and oxygen. disproportionation in the neutral or acidic solution as follows,
if allowed to stand for some time :
The structure of CrO5 is in which Cr is in +6 VI VII IV
3MnO 24   4 H   2MnO4  MnO2  2 H 2 O
Manganate ion Permanganate ion
oxidation state.
2.2.4 Uses of Potassium Dichromate The fused mass is extracted with water and the solution after
filtration is converted into potassium permanganate by
(i) In volumetric analysis, it is used as a primary standard for the
bubbling carbon dioxide, chlorine or ozonised oxygen through
estimation of Fe2+ (ferrous ions) and I– (iodides) in redox
the green solution.
titrations.
(ii) In industry, it is used 3K 2 MnO 4  2CO2 
 2KMnO 4  MnO 2  2K 2 CO3
(a) In chrome tanning in leather industry. 2K 2 MnO4  Cl2 
 2KMnO4  2KCl
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. 24H2O 2K 2 MnO4  H 2 O  O3   2KMnO4  2KOH  O2
and other industrially important compounds such as Cr2O3, The carbon dioxide process is uneconomical as one third of the
CrO3, CrO2Cl2, K2CrO4, CrCl3 etc. original manganate is reconverted to manganese dioxide. However,
(c) In calico printing and dyeing. this process has the advantage that the potassium carbonate
(d) In photography and in hardening gelatine film. formed as a by-product can be used for the oxidative fusion of
(iii) In organic chemistry, it is used as an oxidising agent. manganese dioxide. In the chlorine process, potassium chloride
obtained as a by-product is lost.

NOTE : 2.3.2 Structure of Manganate and Permanganate ions

Both manganate  MnO 4  and permanganate  MnO 4  ions are
2 
Unlike K2Cr2O7, Na2Cr2O7 is not used in volumetric analysis
because it is deliquescent.
tetrahedral. Here the  -bonding takes place by overlap of p
orbitals of oxygen with d orbitals of manganese. The green
2.3 Potassium Permanganate (KMnO4) manganate ion is paramagnetic because of one unpaired electron
but the permanganate ion is diamagnetic due to the absence of
2.3.1 Preparation Methods any unpaired electron.
On a large scale, it is prepared from the mineral, pyrolusite, MnO2. Its intense colour and diamagnetism along with temperature-
The preparation involves the following two stesp: dependent weak paramagnetism can be explained by molecular
(i) Conversion of MnO2 into Potassium Manganate: orbital theory.
The finely powdered pyrolusite mineral is fused with
potassium hydroxide or potassium carbonate in the presence
of air or oxidising agent such as potassium nitrate or
potassium chlorate when green coloured potassium
manganate is formed.

2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2 O
Potassium manganate
Fig 13.8 : Structure of manganate and permanganate ions
2MnO2 + 2K2CO3 + O2 
 2K2MnO4 + 2 CO2

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d AND f BLOCK ELEMENTS 203
2.3.3 Properties of Potassium Permanganate (iii) It oxidises nitrites  NO 

2 to nitrates  NO  , arsenites

3

(a) Colour : Potassium permanganate exists as deep purple black

prisms with a greenish lustre which become dull in air due to  AsO 
3
3 to arsentates  AsO 
3
4 and sulphites and
superficial reduction. thiosulphates to sulphates.
(b) Solubility : It is moderately soluble in water at room
2KMnO4  3H 2SO4  5KNO2 
 K 2SO4  2MnSO4 
temperature and it is more soluble in hot water.
(c) Action of Heat : When heated to 513 K, it readily decomposes 3H 2 O  5KNO3
giving oxygen. (iv) It oxidises oxalates or oxalic acid to CO2
2KMnO 4 
 K 2 MnO 4  MnO2  O 2 2KMnO4  3H 2SO4  5C2 H 2 O4 
 K 2SO4  2MnSO4 
Pot. manganate
8H 2 O  10 CO2
At red heat, potassium manganate formed decomposes into
potassium manganite (K2MnO3) and oxygen. (v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous salt
2K 2 MnO4   2K 2 MnO3  O2 to ferric salt).
(d) Action of heat in current of hydrogen : When heated in a 2KMnO4  8H 2SO4  10FeSO4 
 K 2SO4  2MnSO4 
current of H2, solid KMnO4 gives KOH, MnO and water
vapours. 5Fe2  SO4 3  8H 2 O
 (vi) It oxidises H2O2 to H2O and O2. This is because acidified
2KMnO 4  5H 2 
 2KOH  2MnO  4H 2 O
KMnO4 is a stronger oxidising agent than H2O2.
(e) Oxidising Property. Potassium permanganate is powerful
oxidising agent. The actual course of reaction depends on 2KMnO4  3H 2SO4  5H 2 O2 
 K 2SO4  2MnSO4 
the use of the permanganate in (a) acidic medium (b) neutral
8H 2 O  5O 2
medium or (c) alkaline medium.
In acidic medium : Potassium permanganate in the presence of (vii) It oxidises potassium iodide to iodine
dil. sulphuric acid, i.e., in acidic medium, acts as a strong oxidising 2KMnO 4  3H 2 SO 4  10KI 
 K 2SO 4  2MnSO 4 
agent because of the reaction
8H 2 O  5I 2
 K 2 SO 4  2MnSO 4  3H 2 O  5  O 
2KMnO 4  3H 2 SO 4 
(viii) It oxidises HX (where X = Cl, Br, I) to X2
or MnO4  8H   5 e 
 Mn 2   4H 2 O.
2KMnO4  3H 2SO4  10 HX 
 K 2SO4  2MnSO4 

Since in the above reaction, MnO ion gains 5 electrons of five
4 8H 2 O  5X 2
atoms of oxygen are available from two molecules of KMnO4.
(ix) It oxidises ethyl alcohol to acetaldehyde
Hence.
2KMnO 4  3H 2SO 4  5C 2 H5 OH  K 2 SO 4
Mol. wt. 158
Eq. wt. of KMnO 4    31.6  2MnSO 4  5CH 3 CHO  8H 2 O
5 5
Some oxidizing properties of KMnO4 in the acidic medium: In neutral solution :
These are given below : Potassium permanganate acts as a moderate oxidising agent in
(i) It oxidises H2S to S. neutral aqueous solution because of the reaction :
 2KOH  2MnO 2  3  O 
2KMnO4  H 2 O 
2KMnO 4  3H 2SO 4  5H 2S 
 K 2SO 4  2MnSO 4
or
8H2O 5S
MnO 4  2H 2 O  3 e 
 MnO2  4OH 
(ii) It oxidises sulphur dioxide to sulphuric acid.
2KMnO4  5 SO2  2H 2 O 
 K 2SO4  2MnSO4  2H 2SO4

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204 d AND f BLOCK ELEMENTS
or
Thus, MnO4 ion gains 3 electrons. Also, according to the above  
I  6OH   IO3  3H 2 O  6 e 
equation, in neutral medium, from two moles of permanganate,
In this case, iodine is not liberated unlike the case of acidic
three oxygen atoms are available. In fact, during the course of
medium.
reaction, the alkali generated renders the medium alkaline even
when we start with neutral solutions. Hence, Eq. wt. of KMnO4 in Similar reaction takes place with KBr.
(ii) It oxidises olefinic compounds to glycols, i.e., when an olefinic
neutral or weakly alkaline medium
compound is shaken with alkaline KMnO4, pink colour of
Mol. wt. 158 KMnO4 is discharged.
   52.67
3 3 CH 2 CH OH
Some oxidizing properties of KMnO4 in the neutral medium. These Alkaline  | 2
||  H 2 O   O  
are given below : CH 2 KMnO4 CH OH
2
(i) It oxidises hot manganous sulphate to manganese dioxide. Ethylene Ethylene glycol

2KMnO4  3MnSO4  2H 2 O 
 K 2SO 4  2H 2SO 4  5MnO2 Alkaline KMnO4 used for this test is known as Baeyer’s
Presence of ZnSO4 or ZnO catalyses the oxidation. reagent. It is used for oxidation of a number of organic
compounds.
(ii) It oxidises sodium thiosulphate to sodium sulphate.
8KMnO4  3Na 2S2 O3  H 2 O 
 3K 2SO 4  8MnO2 
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,
In alkaline solution : In strongly alkaline solution, MnO 24 
therefore, always first standardised with a standard solution
(manganate) ion is produced. of oxalic acid.
 2K 2 MnO 4  H 2 O   O 
2KMnO 4  2KOH  (ii) Volumetric titrations inolving KMnO4 are carried out only in
or presence of dilute H2SO4 but not in the presene of HCl or
  HNO3. This is because oxygen produced from KMnO4 + dill.
 MnO 42 
MnO  e 
4
H2SO4 is used only for oxidizing the reducing agent. Moreover,
Mol. wt. 158 H2SO4 does not give any oxygen of its own to oxidize the
 Eq. wt. of KMnO 4    158
1 1 reducing agent. In case HCl is used, the oxygen produced
from KMnO4 + HCl is partly used up to oxidize HCl to chlorine
Potassium manganate is also further reduced to MnO2 when a
and in case HNO3 is used, it itself acts as oxidizing agent and
reducing agent is present. partly oxidizes the reducing agent.
 MnO 2  2KOH  O 
K 2 MnO 4  H 2 O  (iii) It is used as a strong oxidising agent in the laboratory as well
as in industry. Alkaline potassium permanganate is used for
or MnO24   2H 2 O  2 e  
 MnO2  4OH  testing unsaturation in organic chemistry and is known as
So the complete reaction is : Baeyer’s reagent.
 2MnO 2  2 KOH  3 O
2KMnO 4  H 2 O  (iv) Potassium permanganate is also widely used as a disinfectant
or and germicide. A very dilute solution of permanganate is used
for washing wounds and gargling for mouth sore. It is also
MnO 4  2H 2 O  3 e   MnO2  4OH 
used for purifying water of stinking wells.
which is the same as that for neutral medium. Hence, equivalent
(v) Because of its strong oxidizing power, it is also used for
weight of KMnO4 in weakly alkaline medium is same as that in the
bleaching of wool, cotton, silk and other textile fibres and
neutral medium, viz., 52.67
also for decolourisation of oils.
Some oxidizing properties of KMnO4 in the alkaline medium:
These are given below :
(i) It oxidises potassium iodide to potassium iodate.

2KMnO 4  H 2 O  KI 
 2MnO 2  2KOH  KIO3
Pot. iodate

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d AND f BLOCK ELEMENTS 205

THE f-BLOCK ELEMENTS

1. 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
NOTE :
lanthanide series or 4f series. Some times, lanthanoides are
collectively represented by symbol Ln. The 4f electrons in the antipenultimate shell are very effectively
shielded from their chemical environment outside the atom by
the 5s and 5p electrons. Consequently the 4f electrons do not
2.1 Electronic Confignration take part in bonding. Whether the f orbitals are filled or empty
These elements have electronic configration [Xe]4f1-14 5d0-1 6s2. has little effect on the normal chemical properties. However, it
They have 6s2 common but with variable occpancy of 4f and 5d does affect their spectra and their magnetic properties.
level. The electronic conigurations of all tripostive ions are of the
form 4f1-14.
Table 13.12 : Electronic Configuration and Oxidation States of Lanthanoides
Element Electronic Electronic Oxidation States
Configuration Configuration of M3+
Lanthanum La [Xe] 5d1 6s2 [Xe] +3
Cerium Ce [Xe] 4f1 5d1 6s2 [Xe] 4f 1 +3 (+ 4)
Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)
Neodymium Nd [Xe] 4f 4
6s 2
[Xe] 4f 3
(+2) +3
Promethium Pm [Xe] 4f 5
6s 2
[Xe] 4f 4
(+2) +3
Samarium Sm [Xe] 4f 6 6s2 [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 6s2 [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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206 d AND f BLOCK ELEMENTS

2.3 Atomic and Ionic Radii of the third transition series to be very similar to those of the
corresponding members of the second series. The almost identical
(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

Fig 13.9 : Trends in ionic radii of lanthanoids

Table 13.13 : Atomic and Ionic Radii of Lanthanoides

Atomic Electronic configurations Radii/pm
Name Symbol
Number Ln Ln2+ Ln3+ Ln 4+
Ln Ln3+
57 Lanthanum La 5d16s2 5d1 4f0 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103
59 Praseodymium Pr 4f36s2 4f3 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f56s2 4f5 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
63 Europium Eu 4f76s2 4f7 4f6 199 95
64 Gadolinium Gd 4f75d16s2 4f75d1 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 176 89
68 Erbium Er 4f126s2 4f12 4f11 175 88
69 Thulium Tm 4f136s2 4f13 4f12 174 87
70 Ytterbium Yb 4f146s2 4f14 4f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 – –

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d AND f BLOCK ELEMENTS 207
2.4 Magnetic Behaviour They form oxides M2O3 and hydroxides M(OH)3. The oxides and
hydroxides are basic like alkaline earth metal oxides and hydroxides.
Paramagnetism is shown by the positive ions of lanthanides except
La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). This 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.
Fig 13.10 : Chemical reactions of the lanthanoids
NOTE :
Separation of the Lanthanide Elements
The hydroxides Ln(OH) 3 are precipitated as gelationous
Since the change in ionic radius is very small, the chemical
precipitates by the addition of NH4OH to aqueous solutions. These
properties are similar. This makes the separation of the element in
hydroxides are ionic and basic. They are less basic than Ca(OH)2
pure state difficult. Separation is done by Ion Exchange methods
which is based on the ionic size. but more basic than Al(OH)3 which is amphoteric. The metals,
oxides and hydroxides all dissolve in dilute acids, forming salts.
2.5 Colour Ln(OH)3 are sufficiently basic to absorb CO2 from the air and form
carbonates. The basicity decreases as the ionic radius decreases
The lanthanides are silvery white metals. However, most of the
trivalent metal ions are coloured, both in the solid state and in from Ce to Lu. Thus Ce(OH)3 is the most basic, and Lu(OH3),
aqueous solution. This is due to the partly filled-f-orbitals which which is the least basic, is intermediate between Scandium and
permit f-f transition. Yttrium in basic strength. The decrease in basic properties is
illustrated by the hydroxides of the later elements dissolving in
NOTE : hot concentrated NaOH, forming complexes.
Lanthanides ions with x f electrons have a similar colour to those
Yb(OH)3 + 3NaOH  3Na+ + [Yb(OH)6]3–
with (14–x) f electrons e.g., La3+ and Lu3+ are colourless, Sm3+
Lu(OH)3 + 3NaOH  3Na+ + [Lu(OH)6]3–
and Dy3+ are yellow and Eu3+ and Tb3+ are pink.

