2nd Year Chemistry Sc2 Chemistry

BUREAU’S
HIGHER SECONDARY (+2)
VOL. - II
Dr. A. K. Das Dr. H. K. Patnaik
Former Chairman, CHSE, Odisha Former Principal, Govt. College,
Bhubaneswar. Rourkela.
Dr. S. Behera Dr. G. C. Dash
Former Principal, D. D. College, Former Principal,
Keonjhar. S.C.S. (Autonomous) College, Puri.
Dr. A. K. Panigrahi Dr. Hrushikesh Mohanty
Former Director, Odisha State Bureau of Associate Professor & HOD, Chemistry,
Textbook Preparation and Production, B.J.B. Autonomous College, Bhaubaneswar.
Bhubaneswar. Dr. Santosini Patra
Dr. B. C. Singh Associate Professor in Chemistry
Former Professor of Chemistry, R.D. Women's University, Bhubaneswar
Ravenshaw College, Cuttack.
Dr. Panchanan Gouda
Dr. B. K. Mohapatra Associate Professor & H.O.D., Chemistry,
Former Chairman, CHSE, Odisha, Khallikote University, Berhampur.
Bhubaneswar.
Dr. I. B. Mohanty
Dr. J. N. Kar Deputy Director
Former Principal, Govt. College, Phulbani. Department of Higher Education, Odisha
Dr. Sakuntala Jena

Asst. Professor, Department of Chemistry,
Govt. Women's College, Dhenkanal.
PUBLISHED BY
THE ODISHA STATE BUREAU OF TEXTBOOK
PREPARATION AND PRODUCTION
PUSTAK BHAVAN, BHUBANESWAR.
Published by :
THE ODISHA STATE BUREAU OF TEXTBOOK PREPARATION AND PRODUCTION,
Pustak Bhavan, Bhubaneswar, Odisha, India.
First Edition : 2000 / 7000

Revised and Enlarged Edition : 2002 / 3000
Revised Edition : 2004 / 1000
Revised Edition : 2006 / 1000
Revised Edition : 2008/2000
Reprint - 2010/2000
Revised Edition : 2013/2000
New Edition : 2017 / 5000
Publication No : 197
ISBN : 978-81-8005-388-7
© Reserved by the Odisha State Bureau of Textbook Preparation and Production,

Bhubaneswar. No part of this publication may be reproduced in any form without the
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FOREWORD
(New Edition - 2017)
The Council of Higher Secondary Education, Odisha has revised the Courses of Studies
in Chemistry for its Examination, 2018 and onwards. It is really heartening to know that the
Chemistry, Vol-II is an exclusive textbook of CHSE and is being published by the Odisha State
Bureau of Text Book Preparation and Production, Bhubaneswar.
I acknowledge with thanks to the Board of Writers and Reviewers who have worked
hard in writing the chapters of the book and setting new pattern of questions as per the requirement
of the new syllabus of CHSE.
I would like to express my thanks to Dr. Jibanananda Kar, Dr. Akhil Krishna Panigrahi,
Dr. Gobinda Chandra Dash, Dr. Hrushikesh Mohanty, Dr. Panchanan Gouda, Dr. Santosini Patra
and Dr. Sakuntala Jena for taking pain and strain of doing arduous work in preparing the book
within the frame work of the new syllabus of CHSE.
Improvement has no limit especially when one aims at excellence. The Bureau welcomes
constructive suggestions from the students as well as the teachers to make the book more
purposeful.
Sri Umakanta Tripathy