2.7 Uses of Lanthanides

2.6 Chemical Reactivity The lanthanoids are mainly used for :
Chemically the earlier members of the lanthanide series are quite (i) Production of alloy steels for plates and pipes
similar to calcium but, with increasing atomic number, they behave (ii) Production of Mischmetall, it is an alloy containing (95%)
more like aluminium. lanthanoid metals + (5%) iron + traces of S, C, Ca and Al.
These metals combine with hydrogen when gently heated in (iii) Mischmetall is used as Mg based alloy to produce bullets
hydrogen gas to from hydrides (LnH3). shell and lighter flints.
When these metals are heated with carbon, they give carbides, (iv) Mixed oxides of lanthanoids are used as catalyst in petroleum
Ln3C, Ln2C3 and LnC2. cracking.
They liberate hydrogen from dilute acids and burn in halogens to (v) Some lanthanide oxides are used as phosphors in television
form halides (LnX3). screens and similar fluorescing surfaces.

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3. The Actinides Series 3.2 Atomic and Ionic Radii

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

Table 13.14 : General Characteristics of Actinoids

Atomic Electronic Configurations Radii/pm Oxidation

Name Symbol
Number M M3+ M4+ M3+ M4+ States
89 Actinium Ac 6d17s2 5f0 111 3
90 Thorium Th 6d27s2 5f1 5f 0
99 4
91 Protactinium Pa 5f26d17s2 5f2 5f1 96 3, 4, 5
92 Uranium U 5f36d17s2 5f3 5f2 103 93 3, 4, 5, 6
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92 3, 4, 5, 6, 7
94 Plutonium Pu 5f67s2 5f5 5f4 100 90 3, 4, 5, 6, 7
95 Americium Am 5f77s2 5f6 5f5 99 89 3, 4, 5, 6
96 Curium Cm 5f76d17s2 5f7 5f6 99 88 3, 4
97 Berkelium Bk 5f97s2 5f8 5f7 98 87 3, 4
98 Callifornium Cf 5f107s2 5f9 5f8 98 86 3
99 Einstenium Es 5f117s2 5f10 5f9 – – 3
100 Fermium Fm 5f127s2 5f11 5f10 – – 3
101 Mendelevium Md 5f137s2 5f12 5f11 – – 3
102 Nobelium No 5f147s2 5f13 5f12 – – 3
103 Lawrencium Lr 5f146d17s2 5f14 5f13 – – 3

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d AND f BLOCK ELEMENTS 209
3.4 Magnetic Behaviour 4. Comparison of Lanthanides
Like lanthanides, the actinides are strongly paramagnetic. The
variation in magnetic susceptibility of actinides with the increasing
and Actinides
number of unpaired electrons is similar to that of lanthanides but Similarities :
the values are higher for the actinides than the lanthanides. As both lanthanides and actinides involve filling of f-orbitals,
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 (iv) Actinides exhibit actinide contraction like lanthanide
having seven 5f-electrons (i.e., exactly half-filled f-subshell) are contraction shown by lanthanides.
colourless. The cations containing 2 to 6 electrons in the 5f- Differences :
subshell are coloured both in the crystalline state as well as in
The show differences in some of their characteristics as follows :
aqueous solution. The colour arises due to f–f transition e.g. Ac3+
(5f 0) = colourless, U3+ (5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+ (5f 5) =
Table 13.15 : Difference between Lanthanides and
Voilet, Am3+ (5f 6) = Pink, Cm3+ (5f 7) = Colourless, Th3+ (5f 0) =
Colourless as so on.
Actinides
Lanthanides Actinides
3.6 Chemical Reactivity (i) Besides + 3 oxidation (i) Besides +3 oxidation
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.
(vii) Their magnetic (vii) Their magnetic
Fig 13.11 : Chemical reactions of the actinides properties can be explained properties cannot be
easily. explained easily.

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d and f Block Elements
210 d AND f BLOCK ELEMENTS

Summary
d-Block Elements f-Block Elements
 d-block elements are those in which the last electron goes to  The elements in which the last electron enters f-orbital of (n-
(n-1) d-orbitals. 2)th shell are called f-block elements. f-block elements are of
 General electronic configurations of d-block elements is : two types lanthanides and actinides.
ns , (n-1)d
1-2 1-10
 General electronic configuration of f-block elements is ns2,
 Transition metals have high values of melting and boiling (n-1)d0-1, (n-2)f1-14
points which are due to the presence of strong metallic  + 3 oxidation state (O.S.) is the most stable O.S. of
bonding in these metals. lanthanides.
 Due to lanthanide contraction, atomic radii for the elements  There is a steady decrease in atomic and ionic (M³+ ions)
of 3rd transition series are almost equal to those for the radii of lanthanides. This steady decrease in atomic and ionic
elements of 2nd transition series. radii is called lanthanide contraction.
 The values of ionisation energies increase as we move from  Magnetic moment value of lanthanides and actinides is
left to right in each series. calculated by considering both orbital spin contribution. µeff
 Except for Cu, E°red values for other metals of Ist transition value is given by µeff = 4S (S+1)+L(L+1) B.M, here S spin
series are negative. quantum number and L= orbital quantum number
 Excepting a few metals, most of the metals show several  Mischmetal is an important alloy of lanthanides. It contains
oxidation states. This is due to the fact that (n-1)d and ns 90% lanthanides (La= 40%, Ce and other lanthanides= 50%)
orbitals have almost the same energy. , Fe = 5% and traces of other elements like C, S, Al, Ca.
 Transition metal ions which contain partially filled d-orbitals  The actinide elements lying beyond U (Np-93 to Lw-103) are
are usually coloured. The colour arises because of d-d called trans-uranic or trans-uranium elements.
transition. Transition metal ions with d or d configuration
0 10
 Unlike lanthanides, actinides show a large number of
are colourless because d-d transition is not possible in such oxidation states.
ions.  Actinides have lower values of ionisation energies.
 Transition metals form interstitial compounds.  Most of actinide halides form complex compounds with alkali
 Many transition metals and their alloys and compounds act metal halides. The degree of complex formation for the ions
as catalysts in many chemical reactions. 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
d AND f BLOCK ELEMENTS 211

SCAN CODE
d and f Block Elements
212 d AND f BLOCK ELEMENTS

EXERCISE – 1: Basic Objective Questions

General Introduction of d Block Elements 9. Transition elements
(a) exhibit inert-pair effect
1. Transition elements have (b) show nonmetallic character
(a) completely filled ‘d’ levels (c) do not form complex compounds
(b) completely filled ‘s’ levels and d levels (d) exhibit variable oxidation states
(c) incompletely filled ‘s’ levels and completely filled ‘d’ 10. The electronic configuration of chromium is actually
levels [Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
(d) incompletely filled ‘d’ levels is because
2. The general electronic configuration of the transition (a) an exactly half-filled d level gives additional
elements is stability, according to the Hund’s rule of maximum
(a) (n – 1)d10 (n + 1)s2 multiplicity
(b) (n – 1)d1–10 (n + 1)s1–2 (b) the 4s orbital has higher energy than the 3d orbitals
(c) (n – 1)d1–10 np6 ns2 (c) the 4s orbitals has lower energy than the 3d orbitals
(d) (n – 1)d1–10 ns1–2 (d) the 3d and 4s orbitals have equal energies and
3. Which of the following elements has completely filled d hence electron migration occurs readily
orbitals (the d10 configuration) ? 11. The last electron of a d-block element occupies the
(a) Co (b) Cr orbital
(c) Hg (d) Ni (a) (n – 1)d (b) nd
4. In which of the following transition elements are the (c) np (d) (n – 1)s
d orbitals completely filled ? 12. Transition metals
(a) Zn (b) Hg (a) form only ionic compounds
(c) Cd (d) Ag (b) form exclusively covalent compounds
5. Which of the following statements is correct? (c) may form either ionic or covalent compounds
(a) d-block contains inner-transition elements depending on the condition
(b) In transition elements, electrons are progressively (d) exclusively form coordination compounds but no
filled in d and p-orbitals simple compounds
(c) Elements of inner-transition elements belongs to
Classification of d Block Elements
group 3
(d) d and p-block elements are called transition and 13. Among the transition metals, the melting points of Zn,
inner-transition elements respectively Cd and Hg are relatively low because
6. The electronic configuration of silver is (a) their d shells are not completely filled
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1 (b) their d electrons do not participate in metallic
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2 bonding
7. The electronic configuration of palladium is (c) their densities are higher
(a) [Ar]3d84s2 (b) [Kr]4d85s2 (d) all of the above
(c) [Kr]5d86s2 (d) [Kr]4d105s0 14. The noble character of platinum and gold is favoured by
8. The electronic configuration of platinum is (a) high enthalpies of sublimation, high ionization
(a) [Xe] 4f145d96s1 (b) [Xe] 4f145d106s2 energies and low enthalpies of solvation
(c) [Rn] 5f146d107s2 (d) [Rn] 5f146d97s1 (b) high enthalpies of sublimation, low ionization
energies and low enthalpies of solvation
(c) low enthalpies of sublimation, high ionization
energies and low enthalpies of solvation
(d) high enthalpies of sublimation, high ionization
energies and high enthalpies of solvation
d AND f BLOCK ELEMENTS 213

15. Which one of the following is a d-block element ? 24. The atom of which one of the following elements has the
(a) Gd (b) Hs highest number of unpaired electrons ?
(a) 25 Mn (b) 24 Cr
(c) Es (d) Cs
(c) 96 Cm (d) 26 Fe
16. Which of the following statements is correct ?
25. Which one of the following ions is colourless ?
(a) The second-row elements have smaller radii than the
corresponding third-row ones. + 2+
(a) Cu (b) Co
(b) Because of lanthanide contraction, the radii of the
2+ 3+
third-row elements are almost the same as those of the (c) Ni (d) Fe
first-row elements. 26. Which of the following species is/are paramagnetic ?
(c) Because of lanthanide contraction, the radii of the
2+ 0 2+ 4+
third-row elements are almost the same as those of the Fe , Zn , Hg , Ti
second-row elements. 2+ 0 4+
(d) Because of lanthanide contraction, the separation of (a) Fe only (b) Zn and Ti
second-row elements from one another is easier. 2+ 2+ 0 2+
(c) Fe and Hg (d) Zn and Hg
Physical Properties of d Block Elements 27. Which of the following metals does not show variable
oxidation states ?
17. The highest possible oxidation state shown by osmium (a) Mercury (b) Zinc
in its compounds is (c) Gold (d) Silver
(a) +4 (b) +8 28. The covalent radii of transition metals decrease from left
(c) +6 (d) +10 to right in a period because
18. Which of the following ions is paramagnetic ? (a) the densities of the metals decrease with increasing
(a) Zn2+ (b) N3–
atomic number due to poor shielding of electrons
(c) Mn4+ (d) Cu+
19. Which of the following ions is diamagnetic ? (b) the screening of nuclear charge by d electrons is
(a) Ni2+ (b) Ti4+ poor and hence the nuclear charge attracts all the
3+
(c) Cr (d) Co3+
3+ electrons strongly, causing a decrease in size
20. Number of unpaired electrons in Mn is
(c) the ionization energies also decrease
(a) 2 (b) 3 correspondingly
(c) 4 (d) 5
(d) the metallic character decreases as the atomic
21. Which one of the following statements is not true with number increases
regard to transition elements ?
29. For a given ion, the magnetic moment is 2.83 BM. The
(a) They readily form complex compounds total spin (s) of all the unpaired electrons is
(b) They show variable oxidation states
(a) 2 (b) 1
(c) All their ions are colourless
(c) 3/2 (d) ½
(d) Their ions contain partially filled d-electrons 30. Among the following series of transition metal ions, the
22. Which of the following ions has the least magnetic one in which all metal ions have 3d2, electronic
moment? configuration is (At. no. Ti = 22 ; V = 23 ; Cr = 24, Mn
2+ 2+ = 25)
(a) Cu (b) Ni
3+ 2+ 3+ 4+
3+ 2+ (a) Ti , V , Cr , Mn
(c) Co (d) Fe
23. The ion of least magnetic moment among the following + 4+ 6+ 7+
(b) Ti , V , Cr , Mn
is
3+ 2+ 4+ 3+ 2+ 3+
(a) Ti (b) Ni (c) Ti ,V , Cr , Mn
2+ 2+ 2+ 3+ 4+ 5+
(c) Co (d) Mn (d) Ti , V , Cr , Mn
214 d AND f BLOCK ELEMENTS

31. Which of the following statements concerning transition (d) Cu, CuSO4, Cu2I2 and CuI2
elements is false ?
37. Which one of the following sets correctly represent the
(a) They are all metals increase in the paramagnetic property of the ions?
(b) They easily form complex coordination compounds 2+ 2+ 2+ 2+
(a) Cu < V < Cr < Mn
(c)They form compounds containing unpaired electrons 2+ 2+ 2+ 2+
(b) Cu < Cr < V < Mn
and their ions are mostly coloured
2+ 2+ 2+ 2+
(d)They show multiple oxidation states always differing (c) Cu > V > Cr > Mn
by units of two 2+ 2+ 2+ 2+
(d) V < Cu < Cr < Mn
32. Mercury is a liquid metal because Chemical Properties of d Block Elements
(a) it has a completely filled s-orbital
(b) it has a small atomic size 38. The oxidation states shown by transition elements is
related to their
(c) it has a completely filled d-orbital that prevents
(a) electropositive characters
d-d overlapping of orbitals
(b) electronic configurations
(d) it has a completely filled d-orbital that causes d-d (c) atomic weights
overlapping (d) atomic sizes
33. The spin only magnetic moment of Fe3+ ion (in BM) is
39. Which of the following statements is not true?
approximately
(a) Beyond Mn, only Fe and Co form trihalides with
(a) 4 (b) 7
fluorine
(c) 5 (d) 6
(b) MnO3F is the compound in which oxidation state of
2+ Mn is +7
34. Experimental value of magnetic moment of Mn
complex is 5.96 BM. This indicates (c) The oxidation state of Cr is highest in CrCl4
(a) axial and orbital motion of electron in same direction (d) Fluorine stabilises the highest oxidation state due to
its higher lattice energy
(b) axial and orbital motion of electron in opposite
direction 40. Which of the following ions is colourless in solution ?
(c) electron does not exhibit orbital motion, it only (a) V3+ (b) Cr3+
exhibits axial motion (c) Co2+ (d) Sc3+
41. Which of the following ions has the maximum number
(d) electron does not axial motion, it only exhibits orbital
of unpaired d electrons ?
motion
(a) Fe3+ (b) V3+
35. The magnetic moment of a transition metal ion is 15 3+
(c) Ti (d) Mg2+
BM. Therefore, the number of unpaired electrons present
42. Which of the following ions possesses the maximum
in it is
number of unpaired electrons ?
(a) 4 (b) 1 (a) Ni2+ (b) Fe2+
(c) 2 (d) 3 (c) Cu+ (d) Zn2+
36. A transition metal ‘A’ has ‘spin-only’ magnetic moment 43. Which of the following does not possess unpaired
value of 1.8 BM. When it is reacted with dilute sulphuric electrons ?
acid in the presence of air, a compound ‘B’ is formed. (a) Co3+ (b) Cu2+
‘B’ reacts with compound ‘C’ to give compound ‘D’ 2+
(c) Ti (d) Hg2+
with liberation of iodine. Then, the metal A and
compounds B, C and D are respectively 44. Which of the following electronic configurations
represents Fe3+ ?
(a) Ti, TiSO4, KI and TiI2
(a) [Ar]3d64s2 (b) [Ar]3d54s1
(b) Zn, ZnSO4, KI and Zn2I2 (c) [Ar]3d54s2 (d) [Ar]3d54s0
(c) Cu, CuSO4, KI and Cu2I2
d AND f BLOCK ELEMENTS 215

45. Which of the following ions is expected to the coloured 54. Which of the following is an incorrect statement?
in solution ? (a) The lowest oxide of a transition metal is acidic
(a) Cu+ (b) Cu2+ whereas the highest one is usually basic.
(c) Ti 4+
(d) Sc3+ (b) A transition metal usually exhibits higher oxidation
46. The transition elements are states in its fluorides than in its iodides.
(a) more reactive than group 1 elements
(c) Transition metal halides become more covalent with
(b) more reactive than group 2 elements
the increasing oxidation state of the transition metal and
(c) less reactive than group 1 elements but more reactive
are more susceptible to hydrolysis.
than group 2 elements
(d) less reactive than group 1 and 2 elements (d) The highest oxide of a transition metal is acidic
whereas the lowest one is usually basic.
47. The transition metals sometimes form
nonstoichiometric compounds. These compounds have 55. Which one of the following ionic species will impart
(a) definite structures and definite proportions colour to an aqueous solution ?
(b) indefinite structures and definite proportions (a) Ti4+ (b) Cu+
(c) definite structures and indefinite proportions (c) Zn2+ (d) Cr3+
(d) indefinite structures and indefinite proportions
56. Which of the following oxides of chromium is
48. The maximum number of unpaired electrons is present amphoteric in nature?
in
(a) CrO (b) CrO3
(a) Fe (b) Cu
(c) Cr2O3 (d) CrO5
(c) Co (d) Ni
57. Which of the following statements is incorrect ?
49. The stability of ferric ion is due to
(a) The compounds formed by the 3d transition metals
(a) half-filled f-orbitals
in lower valence states are ionic but those in higher
(b) half-filled d-orbitals
valence states are covalent.
(c) completely filled f-orbitals
(b) The 4d and 5d transition metals form less ionic
(d) completely filled d-orbitals compounds than do the 3d transition metals.
50. The maximum oxidation state shown by Mn in its (c) The compounds formed by the 3d transition metals
compounds is
are less ionic than the corresponding compounds
(a) +4 (b) +5 formed by the 4d and 5d transition metals.
(c) +6 (d) +7 (d) The ionization energies of 3d, 4d and 5d transition
51. The highest oxidation state exhibited by transition metals are greater than those of group 1 and 2 metals.
metals is 58. Ammonia will not form complex with
(a) +7 (b) +8 2+ 2+
(a) Ag (b) Pb
(c) +6 (d) +5
2+ 2+
52. A transition metal ion exists in its highest oxidation (c) Cu (d) Cd
state. It is expected to behave as 59. Which of the following pairs of transition metal ions are
(a) a chelating agent the stronger oxidising agents in aqueous solutions ?
(b) a central metal in a coordination compound (a) V 2  and Cr 2  (b) Ti 2  and Cr 2 
(c) an oxidising agent (c) Mn 3 and Co3 (d) V 2  and Fe 2 
(d) a reducing agent 60. The coordination number in an ....... complex may
53. The formula of mercurous ion is increase to 8.
+ (a) cobalt (b) osmium
(a) Hg (b) Hg2
(c) nickel (d) iron
(c) Hg 22  (d) None of these
216 d AND f BLOCK ELEMENTS

61. The titanium (atomic number 22) compound that 69. The pair, that referred as ‘chemical twins’ is
does not exist is (a) Ac, Cf (b) Hg, Ta
(a) TiO (b) TiO2 (c) Tc, Re (d) La, Ac
(c) K2TiF6 (d) K2TiO4
Potassium Permanganate
62. The acidic, basic or amphoteric nature of Mn2O7,
V2O5 and CrO are respectively, 70. Which of the following compounds is green in colour ?
(a) acidic, acidic and basic (a) KMnO4 (b) (NH4)2Cr2O7
(b) basic, amphoteric and acidic (c) MnO2 (d) K2MnO4
(c) acidic, amphoteric and basic 71. KMnO4 is manufactured on a large scale by
(d) acidic, basic and amphoteric (a) fusing MnO2 with KOH and then oxidizing the fused
63. In which of the following ions, d–d transition is not mixture with KNO3
possible?
(b) fusing MnO2 with Na2CO3 in the presence of O2
3+ 4+
(a) Cr (b) Ti (c) fusing MnO2 with KOH and KNO3 to form K2MnO4
2+ 2+ which is then electrolytically oxidized in an alkaline
(c) Cu (d) Mn
solution
64. Copper exhibits only +2 oxidation state in its stable
compounds. Why ? (d) fusing MnO2 with KNO3 and then acidifying the
(a) Copper is transition metal in +2 state. fused mixture

(b) +2 state compounds of copper are formed by 72. MnO 4 is prepared by treating a solution containing
exothermic reactions. Mn2+ ions with a very strong oxidizing agent such as
(c) Electron configuration of copper in +2 state is (a) PbO2 (b) C 2 O 42 
9 0 (c) I2 (d) Fe3+
[Ar]3d 4s .
(d) Copper gives coloured compounds in +2 state. 73. KMnO4 in an acidic medium will not oxidize
4 (a) NO 2 (b) SO 24 
65. A transition element X has the configuration [Ar]d in
its +3 oxidation state. Its atomic number is (c) HN3 (d) H2O2
(a) 25 (b) 26 74. Which of the following is an incorrect statement ?
(c) 22 (d) 19 (a) In a redox reaction in acidic medium, KMnO4
66. Among K, Ca, Fe and Zn, the element which can form produces Mn2+ ions.
more than one binary compound with chlorine (b) In a redox reaction in strongly alkaline medium,
is KMnO4 produces MnO 24  ions.
(a) Fe (b) Zn
(c) In a redox reaction in neutral medium, KMnO4
(c) K (d) Ca produces MnO2.
67. Which of the following metals form amphoteric
(d) In a redox reaction in alkaline medium, KMnO4
oxide ?
produces Mn2O7.
(a) Fe (b) Cu
75. KMnO4 in an acidic medium oxidizes
(c) Zn (d) Ca
2
68. When Zn is treated with excess of NaOH, the product (a) C2 O4 to CO2 (b) N2H4 to N2
obtained is  2
(c) HSO 3 to SO 4 (d) all of these
(a) Zn(OH)2 (b) ZnOH
(c) Na2ZnO2 (d) None of these
d AND f BLOCK ELEMENTS 217

Potassium Dichromate (d) fusing sodium dichromate with carbon

84. Chromyl chloride, CrO2Cl2, is prepared by heating a
mixture of
76. CrO 24  reacts with H+ as
(a) NaCl, K2Cr2O7 and NaOH
2CrO 24   2H   Cr2 O 72   H 2 O
(b) NaCl, K2Cr2O7 and concentrated H2SO4
The change in oxidation number of Cr is
(c) NaCl, K2Cr2O7 and MnO2
(a) +5 (b) +7
(d) CrO3 and NaCl
(c) +6 (d) zero
77. When hydrogen peroxide is added to an acidic solution 85. Which is the correct statement about Cr2 O 72  structure?
of a dichromate, the most probable product is (a) It has neither Cr – Cr bonds nor O–O bonds
(a) K2CrO4 (b) CrO3
(b) It has one Cr – Cr bond and six O – O bonds
(c) Cr2O3 (d) CrO5 (c) It has no Cr – Cr bond and has six O – O bonds
78. Acidified K2Cr2O7 on treatment with KI produces (d) It has one Cr – Cr bond and seven Cr – O bonds
(a) KIO3 (b) I2 86. Assertion : Solution of Na2CrO4 in water is intensely
(c) KIO4 (d) I 
3
coloured.
79. Na2CrO4 on treatment with lead acetate gives a Reason : Oxidation state of Cr in Na2CrO4 is +VI.
precipitate. This precipitate is dried and the solid is used (a) Both Assertion and Reason are true and Reason is the
as a pigment for road signs and markings. The solid is correct explanation of Assertion.
known as
(b) Both Assertion and Reason are true but Reason is not
(a) white lead (b) chrome green the correct explanation of Assertion.
(c) chrome yellow (d) red lead (c) Assertion is true but Reason is false.
80. Potassium dichromate is used
(d) Both Assertion and Reason are false.
(a) in electroplating Heat
87.  4K 2 CrO 4  3O 2  X .
4K 2 Cr2 O 7   In the above
(b) as a reducing agent
reaction X is
(c) oxidise ferrous ions into ferric ions in acidic media as
(a) CrO3 (b) Cr2O7
an oxidising agent
(d) as an insecticide (c) Cr2O3 (d) CrO5
81. CrO3 dissolves in aqueous NaOH to give 88. When dil. H2SO4 is added to aqueous solution of
(a) CrO 2
4 (b) Cr(OH)2 potassium chromate, yellow colour of solution turnsto
orange colour. It indicates
(c) Cr2 O 72  (d) Cr(OH)3
(a) chromate ions are reduced
2
82. Cr2 O reacts with OH– as
7 (b) chromate ions are oxidised
Cr2 O  2  OH
2
7