Director
Odisha State Bureau of Text Book
Preparation and Production, Pustak Bhavan,
Bhubaneswar, Odisha
PREFACE
India is on the verge of a great leap into the global scientific and technological
advancement in the New Millennium. Our Universities and Council of Higher Secondary
Education have taken up the upgrading of science curriculum as a challenge. Society is becoming
largely knowledge based. To prepare our young students to achieve the goal, Council of Higher
Secondary Education, Odisha has revised the syllabus of all science subjects and has taken up
the challenge to arm our students with advanced scientific education.
The biggest challenge in the present times in the field of scientific education is the
preparation of textbooks suited to the needs of the students. Some of the most experienced,
learned and brilliant teachers of the State have made attempts towards fulfilling the national need
of providing a good textbook in Chemistry for +2 students. As a result the book titled +2 Chemistry
has been prepared in accordance with the new syllabus of C.H.S.E. Odisha which will be effective
for the students who will be admitted in 2016 and onwards. This book has many special features,
the salient ones of which may be enumerated as follows :
(i) The text book has been prepared keeping in view the type of questions set in the
+2 as well as entrance examinations.
(ii) The subject matter has been put in a lucid manner and in a simple language to be
easily followed by the students.
(iii) Large numbers of numerical problems have been worked out.
(iv) Neat diagrams are given to provide suitable explanation of the texts.
(v) Large number of questions of very short answer type, short answer type, multiple
choice type and long answer type including questions of H. S. Examinations are
given in each chapter.
(vi) At the end of every chapter, summary of the topics dealt in the chapter is given
under Chapter at a glance .
The authors express their gratitude to the authorities of C.H.S.E. for accepting them as
the members of Board of Editors and to the ODISHA STATE BUREAU OF TEXTBOOK
PREPARATION AND PRODUCTION for publishing the book. The authors sincerely hope
that their endeavour would fulfil the need of students. There may be minor errors of omissions
and commissions in the book. The authors welcome constructive criticism and suggestions for
the improvement of the book.
Bhubaneswar Board of Writers

14.3.2017
COURSES OF STUDIES IN CHEMISTRY (THEORY)
FOR
HIGHER SECONDARY EXAMINATION
(Effective from 2016 Admission Batch)
SECOND YEAR
Course Structure
Unit Title Marks
I Solid State
II Solutions
III Electrochemistry 23
IV Chemical Kinetics
V Surface Chemistry
..........................................................................................................................
VI Isolation of Elements
VII p-Block Elements
VIII d- and f- Block Elements 19
IX Coordination Compounds
..........................................................................................................................
X Haloalkanes and Haloarenes
XI Alcohols, Phenols and Ethers
XII Aldehydes, Ketones and Carboxylic Acids
XIII Organic Compounds containing Nitrogen 28
XIV Biomolecules
XV Polymers
XVI Chemistry in Everyday Life
Total : 70
Unit - I : Solid State
Classification of solids based on different binding forces: molecular, ionic, covalent
and metallic solids, amorphous and crystalline solids (elementary idea). Unit cell
in two dimensional and three dimensional lattices, calculation of density of unit
cell, packing in solids, packing efficiency, voids, number of atoms per unit cell in
a cubic unit cell, point defects, electrical and magnetic properties.
Band theory of metals, conductors, semiconductors and insulators and n & p type
semiconductors.
Unit II : Solutions
Types of solutions, expression of concentration of solutions of solids in liquids,
solubility of gases in liquids, solid solutions, colligative properties - relative
lowering of vapour pressure, Raoult’s law, elevation of boiling point, depression
of freezing point, osmotic pressure, determination of molecular masses using
colligative properties, abnormal molecular mass, van’t Hoff factor.
Unit III : Electrochemistry
Redox reactions, electrolytes and non-electrolytes, conductance in electrolytic
solutions, specific and molar conductivity, variation of conductivity with
concentration, Kohlrausch’s law, electrolysis and laws of electrolysis (elementary
idea), dry cell electrolytic cells and Galvanic cells, lead accumulator, EMF of a
cell, standard electrode potential, Nernst equation and its application to chemical
cells, Relation between Gibbs energy change and emf of a cell, fuel cells, corrosion.
Unit IV : Chemical Kinetics

Rate of a reaction (Average and instantaneous), factors affecting rate of reaction:
concentration, temperature, catalyst, order and molecularity of a reaction, rate
law and specific rate constant, integrated rate equations and half life (only for
zero and first order reactions), concept of collision theory (elementary idea, no
mathematical treatment). Activation energy, Arrhenius equation.
Unit V : Surface Chemistry