  2CrO 2
4  H2O (c) mono centric complex is converted into dicentric
complex
The change in oxidation number of Cr is (d) oxygen gets removed from chromate ions
(a) +6 (b) +3
89. Which of the following statements is incorrect for CrO3?
(c) zero (d) +4
(a)It is a bright orange solid.
83. Sodium chromate is prepared by
(b) It is commonly called chromic acid.
(a) fusing chromite (FeCr2O4) with NaCl in air
(c) It is prepared by adding concentrated H2SO4 to a
(b) fusing chromite (FeCr2O4) with NaOH in air saturated solution of sodium dichromate.
(c) fusing (NH4)2Cr2O7 with sodium hydrogen (d) The colour arises due to d–d transition.
sulphate in nitrogen
218 d AND f BLOCK ELEMENTS

90. Deep red-yellow vapour of CrO2Cl2 is passed into an 98. Which of the following oxides of manganese is
aqueous solution of NaOH. The solution turns amphoteric ?
(a) yellow due to the formation of Na2Cr2O7 (a) MnO (b) Mn2O3

(b) yellow due to the formation of Na2CrO4 (c) Mn2O7 (d) MnO2

(c) green due to the formation of CrCl3 99. Which of the following oxides of manganese is stable as
well as strongly acidic ?
(d) red due to the formation of Na2CrO4
(a) MnO2 (b) Mn2O7
(c) MnO3 (d) Mn2O3
Other Compounds of d-Block Elements
100. The colourless species is
(a) VCl3 (b) VOSO4
91. Which of the following compounds is colourless?
(a) K2MnO4 (b) HgI2 (c) Na3VO4 (d) [V(H2O)6]SO4 . H2O

(c) ZnSO4 (d) FeSO4 101. An aqueous solution of CoCl2 on addition of excess of
92. The compound ZnSO4 is white because conc. HCl turns blue due to the formation of

(a) charge is transferred from the metal to the oxygen

atoms 2–
(a) [Co(H2O)]Cl2 (b) [Co(H2O)2Cl4]
(b) electron transfer to d level does not occur as the level
is already filled to capacity in zinc 2–
(c) [CoCl4] (d) [Co(H2O)2Cl2]
(c) Zn2+ has d10 configuration and d–d transition occurs 102. The amphoteric oxide among the following is
easily (a) Cr2O3 (b) Mn2O7
(d) Zn2+ ions absorb light of the visible range (c) V2O3 (d) CrO
93. Which one of the following oxides of chromium is basic
in nature ? 103. The solid product formed on heating AgNO3 strongly to
(a) CrO (b) Cr2O3 980 K is
(c) CrO3 (d) Cr2O5 (a) silver carbonate (b) silver nitride
94. The colour of zinc sulphide is (c) silver oxide (d) silver metal
(a) white (b) black 104. CuSO4 when reacts with KCN forms CuCN which is
(c) brown (d) red insoluble in water. It is soluble in excess of KCN, due to
formation of the following complex
95. The value of magnetic moment ( spin only) for Cu2+ in
CuSO4.5H2O is (a) K2[Cu(CN)4] (b) K3[Cu(CN)4]

(a) 5.92 BM (b) 4.92 BM (c) CuCN2 (d) Cu[K Cu(CN)4]

(c) 2.83 BM (d) 1.73 BM 105. The dark blue colour of the solution formed when excess
96. Identify the species having an atom in +6 oxidation state. of ammonia is added to a solution of copper(II) sulphate
 is due to the presence of the ion
(a) MnO4 (b) [Cr(CN)6 ]3
2–
(a) [Cu(OH)4 (H2O)2]
(c)
NiF63  (d) CrO2Cl2
2+
97. Which of the following compounds is expected to be (b) [Cu(H2O)6]
coloured ? 4+
(a) Ag2SO (b) CuF2 (c) [Cu(NH3)2 (H2O)4]

(c) MgF2 (d) CuCl 2+

(d) [Cu(NH3)4 (H2O)2]
d AND f BLOCK ELEMENTS 219

106. Choose the correct reaction to prepare mercurous 115. Silver nitrate solution is kept in brown bottles in
chloride (calomel). laboratory because :

(a) HgCl 2  Hg   (b) Hg  Cl 2 
 (a) it reacts with ordinary white bottles
(b) brown bottles cut the passage of light through
(c) HgCl 2  SnCl 2 
 (d) Both options (a) and (c)
(c) brown bottles do not react with it
107. Calomel on reaction with ammonium hydroxide gives (d) ordinary bottles catalyse its decomposition
(a) HgO (b) Hg2O 116. A white precipitate of AgCl dissolves in excess of :
(c) NH2 – Hg – Hg – Cl (d) HgNH2Cl (I) NH3 (aq) (II) Na2S2O3
(III) NaCN
108. The following is known as “bordeaux mixture”
(a) III only (b) I, II, III
(a) Borax and copper sulphate (c) I, II (d) I only
(b) Orthoboric acid and ferrous sulphate
117. Boiling CuCl2 with Cu in conc. HCl gives :
(c) Sodium borate and zinc sulphate
(d) Copper sulphate and lime (a) CuCl (b) CuCl2
109. Which of the following is red in colour ? (c) H[CuCl2] (d) Cu2Cl
(a) Cu2O (b) CuF 118. Zinc (II) ion on reaction with NaOH first give a white
(c) ZnF2 (d) ZnCl2 precipitate which dissolves in excess of NaOH due to
the formation of :
110. Formula of ammonium manganate is (a) ZnO (b) Zn(OH)2
(a) NH4MnO4 (b) (NH4)2MnO4 (c) [Zn(OH)4]2– (d) [Zn(H2O)4]2+
(c) NH4(MnO4)2 (d) NH4Mn2O4
Uses of d Block Elements
111. Chemically philosopher of wool is :
(a) ZnO (b) BaO 119. Permanent magnets are generally made from the alloy of
(c) HgCl (d) Hg2Cl2 (a) Co (b) Zn
(c) Al (d) Pb
112. Malachite and azurite are used respectively are : 120. In haemoglobin, the metal ion present is
(a) Blue and green pigment 2+ 2+
(a) Fe (b) Zn
(b) Red and green pigment 2+ 2+
(c) Co (d) Cu
(c) Green and blue pigment
121. German silver alloy contains
(d) Green and red pigment (a) zinc, silver and copper
113. HgCl2 is a covalent compound, sparingly soluble in (b) nickel, silver and copper
water, the solubility increases by the addition of (c) germanium, silver and copper
chloride ions due to : (d) zinc, nickel and copper
(a) common ion effect 122. Which of the following is used as purgative ?
(b) formation of complex [HgCl4]2– (a) HgS (b) Hg2Cl2
(c) weakening of Hg – Cl bonds (c) HgCl2 (d) ZnSO4
(d) strong ion-dipole forces
123. Which of the following is used as indelible ink ?
114. Mercury is the only metal that is liquid at 0ºC. This is
due to its : (a) Aqueous CuSO4 solution
(a) Very high ionisation energy and weak metallic (b) Aqueous AgNO3 solution
bond
(c) Aqueous NaCl solution
(b) Low ionisation potential
(c) High atomic weight (d) Aqueous NaOH solution
(d) High vapour pressure
220 d AND f BLOCK ELEMENTS

f-Block Elements General Characteristics of f-Block Elements

124. Lanthanide elements have
(a) similar lattice energies but widely different solvation 132. The electronic configuration of f-block elements is
and ionization energies represented by
(b) similar lattice and solvation energies but widely (a) (n – 2)f1–14 (n – 1)d0–1ns2
different ionization energies (b) (n – 2)f1–14 (n – 1)d0–5ns0–2
(c) similar lattice and ionization energies but widely (c) (n – 2)f1–14 (n – 1)d0–10ns1–2
different hydration energies (d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2
(d) similar lattice energies, solvation energies and 133. Lanthanides are characterized by the filling of the
ionization energies (a) penultimate 4f energy level
125. The electronic configuration of cerium is (b) antipenultimate 4f energy level
(a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1 (c) penultimate 3f energy level
1 2 2
(c) [Xe]4f 5d 6s (d) [Xe]4f25d06s2 (d) antipenultimate 3f energy level
126. Lanthanides are 134. Which of the following statements is correct for the
(a) 14 elements in the sixth period (atomic no. = 90 to lanthanoids ?
103) that are filling 4f sub-level. (a) The 4f electrons do not take part in bonding.
(b) 14 elements in the seventh period (atomic no. = 90 to (b) The 4f electrons can neither be removed to produce
103) that are filling 5f sub-level. ions nor be made to take part in crystal field
(c) 14 elements in the sixth period (atomic no. = 58 to stabilization of complexes.
71) that are filling 4f sub-level. (c) The 4f electrons in the antipenultimate shell are very
(d) 14 elements in the seventh period (atomic no. = 58 to effectively shielded by the 5s and 5p electrons.
71) that are filling 4f sub-level. (d) All of these
127. Which of the following is not an actinide ? 135. The most common and stable oxidation state of a
lanthanide is
(a) Curium (b) Californium
(a) +II (b) +IV
(c) Uranium (d) Terbium
(c) +VII (d) +III
128. Which of the following is not an actinoid ?
136. The atomic and ionic radii (M3+ ions) of lanthanide
(a) Am (b) Cm elements decrease with increasing atomic number. This
(c) Fm (d) Tm effect is called
129. Differentiating electron in inner-transition elements (a) lanthanide contraction
enters in the ........ orbital. (b) lanthanide expansion
(a) s (b) p (c) actinide contraction
(c) d (d) f (d) none of these
130. Identify the incorrect statement among the following. 137. The lanthanoid contraction relates to
(a) d-block elements show irregular and erratic chemical (a) atomic radii
properties among themselves. (b) atomic as well as M3+ radii
(b) La and Lu have partially filled d-orbitals and no other (c) valence electrons
partially filled orbitals.
(d) oxidation states
(c) The chemistry of various lanthanoids is very similar.
138. On which factors, the stability of an oxidation state of
(d) 4f- and 5f - orbitals are equally shielded. lanthanoide elements depends ?
131. The point of dissimilarity between lanthanides and
(a) Enthalpy
actinides is
(a) their outermost shells are partially filled. (b) Internal energy
(b) they show oxidation state of +3 (common). (c) Combined effect of hydration energy and ionisation
(c) they are called inner-transition elements. energy
(d) they are radioactive in nature. (d) Electronic configuration
d AND f BLOCK ELEMENTS 221

139. Lanthanide for which +II and +III oxidation states are 145. Most basic hydroxide among the following is
common is (a) Lu(OH)3 (b) Eu(OH)3
(a) La (b) Nd
(c) Yb(OH)3 (d) Ce(OH)3
(c) Ce (d) Eu
140. Which of the following elements shows the maximum 146. The lanthanoid contraction is responsible for the fact
number of different oxidation states in its compounds ? that
(a) Eu (b) La (a) Zr and Y have about the same radius
(c) Gd (d) Am (b) Zr and Nb have similar oxidation state
141. Lanthanide contraction occurs because (c) Zr and Hf have about the same radius
(a) the 4f electrons, which are gradually added, create a (d) Zr and Zn have the same oxidation state
strong shielding effect 147. More number of oxidation state are exhibited by the
(b) the 4f orbitals are greater in size than the 3d and actinoids than by the lanthanoids. The main reason for
3f orbitals this is
(c) the 5f orbitals strongly penetrate into the 4f orbitals (a) lesser energy difference between 5f- and 6d-orbitals
(d) the poor shielding effect of 4f electrons is coupled than that between 4f- and 5d-orbitals.
with increased attraction between the nucleus and the
(b) greater metallic character of the lanthanoids than that
added electrons
of the corresponding actionoids.
142. The hardness, melting point and boiling point of
elements increase from Ce to Lu because (c) more active nature of the actinoids.
(a) the attraction between the atoms increases as the size (d) more energy difference between 5f and
increases 6d-orbitals than that between 4f and 5d-orbitals.
(b) the attraction between the atoms decreases as the size 4+
increases 148. Ce is stable. This is because of
(c) the attraction between the atoms increases as the size (a) half-filled d-orbitals
decreases (b) all paired electrons in d-orbitals
(d) the attraction between the atoms remains the same as (c) empty orbitals
the size increases.
(d) fully filled d-orbitals
3+ 3+ 3+
143. The correct order of ionic radii of Y , La , Eu and 149. Most common oxidation states of Ce (cerium) are
3+ (a) +3, +4 (b) +2, +3
Lu is
3+ 3+ 3+ 3+ (c) +2, +4 (d) +3, +5
(a) Y < La < Eu < Lu 150. Which of the following statement is correct.
3+ 3+ 3+ 3+ (A) In Lanthanide series metallic radius regularly
(b) Lu < Eu < La < Y
decreases from La to Lu.
3+ 3+ 3+ 3+
(c) La < Eu < Lu < Y (B) La is actually an elements of transition series rather
3+ 3+ 3+ 3+ than lanthanide.
(d) Y < Lu < Eu < La (C) La(OH)3 is less basic than Lu(OH)3
144. Across the lanthanide series, the basicity of the (D) The atomic radius of Zr & Hf are nearly similar
lanthanide hydroxides because of lanthanoid contraction.
(a) increases (a) If A, B and C options are correct.
(b) decreases (b) If A & B both options are correct.
(c) first increases and then decreases (c) If B & D both are options correct.
(d) If A & C both are options correct.
(d) first decreases and then increases
222 d AND f BLOCK ELEMENTS