Adsorption - physisorption and chemisorption, factors affecting adsorption of
gases on solids, catalysts, homogenous and heterogenous activity and selectivity;
enzyme catalysis, colloidal state, distinction between true solutions,colloids and
suspension; lyophilic, lyophobic, multimolecular and macromolecular colloids;
properties of colloids; Tyndall effect, Brownian movement, electrophoresis,
coagulation, emulsion - types of emulsions.
Unit VI : General Principles and Processes of Isolation of Elements

Principles and methods of extraction - concentration, oxidation, reduction -
electrolytic method and refining; occurrence and principles of extraction of
aluminium, copper, zinc and iron.
Unit VII : p - Block Elements

Group15 Elements: General introduction, electronic configuration, occurrence,
oxidation states, trends in physical and chemical properties; Nitrogen : preparation
properties & uses; compounds of nitrogen, preparation and properties of ammonia
and nitric acid, oxides of nitrogen (Structure only); Phosphorus - allotropic forms,
compounds of phosphorus: preparation and properties of phosphine, halides PCl 3,
PCl5 and oxoacids (elementary idea only).
Group 16 Elements: General introduction, electronic configuration, oxidation
states, occurrence, trends in physical and chemical properties, dioxygen:
Preparation, Properties and uses, classification of oxides, Ozone, Sulphur:
allotropic forms; compounds of sulphur: Preparation properties and uses of sulphur
dioxide, sulphuric acid: industrial process of manufacture, properties and uses;
oxoacids of sulphur (Structures only).
Group 17 Elements: General introduction, electronic configuration, oxidation
states, occurrence, trends in physical and chemical properties; compounds of
halogens, Preparation properties and uses of chlorine and hydrochloric
acid,interhalogen compounds, oxoacids of halogens (structure only).
Group 18 Elements : General introduction,electronic configuration, occurrence,
trends in physical and chemical properties, uses.
Unit VIII : d and f Block Elements

General introduction, electronic configuration, occurrence and characteristics of
transition metals, general trends in properties of the first row transition metals -
metallic character, ionization enthalpy, oxidation states, ionic radii, colour, catalytic
property, magnetic properties, interstitial compounds, alloy formation, preparation
and properties of K2 Cr2O7 and KMnO4.
Lanthanoids - Electronic configuration, oxidation states, chemical reactivity and
lanthanoid contraction and its consequences.
Actinoids - Electronic configuration, oxidation states, chemical reactivity and
lanthanoid contraction and its consequences.
Actinoids - Electronic configuration, oxidation states and comparison with
lathanoids.
Unit IX : Coordination Compounds

Coordination compounds - Introduction, ligands, coordination number, colour,
magnetic properties and shapes, IUPAC nomenclature of mononuclear
coordination compounds. Bonding, Werner’s therory, VBT and CFT; structure
and stereoisomerism, importance of coordination compounds (in qualitative
analysis, extraction of metals and biological system).
Unit X : Haloalkanes and Haloarenes

Haloalkanes : Nomenclature, nature of C-X bond, physical and chemical
properties, mechanism of substitution reactions, optical rotation.
Haloarenes : Nature of C - X bond, substitution reactions (Directive influence of
halogen in monosubstituted compounds only.
Uses and environmental effects of - dichloromethane, trichloromethane,
tetrachloromethane, iodoform, freons, DDT, BHC.
Unit XI : Alcohols, Phenols and Ethers