Assertion Reason & Statement type Questions (c) Statement-I and II both are correct.
(d) Statement-I is incorrect and II is correct.
151. Which of the following statements are correct? 156. Given below are two statements :
I. In acidic solution dichromate ions are converted to Statement-I : All the transition elements show typical
chromate ions. metallic properties such as high tensile strength, ductility
II. An acidified solution of K2Cr2O7 liberates iodine from but low thermal and electrical conductivity.
iodides. Statement-II : Zn, Cd & Hg are very hard and have low
III. Potassium dichromate is used as a titrant for Fe ions. volatility.
IV. Ammonium dichromate on heating undergoes In the light of the above statements, choose the most
exothermic decomposition to give Cr2O3 appropriate answer from the options given below:
Choose the correct option. (a) Statement-I is correct while II is incorrect.
(a) I, II and III (b) II, III and IV (b) Both Statement-I and II are incorrect.
(c) I, II and IV (d) Both II and III (c) Statement-I and II both are correct.
152. Consider the following statements about Zr and Hf. (d) Statement-I is incorrect and II is correct.
I. Radii of Zr and Hf are almost identical. 157. Given below are two statements :-
II. It is the consequence of the lanthanoid contraction. Statement I : Cr+2 act as reducing agent and Mn act as
III. Both occur together in nature. oxidising agent.
I V. It is difficult to separate Zr and Hf. Statement-II : E0(M+2/M) value for all 3d-series
The correct statements are (choose the appropriate element's are negative.
option) In the light of the above statements, choose the most
(a) I, II and III (b) I, II and IV appropriate answer from the options given below :
(c) II, III and IV (d) All of these (a) Statement-I is incorrect and II is correct.
153. Consider the following statements. (b) Statement-I and II both are correct.
I. Eu2+ has f 7 configuration and it is a strong reducing (c) Both Statement-I and II are incorrect.
agent. (d) Statement-I is correct while II is incorrect.
II. Yb2+ has f14 configuration and it is a reductant. 158. Given below are two statements :
III. TbIV has half-filled f-orbitals and is an oxidant. Statement-I : Ce+4 is a strong oxidant but Eu+2 is a
The correct statement(s) is/are (choose the appropriate strong reducing agent.
option) Statement-II : All lanthanoid ion in +3 oxidation state
(a) Only I (b) Both II and III are paramagnetic.
(c) Both I and II (d) All of these In the light of the above statements, choose the most
154. Statement I The d-orbitals of the penultimate energy appropriate answer from the options given below:
level in their atoms receive electrons giving rise to the (a) Statement-I and II both are correct.
three rows of the transition metals, i.e. 3d, 4d and 5d. (b) Both Statement-I and II are incorrect.
Statement II The fourth row of 6d is still incomplete. (c) Statement-I is correct while II is incorrect.
(a) Both Statement-I and II are incorrect. (d) Statement-I is incorrect and II is correct.
(b) Statement-I is correct while II is incorrect. 159. Assertion (A) Although Zn is the member of 1st series,
(c) Statement-I and II both are correct. yet not a transition element.
(d) Statement-I is incorrect and II is correct. Reason (R) The orbitals in Zn are completely filled in
155. Given below are two statements : ground as well as in excited state.
Statement-I : Ag is a transition element. (a) If (A) & (R) both are correct and (R) is the correct
Statement-II : Ag atom has completely filled d- orbital explanation of (A).
(4d10) in it's ground state. (b) If (A) & (R) both are correct but (R) is not the correct
In the light of the above statements, choose the most explanation of (A).
appropriate answer from the options given below : (c) (A) is not correct but (R) is incorrect.
(a) Both Statement-I and II are incorrect. (d) (A) & (R) both are correct.
(b) Statement-I is correct while II is incorrect.
d AND f BLOCK ELEMENTS 223

160. Assertion (A) Transition elements exhibit higher (a) If (A) & (R) both are correct and (R) is the correct
enthalpies of atomisation. explanation of (A).
Reason (R) There are large number of unpaired (b) If (A) & (R) both are correct but (R) is not the correct
electrons in their atoms. They have stronger interatomic explanation of (A).
interaction. (c) (A) is not correct but (R) is Incorrect.
(a) If (A) & (R) both are correct and (R) is the correct (d) (A) & (R) both are correct.
explanation of (A). 165. Given below are two statements; one is labelled as
(b) If (A) & (R) both are correct but (R) is not the correct Assertion (A) and the other is labelled as Reason(R).
explanation of (A). Assertion (A) : Eu+2 & Yb+2 are reducing agent.
(c) (A) is not correct but (R) is incorrect. Reason (R) : Both ions have strong tendency to convert
(d) (A) & (R) both are correct. into stable +3 in its aq. solution.
161. Assertion (A) Cr2+ is reducing, while Mn3+ is oxidising In the light of the above statements, choose the most
even both have d4 configuration. appropriate answer from the options given below :
Reason (R) Configuration of Cr changes from d3 to d4 (a) If (A) & (R) both are correct and (R) is the correct
(a) If (A) & (R) both are correct and (R) is the correct explanation of (A).
explanation of (A). (b) If (A) & (R) both are correct but (R) is not the correct
(b) If (A) & (R) both are correct but (R) is not the correct explanation of (A).
explanation of (A). (c) (A) is not correct but (R) is incorrect.
(c) (A) is not correct but (R) is incorrect. (d) (A) & (R) both are correct.
(d) (A) & (R) both are correct.
162. Assertion (A) Transition metals form a large number of Match the following Questions
complex compounds.
Reason (R) It happens due to the comparatively smaller 166. Match the properties given in Column I with the metals
size of the metal ions only. given in Column II and choose the correct option from
(a) If (A) & (R) both are correct and (R) is the correct the codes given below.
explanation of (A). Column I Column II
(b) If (A) & (R) both are correct but (R) is not the correct (Property) (Metal)
explanation of (A). A. Element with highest second 1. Co
(c) (A) is not correct but (R) is incorrect. ionisation enthalpy
(d) (A) & (R) both are correct. B. Element with highest third 2. Cr
163. Assertion (A) Many trivalent lanthanoid ions are ionisation enthalpy
coloured both in solid state and in aqueous solution. C. M in M (CO)6 is 3. Cu
Reason (R) Colour of these ions is due to the presence
D. Element with highest heat of 4. Zn
of f-electrons.
atomisation
(a) If (A) & (R) both are correct and (R) is the correct
Codes
explanation of (A).
A B C D
(b) If (A) & (R) both are correct but (R) is not the correct
(a) 1 2 3 4
explanation of (A).
(b) 3 4 1 2
(c) (A) is not correct but (R) is incorrect.
(c) 4 3 2 1
(d) (A) & (R) both are correct.
(d) 2 1 4 3
164. Given below are two statements; one is labelled as
Assertion (A) and the other is labelled as Reason(R)
Assertion (A) : The 3rd ionisation energy of Gd is
abnormally low.
Reason (R) : Exchange energy of 4f subshell is hight.
In the light of the above statements, choose the most
appropriate answer from the options given below :
224 d AND f BLOCK ELEMENTS

167. Match the name of elements given Column I with 170. Match the properties given in Column I with the metals
electronic configuration given in Column II and choose given in Column II.
the correct option from the codes given below.
Column I Column II
Column I Column II
(Name) (Electronic (Property) (Metal)
configuration A. An element which can show+8 1. Mn
(Ln) )
B. 3d block element that can 2. Cr
A. Erbium 1. 4f 76s2
B. Neodymium 2. 4f 116s2 show upto+7 oxidation state.
C. Ytterbium 3. 4f 46s2 C. 3d block element with highest 3. Os
D. Europium 4. 4f 126s2
melting point.
E. Holmium 5. 4f 146s2
Codes 4. Fe
A B C D E Codes
(a) 1 2 3 4 5 A B C
(b) 4 3 5 1 2
(a) 1 2 3
(c) 3 2 1 5 4
(d) 5 4 3 2 1 (b) 3 2 1
168. Match the items given in Column I with that given in (c) 3 1 2
Column II.
(d) 2 3 1
Column I Column II
(Metal) (Oxidation State) 171. Match the properties given in Column I with the metals
A. Titanium p. +2 given in Column II.
B. Iron q. +3 Column I Column II
C. Copper r. +4
(Aqueous solution of salt) (Colour)
D. Manganese s. +5
A B C D A. FeSO4.7H2O 1. Green
(a) p,q,r,s p p,q r B. NiCl2.4H2O 2. Light pink
(b) p,q,r p,q,r p p,q,r,s
C. MnCl2.4H2O 3. Blue
(c) q,r p,q p r,s
(d) p,q,r,s p,q p p,r,s D. CoCl2.6H2O 4. Pale green
169. Match the items given in Column I with that given in E. Cu2Cl2 5. Pink
Column II.
6. Colourless
Column I Column II
A. Cobalt p. Colourless Codes
B. Titanium q. Paramagnetic A B C D E
C. Zinc r. Most common oxidation
(a) 4 3 2 1 1
state is +2
D. Copper s. Magnetic moment is zero (b) 1 2 5 3 4
A B C D (c) 3 2 5 4 6
(a) q,r q p,s q,r (d) 4 1 2 5 6
(b) p,s q q,r p,q,r,s
(c) q p,s qr p,q,r,s
(c) p,q,r q q,s r,s
d AND f BLOCK ELEMENTS 225

172. Match the properties given in Column I with the metals 175. Match the column:
given in Column II. Column I Column II
Column I Column II (Compound) (Properties)
(Property) (Element) (i) K2MnO4 (a) Amphoteric
A. Lanthanoid which shows + 4 1. Pm (ii) KMnO4 (b) Paramagnetic &
oxidation state green coloured
B. Lanthanoid which can show +2 2. Ce (iii) K2Cr2O7 (c) Diamagnetic &
oxidation state purple coloured
C. Radioactive lanthanoid 3. Lu (iv) V2O5 (d) Diamagnetic &
7
D. Lanthanoid which has 4f 4. Eu orange coloured
electronic configuration in +3 (a) i-a, ii-b, iii-c, iv-d
oxidation state (b) i-c, ii-d, iii-b, iv-a
E. Lanthanoid which has 4f14 5. Gd (c) i-b, ii-c, iii-d, iv-a
electronic configuration in +3 (d) i-d, ii-a, iii-b, iv-c
oxidation state
6. Dy
Codes
A B C D E
(a) 2 4 1 5 3
(b) 1 2 5 3 4
(c) 2 3 4 5 1
(d) 3 4 2 1 5
173. Match the column:
Column I Column II
(a) FeSO4.7H2O (p) Green Vitriol
(b) MgSO4.7H2O (q) Blue vitriol
(c) ZnSO4.7H2O (r) Eupsum salt
(d) CuSO4.5H2O (s) White vitriol
(a) a-p, b-v, c-s, d-q
(b) a-r, b-s, s-s, d-p
(c) a-r, b-s, c-p, d-q
(d) a-q, b-p, c-s, d-r
174. Match the column:
Column I Column II
(Composition) (Alloy)
(a) Cu+NI (p) Silver UK coins
(b) Ni+Cu+Zn (q) German silver
(c) Cu+Zn+Sn (r) Gun metal
(d) Ln (95%)+Fe (s) Misch metal
(a) a-p, b-q, c-r, d-s
(b) a-q, b-r, s-s, d-p
(c) a-s, b-q, c-r, d-p
(d) a-q, b-p, c-s, d-r
226 d AND f BLOCK ELEMENTS

EXERCISE – 2: Previous Year Questions

1. Which one of the following ions is the most stable in 9. Out of TiF62  and CoF63  and Cu 2Cl2 and NiCl 24  (Z of Ti =
aqueous solution ? (At. no. Ti = 22, V = 23, Cr = 24, Mn 22, Co = 27, Cu = 29, Ni = 28), the colourless species are
= 25) (CBSE AIPMT 2007)
(CBSE AIPMT, AMU 2009)
3+ 3+
(a) Cr (b) V (a) TiF62  and CoF63  (b) Cu 2Cl 2 and NiCl24 
3+ 3+ (c) TiF62  and Cu 2Cl2 (d) CoF63 and NiCl24 
(c) Ti (d) Mn
2. Acidified potassium permanganate solution is 10. Transition metals show paramagnetic behaviour. This is
decolourised by (AFMC 2007) because of their (AFMC 2009)
(a) bleaching powder (b) white vitriol (a) high lattice energy
(c) Mohr’s salt (d) microcosmic salt (b) variable oxidation state
3. Reason of passivity of iron is (RPMT 2007) (c) characteristic configuration
(a) Fe2O3 (b) Fe3O4 (d) unpaired electrons
(c) FeO (d) Fe2O4 . 3H2O 11. For which of the following pairs, magnetic moment is
4. Essential component of amalgam is (RPMT 2007) same? (AIIMS 2009)
(a) Fe (b) Pb (a) MnCl2, CuSO4 (b) CuCl2, TiCl3
(c) Hg (d) Cr (c) TiO2, CuSO4 (d) TiCl3, NiCl2
5. Identify the incorrect statement among the following 12. Which compound is expected to be coloured ?
(CBSE AIPMT 2007) (CPMT 2009)
(a) There is a decrease in the radii of the atoms or ions (a) CuCl (b) CuF2
as one proceeds from La to Lu.
(b) Lanthanoid contraction is the accumulation of (c) Ag2SO4 (d) MgF2
successive shrinkages. 13. Which of the following is man-made element ?
(c) As a result of lanthanoid contraction, the properties (AFMC 2009)
of 4d-series of the transition elements have no (a) Ra (b) U
similarities with the 5d-series of elements.
(c) Np (d) C
(d) Shielding power of 4f electrons is quite weak.
14. Which of the following pairs has the same size ?
6. What is the correct order of spin only magnetic moment (CBSE AIPMT 2010)
2+ 2+ 2+
(in BM) of Mn , Cr and Ti ? 2+ 4+ 2+ 2+
(a) Zn , Hf (b) Fe , Ni
(AFMC 2008)
4+ 4+ 4+ 4+
2+ 2+ 2+ 2+ 2+ 2+ (c) Zr , Ti (d) Zr , Hf
(a) Mn > Ti > Cr (b) Ti > Cr > Mn
15. Which of the following ions will exhibit colour in
2+ 2+ 2+ 2+ 2+ 2+ aqueous solutions ? (CBSE AIPMT 2010)
(c) Mn > Cr > Ti (d) Cr > Ti > Mn
7. Which of the following compounds is coloured ? 3+ 3+
(a) Sc (Z = 21) (b) La (Z = 57)
(AIIMS 2008) 3+ 3+
(a) TiCl3 (b) FeCl3 (c) Ti (Z = 22) (d) Lu (Z = 71)
16. Which of the following transition metal ions is not
(c) CoCl2 (d) All of these
coloured? (AFMC 2010)
8. Which of the following group of transition metals is + 3+
called coinage metals? (RPMT 2008) (a) Cu (b) V
(a) Cu, Ag, Au (b) Ru, Rh, Pd 2+ 2+
(c) Co (d) Ni
(c) Fe, Co, Ni (d) Os, Ir, Pt
d AND f BLOCK ELEMENTS 227

17. Maximum number of unpaired electrons are present in 24. The catalytic activity of transition metals and their
(CPMT 2010) compounds is ascribed mainly to (Mains 2012)
2+ 2+ (a) their magnetic behaviour
(a) Fe (b) Mn
(b) their unfilled d-orbitals
+ 2+
(c) Cu (d) Cr (c) their ability to adopt variable oxidation states
18. Which of the following has maximum unpaired d- (d) their chemical reactivity.
electrons? (RPMT 2010) 25. Which of the following lanthanoid ions is diamagnetic?
2+ 2+ (Atoms, Ce = 58, Sm = 62, Yb = 70)
(a) Zn (b) Fe
2+ + (CBSE AIPMT 2013)
(c) Ni (d) Cu 2+ 2+
(a) Yb (b) Ce
19. In Cu (at. no. 29) (RPMT 2010)
(a) 13 electrons have spin in one direction and 16 2+ 2+
(c) Sm (d) Eu
electrons in other direction 26. KMnO4 can be prepared from K2MnO4 as per the
(b) 14 electrons have spin in one direction and 15 reaction :
electrons in other direction 3MnO 24  2H 2O  2MnO 4  MnO 2  4OH 
(c) one electron can have spin only in the clockwise –
The reaction can go to completion by removing OH ions
direction
by adding :- (CBSE AIPMT 2013)
(d) None of the above is correct (a) SO2 (b) HCl
20. For the four successive transition elements (Cr, Mn, Fe (c) KOH (d) CO2
and Co), the stability of +2 oxidation state will be there
in which of the following order ? 27. Sc (Z = 21) is a transition element but Zn (Z = 30) is
(CBSE AIPMT 2011) not because (NEET 2013)
3+ 2+
(At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27) (a) both Sc and Zn ions are colourless and form
(a) Cr > Mn > Co > Fe (b) Mn > Fe > Cr > Co white compounds
(c) Fe > Mn > Co > Cr (d) Co > Mn > Fe > Cr (b) in case of Sc, 3d orbitals are partially filled but in Zn
these are filled
21. Acidified K2Cr2O7 solution turns green when
(c) last electron is assumed to be added to 4s level in case
Na2SO3 is added to it. This is due to the formation of of Zn
(CBSE AIPMT 2011) (d) both Sc and Zn do not exhibit variable oxidation
(a) CrSO4 (b) Cr2(SO4)3 states
28. Which of the following statements about the interstitial
(c) CrO 24  (d) Cr2(SO3)3 compounds is incorrect? (NEET 2013)
(a) They are much harder than the pure metal.
22. Which of the statements is not true ?
(b) They have higher melting points than the pure
(CBSE AIPMT 2012) metal.
(a) K2Cr2O7 solution becomes yellow on increasing the (c) They retain metallic conductivity.
pH beyond 7 (d) They are chemically reactive.
29. Magnetic moment 2.83 BM is given by which of the
(b) On passing H2S through acidified K2Cr2O7 following ions ? (At. No. Ti = 22, Cr = 24, Mn = 25, Ni
solution, a milky colour is observed = 28) (AIPMT 2014)
(c) Na2Cr2O7 is preferred over K2Cr2O7 in volumetric 3+ 2+
(a) Ti (b) Ni
analysis 3+ 2+
(c) Cr (d) Mn
(d) K2Cr2O7 solution in acidic medium is orange 30. Reason of lanthanide contraction is (AIPMT 2014)
23. Identify the alloy containing a non-metal as a (a) negligible screening effect of ‘f’ orbitals
(b) increasing nuclear charge
constituent in it. (AIPMT-2012)
(c) decreasing nuclear charge
(a) Invar (b) Steel
(d) decreasing screening effect.
(c) Bell metal (d) Bronze
228 d AND f BLOCK ELEMENTS

31. Because of lanthanoid contraction, which of the (c) 4f and 5d levels being close in energies.
following pairs of elements have nearly same atomic (d) the radioactive nature of actinoids.
radii ? (Numbers in the parenthesis are atomicnumbers.)
38. HgCl2 and I2 both when dissolved in water containing
(AIPMT 2015)
ions the pair of species formed is (NEET 2017)
(a) Zr (40) and Nb (41) (b) Zr (40) and Hf (72)
2 
(c) Zr (40) and Ta (73) (d) Ti (22) and Zr (40) (a) HgI2, (b) HgI 4 , I3
32. The angular momentum of electron in ‘d’ orbital is equal (c) Hg 2 I2 ,I

(d) HgI2 ,I3


to (AIPMT 2015)
39. Name the gas that can readily decolourise acidified
(a) 2 h (b) 2 3h KMnO4 solution. (NEET 2017)
(c) 0 h (d) 6 h (a) SO2 (b) NO2
33. Which of the following processes does not involve (c) P2O5 (d) CO2
oxidation of iron? (NEET 2015) 40. Match the metal ions given in Column I with the spin
(a) Formation of Fe(CO)5 from Fe. magnetic moments of the ions given in Column II and
assign the correct code (NEET 2018)
(b) Liberation of H2 from steam by iron at high
temperature. Column I Column II
(c) Rusting of iron sheets. A. Co3+ i. 8 B.M.
(d) Decolourisation of blue CuSO4 solution by iron. B. Cr3+ ii. 35 B.M.
34. Which one of the following statements is correct when
SO2 is passed through acidified K2Cr2O7solution ? C. Fe3+ iii. 3 B.M.

(NEET 2016) D. Ni2+ iv. 24 B.M.

(a) The solution turns blue. v. 15 B.M.
(b) The solution is decolorized.
A B C D
(c) SO2 is reduced.
(a) i ii iii iv
(d) Green Cr2(SO4)3 is formed. (b) iv i ii iii
35. The electronic configurations of Eu (Atomic No. 63), Gd (c) iv v ii i
(Atomic No. 64) and Tb (Atomic No. 65) are (d) ii iv i ii
(NEET-I 2016) 41. Which one of the following ions exhibits d-d transition
(a) [Xe]4f65d16s2 , [Xe]4f75d16s2 and [Xe]4f85d16s2 and paramagnetic as well? (NEET 2018)
(b) [Xe]4f76s2, [Xe]4f75d1 6s2 and [Xe]4f96s2 (a) CrO42– (b) Cr2O72–
(c) [Xe]4f76s2, [Xe]4f86s2 and [Xe]4f85d1 6s2 (c) MnO4 –
(d) MnO42–
(d) [Xe]4f65d16s2, [Xe]4f75d16s2 and [Xe]4f96s2 42. The manganate and permanganate ions are tetrahedral,
36. Which one of the following statements related to due to: (NEET 2019)
lanthanons is incorrect? (NEET 2016) (a) There is no -bonding
(a) The basicity decreases as the ionic radius decreases (b) The -bonding involves overlap of p-orbitals of
from Pr to Lu. oxygen with p-orbitals of manganese
(b) All the lanthanons are much more reactive than (c) The -bonding involves overlap of d-orbitals of
aluminium. oxygen with d-orbitals of manganese
(c) Ce (+4) solutions are widely used as oxidizing agent (d) The -bonding involves overlap of p-orbitals of
in volumetric analysis. oxygen with d-orbitals of manganese
(d) Europium shows +2 oxidation state. 43. When neutral or faintly alkaline KMnO4 is treated
37. The reason for greater range of oxidation states in with potassium iodide, iodide ion is converted into
actinoids is attributed to (NEET 2017) ‘X’. ‘X’ is (Odisha NEET 2019)
(a) actinoid contraction. (a) I2 (b) IO4–
(b) 5f, 6d and 7s levels having comparable energies. (c) IO3– (d) IO–
d AND f BLOCK ELEMENTS 229

44. The calculated spin only magnetic moment of Cr 2+ 50. The stability of Cu2+ is more than Cu+ salts in aqueous
solution due to
ion is : (NEET 2020)
(a) 5.92 BM (b) 2.84 BM (NEET 2023)
(c) 3.87 BM (d) 4.90 BM (a) enthalpy of atomization
45. Identify the incorrect statement. (NEET 2020) (b) hydration energy
(a) Interstitial compounds are those that are formed (c) second ionisation enthalpy
when small atoms like H, C or N are trapped
(d) first ionisation enthalpy
inside the crystal lattices of metals.
51. Which of the following statements are INCORRECT?
(b) The oxidation state of chromium in CrO24 and A. All the transition metals except scandium form MO
Cr2O72 are not the same. oxides which are ionic.
B. The highest oxidation number corresponding to the
(c) Cr 2+ (d4 ) is a stronger reducing agent than group number in transition metal oxides is attained in
Fe2+ (d6 ) in water. Sc2O3 to Mn2O7.
C. Basic character increases from V2O3 to V2O4 to
(d) The transition metals and their compounds are
V2O5.
known for their catalytic activity due to their
ability to adopt multiple oxidation states and to D. V2O4 dissolves in acids to give VO34 salts.
form complexes. E. CrO is basic but Cr2O3 is amphoteric.
46. Zr (Z = 40) and Hf (Z = 72) have similar atomic and Choose the correct answer from the options given
ionic radii because of: (NEET 2021) below: (NEET 2023)
(a) lanthanoid contraction (a) B and D only (b) C and D only
(b) having similar chemical properties (c) B and C only (d) A and E only
(c) Belonging to same group 52. ‘Spin only’ magnetic moment is same for which of the
(d) diagonal relationship following ions (NEET 2024)
47. The incorrect statement among the following is: A. Ti3+, B. Cr2+
(NEET 2021) C. Mn2+, D. Fe2+
(a) Lanthanoids are good conductors of heat and E. Sc3+
electricity Choose the most appropriate answer from the options
(b) Actinoids are highly reactive metals, especially given below:
when finely divided. (a) A and E only (b) B and C only
(c) Actinoid contraction is greater for element to (c) A and D only (d) B and D only
element than Lanthanoid contraction 53. The Eo value for the Mn3+/Mn2+ couple is more
(d) Most of the trivalent ions are colorless in the solid positive than that of Cr3+/Cr2+ or Fe3+/Fe2+ due to
state. change of (NEET 2024)
48. Gadolinium has a low value of third ionisation (a) d5 to d2 configuration
enthalpy because of (NEET 2022) (b) d4 to d5 configuration
(a) small size (c) d3 to d5 configuration
(b) high exchange enthalpy (d) d5 to d4 configuration
(c) high electronegativity 54. The pair of lanthanoid ions which are diamagnetic is
(d) high basic character (NEET 2024)
49. In the neutral or faintly alkaline medium, KMnO4 3+
(a) Ce and Eu 2+
(b) Gd and Eu3+
3+
oxidises iodide into iodate. The change in oxidation 3+ 3+
state of manganese in this reaction is from (c) Pm and Sm (d) Ce4+ and Yb2+
(NEET 2022)
(a) +7 to +4 (b) +6 to +4
(c) +7 to +3 (d) +6 to +5
230 d AND f BLOCK ELEMENTS