Alcohols : Nomenclature, methods of preparation, physical and chemical
properties (of primary alcohols only), identification of primary, secondary and
tertiary alcohols, mechanism of dehydration, uses with special reference to
methanol and ethanol.
Phenols : Nomenclature, methods of preparation, physical and chemical properties,
acidic nature of phenol, electrophilic substitution reactions, uses of phenols.
Ethers : Nomenclature, methods of preparation, physical and chemical properties
uses.
Unit XII : Aldehydes, Ketones and Carboxylic Acids
Aldehydes and Ketones : Nomenclature, nature of carbonyl group, methods of
preparation, physical and chemical properties, mechanism of nucleophilic addition,
reactivity of alpha hydrogen in aldehydes uses.
Carboxylic Acids : Nomenclature, acidic nature, methods of preparation, physical
and chemical properties, uses.
Unit XIII : Organic compunds containing Nitrogen
Amines : Nomenclature, classification, structure, methods of preparation, physical
and chemical proporties, uses, identification of primary, secondary and teritary
amines.
Cyanide and Isocyanides - will be mentioned at relevant places in context
Diazonium salt - Preparation, chemical reactions and importance in synthetic
organic chemistry.
Unit XIV : Biomolecules
Carbohydrates - Classification (aldoses and ketoses) Monosaccharides (glucose
and fructose), D-L configuration, oligosaccharides (sucrose, lactose, maltose)
polysaccharides (starch, cellulose, glycogen), importance.
Proteins - Elementary idea of a - amino acids, peptide bond, polypeptide, proteins,
structure of proteins-primary secondary, tertiary structure and quaternary
structure(qualitative idea only), denaturation of proteins, enzymes.
Hormones - Elementary idea excluding structure
Vitamins - Classification and functions
Nucleic Acids : DNA and RNA
Unit XV : Polymers
Classification-Natural and synthetic, methods of polymerization(addition and
condensation)co polymerization, some important polymers : natural and synthetic
like polythene, nylon, polyester, bakelite, rubber. Biodegradable and non-
biodegradable polymers.
Unit XVI : Chemistry in Everyday life
Chemicals in medicines - Analgesics, tranquilizers antiseptics, disinfectants,
antimicrobials, antifertility, drugs, antibiotics, antacids, antihistamines.
Chemicals in food - Preservations, artificial sweetening agents, elementary idea
of antioxidants
Cleansing agents - Soap and detergents, cleansing action.
.....
CONTENTS
Chapter Subjects Pages
UNIT - I
CHAPTER - 1 : SOLID STATE 1 - 26
1.1. Characteristic properties of solids, 1.2. Classification of
solids: Crystalline solids, Amorphous solids, Ionic solids,
Covalent solids, Metallic solids, Molecular solids, 1.3. Crystal
lattices and unit cells, Packing in solids, 1.4. Types of cubic
crystals, 1.5. Calculation of density of unit cells, 1.6. Interstices
or Interstitial voids, 1.7. Co-ordination number, 1.8. Point
defects, 1.9. Electric and Magnetic properties of metals: Band
theory of metals, conductors, insulators, semiconductors- n & p
type semiconductors, Magnetic properties of solids.
UNIT - II
CHAPTER - 2 : SOLUTIONS 27 - 67
Characteristics of a solution : Types of solutions, 2.2. Solubility,
2.3. Concentration of a solution, 2.4. Solubility of gases in
liquids, 2.5. Vapour pressure, 2.6. Ideal and non-ideal solutions,
2.7. Colligative properties of dilute solutions- Relative lowering
of vapour pressure, Raoult's law, 2.8. Elevation of boiling point
(Ebullioscopy), 2.9. Depression of freezing point (Cryoscopy),
2.10. Osmotic pressure, 2.11. Abnormal molecular mass, van't
Hoff Factor.
UNIT - III
CHAPTER - 3 : ELECTROCHEMISTRY 68 - 108
3.1. Introduction : Redox reaction, Electrolytes and non-
electrolytes, 3.2. Arrhenius theory of electrolytic dissociation,
3.3. Strong and weak eletrolytes, 3.4. Electrolysis, 3.5. Faraday's
laws of electrolysis, 3.6. Applications of electrolysis,
3.7. Electrolytic conductance : specific, equivalent and molar
conductance, 3.8. Measurement of conductance, 3.9. Effect of
dilution on equivalent conductance, 3.10. Kohlrausch's law,
3.11. Electrochemical cells: Galvanic cell, 3.12. Cell reactions,
3.13. Electrode potential, 3.14. Single electrode potential,
3.15. Nernst equation, 3.16. Electromotive force (E.M.F) of a
cell, 3.17. Electrochemical cells : Primary cells (Dry cells), Lead
accumulator, Nickel-cadmium rechargeable cells, Fuel cells,
3.18. Electrochemical series, Application of electrochemical
series, 3.19. Corrosion.
UNIT - IV
CHAPTER - 4 : CHEMICAL KINETICS 109 - 146
4.1. Types of chemical reactions, 4.2. The rate of a reaction -
Determination of rate of reaction, Instantaneous and Average
rate of reaction, rate constant, units of rate constant, Rate of
reaction and rate constant, Factors influencing the rate of a
reaction : concentration, catalyst, temperature, surface area and
radiations, 4.3. Molecularity of a reaction, 4.4. Order of a
reaction, 4.5. Rate equations - Rate equation of first order
reaction, Rate equation of the zero order reaction, Half life period
and fractional life period, 4.6. Activation Energy, Arrhenius
equation, 4.7. Collision theory for unimolecular reaction.
UNIT - V
CHAPTER - 5 : SURFACE CHEMISTRY 147 - 186
5.1. Adsorption : Types of adsorption - physical adsorption and
chemisorption, 5.2. Adsorption of gases on solids,
5.3. Freundlich's adsorption isotherm, 5.4. Langmuir adsorption
isotherm, 5.5. Applications of adsorption, 5.6. Catalyst :
characteristics of catalyst, types of catalysis : Homogeneous and
Heterogeneous catalysis, 5.7. Enzyme catalysis, 5.8. Effect of
the catalyst on activation energy. 5.9. Adsoption theory of
heterogeneous catalysis, 5.10. Important features of solid
catalysts - Activity and selectively, 5.11. Colloidal state,
5.12. Types of colloidal system - True solutions, colloidal
solution and suspensions, 5.13. Classification of colloids:
Lyophilic and Lyophobic colloids, 5.14. Classification of colloids
on the basis of molecular size - multimolecular, macromolecular
and associated colloids (Micelles), 5.15. Preparation of colloidal
solution, 5.16. Properties of colloidal solution : Tyndall effect,
Brownian movement, zeta potential; Electrophoresis,
Coagulation of colloidal sol (Flocculation), coagulation of
lyophobic sol, lyophobic sol, 5.17. Application of colloids,
5.18. Emulsion : Type of emulsions, properties and uses of
emulsions.
UNIT - VI
CHAPTER - 6 : GENERAL PRINCIPLES AND PROCESSES OF 187 - 230
ISOLATION OF ELEMENTS
6.1. Introduction, 6.2. Occurrence of metal in nature,
6.3. Extraction of metals or Metallurgy : concentration,
calcination and roasting, smelting, reduction of metal oxide to