EXERCISE – 3: Achiever’s Section

Single Choice Questions 8. The solubility of silver bromide in hypo solution is
due to the formation of :
(a) Ag2SO3 (b) Ag2S2O3
1. Which of the following order of given properties are
correct. (c) [Ag(S2O3)]– (d) [Ag(S2O3)2]3–
(A) CrO > Cr2O3 > CrO3 : Melting point 9. Sodium thiosulphate, Na2S2O3. 5H2O is used in
(B) Mn2O7 > Mn2O3 > MnO : Acidic nature photography to :
(C) CrO3 > MoO3 > WO3 : Oxidising nature character (a) Reduce the silver bromide to metallic silver
(D) V2O5 > V2O4 > V2O3 : Basic nature (b) Convert the metallic silver to silver salt
(a) If A & B both options are correct. (c) remove undecomposed AgBr as soluble silver
(b) If A & B and C options are correct. thiosulphate complex
(c) If B & D both are options correct. (d) remove reduced silver
(d) If A & C both are options correct
10. When AgNO3 comes in contact with skin, it leaves a
2. Philosopher’s wool when heated with BaO at 1100ºC
gives the compound : black stain. This is because of :
(a) BaCdO2 (b) Ba + ZnO2 (a) HNO3 produced by hydrolysis of AgNO3

(c) BaO2 + Zn (d) BaZnO2 (b) AgOH produced by hydrolysis of AgNO3

3. Spiegeleisen is an alloy of : (c) Its reduction of silver

(d) Its oxidation to silver oxide
(a) Cu + Zn + Ni (b) Ni + Cr
11. The oxidation state of copper changes when aqueous
(c) Mn + Fe + C (d) Fe + Cr + Ni
copper (II) ions react with :
4. I. As the oxidation number of a metal increases, ionic
character decreases. (I) NaOH (aq) (II) Fe(s)
(III) KI (aq)
II. In case of Mn, Mn2O7 is a covalent green oil
which possess predominantly acidic character and it (a) I, II, III (b) II only
gives HMnO4. (c) II, III (d) I only
III. V2O5 is amphoteric, it gives as well as salts. 12. Fe(OH)2 is precipitated from Fe(II) solutions as a
IV. CrO is basic, while Cr2O3 is amphoteric. white solid but turns dark green and then brown due
The correct set of statements is/are to the formation of :
(choose the appropriate option) (a) Fe(OH)2 and Fe(OH)3 (b) only Fe(OH)3
(a) Only II (b) I, II, III and IV (c) Fe2O3 . (H2O)n (d) Fe2O3 . 2H2O
(c) Both II and III (d) Both II and IV
13. The false statement about iron (III) hydroxide is that :
5. Which of the following is the correct formula for a
compound of scandium and oxygen? (a) it is a weaker base than Fe(OH)2

(a) Sc2O (b) ScO (b) with concentrated KOH, it forms a complex
K3[Fe(OH)6]
(c) Sc3O2 (d) Sc2O3 (c) it gradually loses water and transforms into Fe2O3
6. Oxide of metal cation which is not amphoteric? (d) it exhibits amphoteric properties with acid ones
(a) Al3+ (b) Cr3+ predominating
3+
(c) Fe (d) Zn2+
14. Mercury on heating with aqua-regia gives :
7. Gold dissolves in aqua-regia forming :
(a) Hg(NO3)2 (b) HgCl2
(a) Auric chloride (b) Aurous chloride
(c) Chloroauric acid (d)Aurous nitrate (c) Hg(NO2)2 (d) Hg2Cl2
d AND f BLOCK ELEMENTS 231

15. Which of the following statements regarding copper 21. Assertion : KMnO4 is purple in colour to charge
salts is not true? transfer.
(a) Copper (I) disproportionates to copper and copper Reason : There is no electron present in d-orbitals of
(II) ion in aqueous solution manganese in KMnO4.
(b) Copper (I) can be stablished by the formation of (a) A (b) B
insoluble complex compounds such as CuCl 2 (c) C (d) D
and Cu  CN 2 22. Assertion : KMnO4 has different equivalent weights
(c) Copper (II) oxide is red powder in acid, neutral or alkaline medium.
(d) The water of crystallization of copper sulphate is Reason : In different medium, change in oxidation
five number shown by manganese is altogether different.
16. Ferrous sulphate on heating gives : (a) A (b) B
(a) SO2 and SO3 (b) SO2 only (c) C (d) D
(c) SO3 only (d) H2S only 23. Assertion : AgNO3 reacts with KCN to form white
17. Mercury is transported in containers made of : ppt. of AgCN. This white ppt. disappears when
excess KCN is added.
(a) Ag (b) Pb
Reason : AgCN decomposes to form silver-carbide
(c) Al (d) Fe and evolve N2 gas.
(a) A (b) B
Assertion-Reason Type Questions (c) C (d) D
24. Assertion : CrO3 reacts with HCl to form chromyl
While answering these questions, you are required to choose
any one of the following four responses. chloride gas.
(a) If both Assertion and Reason are correct and the Reason : Chromyl chloride (CrO2Cl2) has tetrahedral
Reason is a correct explanation of the Assertion. shape.
(b) If both Assertion and Reason are correct but Reason is not (a) A (b) B
a correct explanation of the Assertion. (c) C (d) D
(c) If the Assertion is correct but Reason is incorrect. 25. Assertion : Zn(OH)2 is dissolved in both NH4OH
(d) If the Reason is correct but Assertion is incorrect. and NaOH solution.
Reason : Both NaOH and NH4OH being basic can
18. Assertion : The melting point of Mn is more than dissolve amphoteric Zn(OH)2.
that of Fe. (a) A (b) B
Reason : Mn has higher number of unpaired e– than (c) C (d) D
Fe in atomic state.
26. Assertion : CuSO4. 5H2O and FeSO4. 7H2O are blue
(a) A (b) B
(c) C (d) D and green colour compounds respectively.
19. Assertion : Hg is the only metal that is liquid at Reason : Both compounds have their specific colour
due to the phenomenon of polarisation of the anion.
0ºC.
(a) A (b) B
Reason : It has a very high I.P. and weak metallic
bond. (c) C (d) D
(a) A (b) B
(c) C (d) D

20. Assertion : Cu2+ is more stable than Cu+.

Reason : Electrode potential is more important in
determining stable oxidation state than electronic
configuration.
(a) A (b) B
(c) C (d) D
232 d AND f BLOCK ELEMENTS

Comprehension 29. The correct order of basic strength of lanthanoid

hydroxides given below is
Elements of atomic numbers 58 to 71 are called La (OH)3, Lu(OH)3 ,Ce(OH)
lanthanoids or elements of 4f series, are known as I II III
lanthanum as it resembles with them but infact it is (a) I > III > II (b) I < III < II
not a lanthanoid. These elements are also called rare (c) I > II > III (d) I < II < III
earth metals. Due to poor shielding of 4 f, the size of 30. In the separation of lanthanoids using cation
lanthanoids decreases with increase in atomic number exchange column
(lanthanoid contraction). This effect is also used to (a) Lu3+ (b) La3+
separate them.. (c) Dy 3+
(d) Pm3+
27. Which lanthanoid does not occur naturally?
(a) Eu (b) Pm
(c) Gd (d) Lu
28. The pair showing 4f14 configuration is
(a) Tm and Lu (b) Dy and Pm
(c) Lu and La (d) Yb and Lu
d AND f BLOCK ELEMENTS 233

Notes:

Find Answer Key and Detailed Solutions at the end of this book
:

d AND f BLOCK ELEMENTS

234 ANSWER KEY

Answer Key
CHAPTER - 6: CARBOXYLIC ACID AND ITS DERIVATIVES
Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (b) 2.(c) 3. (c) 4. (c) 97. (a) 98. (d) 99. (c) 100. (a)
5. (a) 6. (d) 7. (c) 8. (d) 101. (c) 102. (d) 103. (b) 104. (c)
9. (c) 10. (b) 11. (d) 12. (d) 105. (d) 106. (d) 107. (b) 108. (b)
13. (d) 14. (d) 15. (b) 16. (d) 109. (c) 110. (b) 111. (a) 112. (a)
17. (c) 18. (c) 19. (d) 20. (c) 113. (d) 114. (a) 115. (c) 116. (d)
21. (c) 22. (a) 23. (a) 24. (a) 117. (d) 118. (b) 119. (b) 120. (d)
25. (b) 26. (d) 27. (c) 28. (c) 121. (a) 122. (a) 123. (c) 124. (a)
29. (b) 30. (d) 31. (a) 32. (d) 125. (a) 126. (a) 127. (d) 128. (b)
33. (c) 34. (c) 35. (c) 36. (c) 129. (b) 130. (a) 131. (d) 132. (c)
37. (d) 38. (a) 39. (a) 40. (a) 133. (a) 134. (d) 135. (d) 136. (a)
41. (b) 42. (a) 43. (d) 44. (a) 137. (b) 138. (a) 139. (d) 140. (b)
45. (c) 46. (c) 47. (c) 48. (d) 141. (a) 142. (a) 143. (a) 144. (a)
49. (c) 50. (b) 51. (b) 52. (c) 145. (c) 146. (d) 147. (d) 148. (d)
53. (b) 54. (d) 55. (b) 56. (c) 149. (b) 150. (b) 151. (c) 152. (a)
57. (b) 58. (d) 59. (a) 60. (c) 153. (d) 154. (c) 155. (d) 156. (a)
61. (d) 62. (a) 63. (c) 64. (b) 157. (a) 158. (a) 159. (b) 160. (d)
65. (c) 66. (d) 67. (d) 68. (d)
69. (c) 70. (d) 71. (c) 72. (c)
73. (c) 74. (d) 75. (b) 76. (b)
77. (a) 78. (b) 79. (c) 80. (a)
81. (c) 82. (b) 83. (a) 84. (d)
85. (a) 86. (d) 87. (d) 88. (d)
89. (a) 90. (a) 91. (b) 92. (a)
93. (d) 94. (c) 95. (c) 96. (b)
ANSWER KEY 235

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (b) 2. (b) 3. (a) 4. (a) 1. (c) 2. (a) 3. (a) 4. (c)

5. (c) 6. (c) 7. (c) 8. (b) 5. (a) 6. (c) 7. (b) 8. (a)
9. (c) 10. (a) 11. (b) 12. (a) 9. (d) 10. (b) 11. (c) 12. (a)
13. (d) 14. (c) 15. (d) 16. (a) 13. (a) 14. (b) 15. (a) 16. (a)
17. (c) 18. (b) 19. (d) 20. (c) 17. (c) 18. (d) 19. (b) 20. (b)
21. (d) 22. (c) 23. (c) 24. (d) 21. (c) 22. (b) 23. (b) 24. (b)
25. (b) 26. (d) 27. (a) 28. (c) 25. (b) 26. (d) 27. (a) 28. (c)
29. (a) 30. (b) 31. (d) 32. (d) 29. (b) 30. (a)
33. (c) 34. (a) 35. (a) 36. (a)
37. (a) 38. (d) 39. (c) 40. (d)
41. (a) 42. (b) 43. (c) 44. (b)
45. (b) 46. (d) 47. (c) 48. (c)
49. (b) 50. (d) 51. (a) 52. (c)
53. (b)
236 ANSWER KEY

Answer Key
CHAPTER - 7: AMINES
Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (b) 2. (d) 3. (a) 4. (c) 93. (c) 94. (d) 95. (b) 96. (b)
5. (d) 6. (a) 7. (b) 8. (a) 97. (b) 98. (b) 99. (a) 100. (a)
9. (d) 10. (d) 11. (d) 12. (d) 101. (c) 102. (c) 103. (c) 104. (d)
13. (c) 14. (a) 15. (c) 16. (c) 105. (d) 106. (a) 107. (a) 108. (a)
17. (c) 18. (d) 19. (d) 20. (a) 109. (c) 110. (c) 111. (d) 112. (d)
21. (b) 22. (a) 23. (a) 24. (d) 113. (b) 114. (a) 115. (c) 116. (b)
25. (b) 26. (c) 27. (c) 28. (d) 117. (a) 118. (c) 119. (c) 120. (b)
29. (b) 30. (d) 31. (a) 32. (c) 121. (b) 122. (a) 123. (b) 124. (c)
33. (c) 34. (c) 35. (c) 36. (a) 125. (c) 126. (a) 127. (a) 128. (d)
37. (c) 38. (c) 39. (d) 40. (d) 129. (b) 130. (a) 131. (b) 132. (b)
41. (d) 42. (b) 43. (d) 44. (a) 133. (b) 134. (a) 135. (c) 136. (b)
45. (d) 46. (c) 47. (d) 48. (d) 137. (c) 138. (b) 139. (b) 140. (a)
49. (b) 50. (b) 51. (b) 52. (d) 141. (a) 142. (c) 143. (d) 144. (d)
53. (c) 54. (a) 55. (b) 56. (d) 145. (c) 146. (a) 147. (b) 148. (d)
57. (a) 58. (c) 59. (b) 60. (b) 149. (b) 150. (b) 151. (c) 152. (c)
61. (c) 62. (b) 63. (d) 64. (b) 153. (d) 154. (d) 155. (d) 156. (c)
65. (a) 66. (a) 67. (c) 68. (c) 157. (d) 158. (a) 159. (c) 160. (a)
69. (b) 70. (b) 71. (d) 72. (c) 161. (a) 162. (a) 163. (a) 164. (c)
73. (a) 74. (b) 75. (c) 76. (a) 165. (c) 166. (a) 167. (b) 168. (a)
77. (d) 78. (b) 79. (c) 80. (a) 169. (a) 170. (c) 171. (d) 172. (c)
81. (d) 82. (c) 83. (c) 84. (c) 173. (a) 174. (a) 175. (c)
85. (a) 86. (b) 87. (a) 88. (d)
89. (c) 90. (d) 91. (a) 92. (d)
ANSWER KEY 237