free metal, 6.4. Thermodynamic principles of metallurgy,
6.5. Extraction of iron from its oxide ores. 6.6. Copper :
Extraction, 6.7 Zinc-Extraction, 6.8. Electrochemical principles
of metallurgy - Extraction of Aluminium, 6.9. Extraction of non-
metals by oxidation-Isolation of chlorine, 6.10. Refining of
metals, 6.11. Uses of metals.
UNIT - VII
p-BLOCK ELEMENTS
CHAPTER - 7 : GROUP 15 ELEMENTS : NITROGEN FAMILY 231 - 259
7.1. Occurrence, 7.2. Trends in physical properties, 7.3. Trends
in chemical properties, 7.4. Anomalous behaviour of Nitrogen,
7.5. Dinitrogen : Preparation, properties and uses,
7.6. Compounds of Nitrogen : Preparation, properties and uses
of Ammonia, 7.7. Preparation, properties and uses of Nitric acid,
7.8 Oxides of Nitrogen - their structures. 7.9. Phosphorus :
Allotropic forms, 7.10. Preparation, properties and uses of
phosphine (PH3), 7.11. Phosphorus halides : preparation and
properties of phosphorus trichloride and phosphorus
pentachloride, their structures, 7.12. Oxo acids of phosphorus :
Formulae, oxidation state of phosphorus in them, their structures.
CHAPTER - 8 : GROUP 16 ELEMENTS : OXYGEN FAMILY 260 - 294

8.1. Occurrence, 8.2. Trends in physical properties, 8.3 Trends
in chemical properties, 8.4. Anomalous behaviour of oxygen,
8.5. Dioxygen : preparation, properties and uses.
8.6. Classification of oxides, 8.7. Ozone, 8.8. Sulphur :
Allotropic forms of sulphur, 8.9. Sulphur dioxide : preparation,
properties and uses. 8.10. Sulphuric acid (H2SO4) - Laboratory
and Industrial process of manufacture, properties and uses,
8.11. Oxo-acids sulphur - structures.
CHAPTER - 9 : EQUILIBRIA 295 - 324

9.1. Occurrence, 9.2. Trends in physical properties, 9.3. Trends
in chemical properties, 9.4. Anomalous behaviour of fluorine,
9.5. Chlorine : preparation, properties and uses, 9.6. Hydrogen
chloride (Hydrochloric acid) : preparation, properties and uses,
9.7. Oxoacids of halogen : their structures, 9.8. Interhalogen
compounds or Interhalogens : preparation, properties, structures
and uses, 9.9. Pesudo halides or Pseudohalogens.
CHAPTER - 10 : GROUP 18 ELEMENTS : NOBLE GASES 325 - 341

10.1. Introduction, 10.2. Occurrence, 10.3. Position of inert gases
in the Periodic table, 10.4. Properties of Zero group elements,
10.5. Chemical properties - compounds of zero group elements -
their properties, structures and uses.
UNIT - VIII
d - AND f - BLOCK ELEMENTS
CHAPTER - 11 : d - BLOCK ELEMENTS : TRANSITION ELEMENTS 342 - 360
11.1. Transition metals, 11.2. General characteristics of transition
elements : atomic radii, ionisation enthalpy, metallic properties,
densities, melting and boiling points, variable oxidation states,
formation of coloured compounds, formation of complex
compounds, paramagnetism, catalytic activity and formation of
alloys and interstitial compounds. 11.3. Potassium dichromate -
preparation, properties and uses, 11.4. Potassium permanganate
- preparation, properties and uses.
CHAPTER - 12 : THE f-BLOCK ELEMENTS 361 - 371

THE LANTHANOIDS AND THE ACTINOIDS
12.1. Introduction, 12.2. The lanthanoids-electronic
configuration, atomic and ionic sizes, lanthanoid contraction and
its consequences, oxidation states, General characteristics of
lanthanoids, uses, 12.3. The Actinoids : Electronic configuration,
oxidation states, Ionic sizes and Actinoid contraction, General
characteristics of actinoids, uses, 12.4. Comparison between
Lanthanoids and Actinoids.
UNIT - IX
CHAPTER - 13 : CO-ORDINATION COMPOUNDS 372- 404
13.1. Normal salt, 13.2. Double salts, 13.3. Co-ordination
compounds, 13.4. Definition of some important terms: co-
ordination complex, central ion, Ligands, co-ordination number,
co-ordination sphere, Types of ligands, 13.5. Werner's co-
ordination theory, 13.6. Nomenclature of co-ordination
compounds, IUPAC system, 13.7. Isomerism in co-ordination
compounds, 13.8. Bonding in co-ordination compounds: The

Valence Bond theory, The Crystal Field theory, 13.9. Bonding
in metal carbonyls, 13.10. Stability of co-ordination compounds,
13.11. Importance of co-ordination compounds : In qualitative
analysis, extraction of metals and in biological systems.
13.12. Organometallic compounds.
UNIT - X
HALOGENATED HYDROCARBONS
(HALOALKANES AND HALOARENES)
CHAPTER - 14 : HALOALKANES (ALKYL HALIDES) 405 - 421
14.1 Introduction, 14.2. Classification, 14.3. Monohalogen
derivatives of alkanes, 14.4. Nomenclature, 14.5. Methods of
preparation, 14.6. Properties - physical properties, chemical
properties - Elimination reactions, mechanism of Nucleophilic
substitution reactions : SN1 and SN2 mechanism, Reactions of
alkyl halides.
HALOARENES (ARYL HALIDES) 422 - 446