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (b) 2. (b) 3. (d) 4. (a) 1. (c) 2. (c) 3. (d) 4. (d)

5. (a) 6. (c) 7. (b) 8. (c) 5. (d) 6. (c) 7. (d) 8. (d)
9. (d) 10. (a) 11. (c) 12. (c) 9. (b) 10. (c) 11. (a) 12. (b)
13. (b) 14. (c) 15. (c) 16. (a) 13. (a) 14. (d) 15. (a) 16. (b)
17. (b) 18. (a) 19. (a) 20. (d) 17. (c) 18. (c) 19. (c) 20. (a)
21. (b) 22. (c) 23. (c) 24. (a) 21. (a) 22. (a) 23. (a) 24. (a)
25. (b) 26. (d) 27. (a) 28. (d) 25. (d) 26. (d) 27. (b) 28. (d)
29. (b) 30. (d) 31. (b) 32. (a) 29. (a) 30. (c)
33. (c) 34. (b) 35. (d) 36. (d)
37. (b) 38. (c) 39. (d) 40. (d)
41. (d) 42. (b) 43. (c) 44. (a)
45. (c) 46. (d) 47. (c) 48. (d)
49. (c) 50. (d) 51. (c) 52. (d)
53. (a) 54. (b) 55. (d) 56. (d)
238 ANSWER KEY

Answer Key
CHAPTER - 8: BIOMOLECULES
Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (d) 2.(a) 3. (a) 4. (a) 101. (c) 102. (a) 103. (a) 104. (d)
5. (a) 6. (b) 7. (c) 8. (d) 105. (b) 106. (b) 107. (a) 108. (b)
9. (d) 10. (b) 11. (a) 12. (c) 109. (b) 110. (d) 111. (a) 112. (b)
13. (b) 14. (a) 15. (c) 16. (a) 113. (c) 114. (d) 115. (d) 116. (a)
17. (a) 18. (d) 19. (c) 20. (c) 117. (c) 118. (d) 119. (b) 120. (d)
21. (d) 22. (d) 23. (d) 24. (b) 121. (c) 122. (d) 123. (a) 124. (c)
25. (a) 26. (b) 27. (c) 28. (d) 125. (c) 126. (c) 127. (c) 128. (d)
29. (b) 30. (a) 31. (b) 32. (d) 129. (b) 130. (b) 131. (c) 132. (a)
33. (d) 34. (a) 35. (c) 36. (a) 133. (c) 134. (b) 135. (c) 136. (d)
37. (c) 38. (c) 39. (a) 40. (d) 137. (b) 138. (a) 139. (a) 140. (c)
41. (d) 42. (d) 43. (a) 44. (b) 141. (d) 142. (b) 143. (b) 144. (d)
45. (b) 46. (a) 47. (d) 48. (a) 145. (a) 146. (c) 147. (c) 148. (b)
49. (d) 50. (a) 51. (b) 52. (d) 149. (b) 150. (d) 151. (b) 152. (b)
53. (c) 54. (c) 55. (b) 56. (b) 153. (c) 154. (b) 155. (d) 156. (a)
57. (d) 58. (c) 59. (d) 60. (d) 157. (d) 158. (d) 159. (c) 160. (b)
61. (a) 62. (c) 63. (c) 64. (d) 161. (c) 162. (b) 163. (a) 164. (d)
65. (d) 66. (d) 67. (c) 68. (b) 165. (d) 166. (b) 167. (d) 168. (b)
69. (c) 70. (d) 71. (c) 72. (a) 169. (b) 170. (a)
73. (d) 74. (b) 75. (d) 76. (a)
77. (d) 78. (b) 79. (a) 80. (d)
81. (c) 82. (a) 83. (b) 84. (a)
85. (c) 86. (d) 87. (b) 88. (d)
89. (d) 90. (d) 91. (b) 92. (b)
93. (d) 94. (b) 95. (c) 96. (d)
97. (c) 98. (d) 99. (b) 100. (c)
ANSWER KEY 239

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (c) 2. (a) 3. (d) 4. (a) 1. (c) 2. (a) 3. (c) 4. (b)

5. (b) 6. (d) 7. (d) 8. (a) 5. (d) 6. (b) 7. (b) 8. (d)
9. (c) 10. (c) 11. (a) 12. (d) 9. (a) 10. (b) 11. (c) 12. (c)
13. (d) 14. (a) 15. (b) 16. (a) 13. (c) 14. (b) 15. (a) 16. (a)
17. (c) 18. (c) 19. (a) 20. (d) 17. (c) 18. (a) 19. (b) 20. (b)
21. (b) 22. (d) 23. (b) 24. (a) 21. (c) 22. (b) 23. (a) 24. (a)
25. (c) 26. (d) 27. (b) 28. (b) 25. (c) 26. (e) 27. (b) 28. (a)
29. (a) 30. (b) 31. (c) 32. (b) 29. (e) 30. (a)
33. (c) 34. (a) 35. (d) 36. (d)
37. (b) 38. (a) 39. (c) 40. (d)
41. (c) 42. (a) 43. (a) 44. (d)
45. (d) 46. (d) 47. (b) 48. (a)
49. (c) 50. (c) 51. (c) 52. (b)
53. (b)
240 ANSWER KEY

Answer Key
CHAPTER - 9: p-BLOCK ELEMENTS (GROUP 15-18)
Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (a) 2. (a) 3. (d) 4. (a) 93. (c) 94. (c) 95. (b) 96. (d)
5. (b) 6. (a) 7. (d) 8. (d) 97. (c) 98. (c) 99. (d) 100. (b)
9. (a) 10. (d) 11. (b) 12. (c) 101. (c) 102. (a) 103. (a) 104. (b)
13. (a) 14. (d) 15. (a) 16. (a) 105. (a) 106. (b) 107. (d) 108. (a)
17. (d) 18. (d) 19. (d) 20. (d) 109. (b) 110. (c) 111. (a) 112. (a)
21. (a) 22. (a) 23. (c) 24. (d) 113. (d) 114. (b) 115. (b) 116. (c)
25. (d) 26. (a) 27. (c) 28. (d) 117. (a) 118. (d) 119. (b) 120. (d)
29. (a) 30. (b) 31. (c) 32. (d) 121. (a) 122. (d) 123. (c) 124. (b)
33. (c) 34. (d) 35. (c) 36. (b) 125. (d) 126. (b) 127. (c) 128. (a)
37. (c) 38. (a) 39. (d) 40. (b) 129. (d) 130. (b) 131. (d) 132. (c)
41. (c) 42. (d) 43. (b) 44. (d) 133. (b) 134. (d) 135. (b) 136. (b)
45. (d) 46. (b) 47. (d) 48. (c) 137. (d) 138. (d) 139. (d) 140. (a)
49. (c) 50. (c) 51. (a) 52. (a) 141. (c) 142. (b) 143. (c) 144. (a)
53. (a) 54. (c) 55. (d) 56. (c) 145. (d) 146. (c) 147. (d) 148. (c)
57. (a) 58. (b) 59. (a) 60. (a) 149. (d) 150. (a)
61. (c) 62. (a) 63. (d) 64. (c)
65. (b) 66. (d) 67. (b) 68. (b)
69. (a) 70. (a) 71. (b) 72. (c)
73. (d) 74. (a) 75. (d) 76. (b)
77. (c) 78. (d) 79. (c) 80. (d)
81. (a) 82. (d) 83. (c) 84. (d)
85. (b) 86. (a) 87. (a) 88. (c)
89. (d) 90. (b) 91. (a) 92. (c)
ANSWER KEY 241
Exercise- 2: Previous Year Questions Exercise - 3: Achiever’s Section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (a) 2. (b) 3. (b) 4. (a) 1. (b) 2. (d) 3. (c) 4. (d)

5. (d) 6. (b) 7. (c) 8. (b) 5. (b) 6. (b) 7. (b) 8. (c)
9. (c) 10. (b) 11. (c) 12. (d) 9. (a) 10. (b) 11. (b) 12. (a)
13. (c) 14. (a) 15. (a) 16. (a) 13. (a) 14. (d) 15. (a) 16. (d)
17. (c) 18. (c) 19. (d) 20. (b) 17. (d) 18. (b) 19. (b) 20. (d)
21. (d) 22. (d) 23. (b) 24. (d) 21. (d) 22. (c) 23. (b) 24. (c)
25. (c) 26. (c) 27. (b) 28. (d) 25. (c) 26. (d) 27. (a) 28. (b)
29. (c) 30. (a) 31. (b) 32. (c) 29. (b) 30. (b)
33. (b) 34. (b) 35. (a) 36. (d)
37. (a) 38. (a) 39. (a) 40. (b)
41. (a) 42. (a) 43. (a) 44. (c)
45. (c) 46. (a) 47. (c) 48. (c)
49. (d) 50. (c) 51. (a) 52. (b)
53. (b) 54. (a) 55. (c) 56. (d)
242 ANSWER KEY

Answer Key
CHAPTER - 10: d AND f BLOCK ELEMENTS
Exercise- 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (d) 2.(d) 3. (c) 4. (d) 97. (b) 98. (d) 99. (b) 100. (c)
5. (c) 6. (c) 7. (d) 8. (a) 101. (c) 102. (a) 103. (d) 104. (b)
9. (d) 10. (a) 11. (a) 12. (c) 105. (d) 106. (d) 107. (d) 108. (d)
13. (b) 14. (a) 15. (b) 16. (c) 109. (a) 110. (b) 111. (a) 112. (c)
17. (b) 18. (c) 19. (b) 20. (c) 113. (b) 114. (a) 115. (b) 116. (b)
21. (c) 22. (a) 23. (a) 24. (c) 117. (c) 118. (c) 119. (a) 120. (a)
25. (a) 26. (a) 27. (b) 28. (b) 121. (d) 122. (b) 123. (b) 124. (d)
29. (b) 30. (d) 31. (d) 32. (a) 125. (a) 126. (c) 127. (d) 128. (d)
33. (d) 34. (a) 35. (d) 36. (c) 129. (d) 130. (d) 131. (d) 132. (a)
37. (a) 38. (b) 39. (c) 40. (d) 133. (b) 134. (d) 135. (d) 136. (a)
41. (a) 42. (b) 43. (d) 44. (d) 137. (b) 138. (c) 139. (d) 140. (d)
45. (b) 46. (d) 47. (d) 48. (a) 141. (d) 142. (c) 143. (d) 144. (b)
49. (b) 50. (d) 51. (b) 52. (c) 145. (d) 146. (c) 147. (a) 148. (c)
53. (c) 54. (a) 55. (d) 56. (c) 149. (a) 150. (c) 151. (c) 152. (d)
57. (c) 58. (b) 59. (c) 60. (b) 153. (d) 154. (c) 155. (c) 156. (b)
61. (d) 62. (c) 63. (b) 64. (b) 157. (d) 158. (c) 159. (a) 160. (a)
65. (a) 66. (a) 67. (c) 68. (c) 161. (c) 162. (c) 163. (a) 164. (a)
69. (c) 70. (d) 71. (c) 72. (a) 165. (a) 166. (b) 167. (b) 168. (b)
73. (b) 74. (d) 75. (d) 76. (d) 169. (a) 170. (c) 171. (d) 172. (a)
77. (d) 78. (b) 79. (c) 80. (c) 173. (a) 174. (a) 175. (c)
81. (a) 82. (c) 83. (b) 84. (b)
85. (a) 86. (b) 87. (c) 88. (c)
89. (d) 90. (b) 91. (c) 92. (b)
93. (d) 94. (a) 95. (d) 96. (d)
ANSWER KEY 243

Exercise - 2: Previous Year Questions EXERCISE - 3: Achiever’s Section

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1. (a) 2.(c) 3. (b) 4. (c) 1. (b) 2. (d) 3. (c) 4. (b)

5. (c) 6. (c) 7. (d) 8. (a) 5. (d) 6. (c) 7. (c) 8. (d)
9. (c) 10. (d) 11. (b) 12. (b) 9. (c) 10. (c) 11. (c) 12. (c)
13. (c) 14. (d) 15. (c) 16. (a) 13. (d) 14. (b) 15. (c) 16. (a)
17. (b) 18. (b) 19. (b) 20. (b) 17. (d) 18. (d) 19. (a) 20. (a)
21. (b) 22. (c) 23. (b) 24. (c) 21. (b) 22. (a) 23. (c) 24. (b)
25. (a) 26. (d) 27. (b) 28. (d) 25. (c) 26. (c) 27. (b) 28. (d)
29. (b) 30. (a) 31. (b) 32. (d) 29. (b) 30. (a)
33. (a) 34. (d) 35. (b) 36. (b)
37. (b) 38. (b) 39. (a) 40. (c)
41. (d) 42. (d) 43. (c) 44. (d)
45. (b) 46. (a) 47. (d) 48. (b)
49. (a) 50. (b) 51. (b) 52. (d)
53. (b) 54. (d)