14.7. Nomenclature of halogen compounds, 14.8. Methods of
preparation of haloarenes, 14.9. Properties : Physical properties,
chemical properties : Nucleophilic substitution of aromatic
halogen-mechanism, Electrophilic substitution reactions,
directive influence of halogen in monosubstituted compounds,
Miscellaneous reactions, 14.10. Chlorobenzene-preparation and
properties, 14.11. Polyhalogen compounds : DDT, BHC,
Trichloromethane or chloroform, Tetrachloromethane or carbon
tetrachloride, Freons, 14.12. Arylalkalyl halides.
UNIT - XI
ALCOHOLS, PHENOLS AND ETHERS
CHAPTER - 15 : ALCOHOLS 447 - 486
15.1. Introduction, 15.2. Classification of alcohols, 15.3.
Monohydric alcohols, 15.4. Nomenclature of monohydric
alcohols, 15.5. Isomerism in alcohols, 15.6. General methods
of preparation, 15.7. Properties : Physical properties, Chemical
properties, 15.8. Distinction between primary, secondary and
tertiary alcohols, 15.9. Tests for alcoholic –OH group,

15.10. Manufacture of methyl alcohol from destructive
distillation of wood, 15.11. Manufacture of ethyl alcohol from
starchy materials 15.12. Some important conversions.
CHAPTER - 16 : PHENOLS 487 - 500

16.1. Methods of preparation, 16.2. Properties - Physical
properties, chemical properties : Acidity of phenols, esterification
reaction, Electrophilic substitution reactions with mechanism,
oxidation reaction and reaction with zinc dust.
CHAPTER - 17 : ETHERS 501 - 521

17.1. Classification of ethers, 17.2. Nomenclature of ethers,
17.3. Structure of ethers, 17.4. Preparation ethers, 17.5. Physical
properties of ethers, 17.6. Chemical properties : Reactions with
mechanism, 17.7 Uses of ethers.
UNIT - XII
CHAPTER - 18 : ALDEHYDES AND KETONES 522 - 598
18.1. Introduction, 18.2. Nomenclature of carbonyl compounds,
18.3. Isomerism in aldehydes and ketones, 18.4. Structure of
carbonyl group, 18.5. General methods of preparation of
aldehydes and ketones, 18.6. Special methods of preparation
for aromatic carbonyl compounds, 18.7. Properties of aldehydes
and ketones : Physical properties, Chemical properties -
Nucleophilic addition reactions with mechanism, reactions due
to a - hydrogen of aldehydes, oxidation reactions, Miscellaneous
reactions - reaction with NH3, Cannizzaro's reaction, Reaction
with PCl5, Reduction reactions, Reaction with primary amines,
Electrophilic substitution reactions in aromatic aldehydes and
ketones, 18.8. Uses of aldehydes and ketones, 18.9. Important
conversions.
CHAPTER - 19 : CARBOXYLIC ACIDS 599 - 642
1 9 . 1 . G e n e r a l i n t r o d u c t i o n , 1 9 . 2 . N o me n c l a t u r e ,
19.3. Isomerism, 19.4. Methods of preparation, 19.5. General
properties : Physical and chemical properties, 19.6. Tests,
19.7. Uses of carboxylic acids, Some important conversions.
UNIT - XIII
ORGANIC COMPOUNDS CONTAINING NITROGEN
CHAPTER - 20 : AMINES 643 - 673

20.1. Introduction, 20.2. Types of Amines - Aliphatic amines
and Arylmines, 20.3. Nomenclature, 20.4. Isomerism, 20.5.
General methods of preparation, 20.6. General properties :
Basicity of aliphatic amines, basicity of aromatic amines,
Physical properties, chemical properties, 20.7. Tests, 20.8.
Separation of primary, secondary and tertiary amines, 20.9. Uses,
20.10. Conversions, 20.11. Distinction between primary,
secondary and tertiary amines, 20.12. Cyanides and Isocyanides.
CHAPTER - 21 : ARYL DIAZONIUM SALTS 674 - 684

21.1. Preparation of Benzene diazonium chloride, 21.2.
Properties : Physical and chemical properties : Importance in
synthetic organic chemistry through various reactions. 21.3.
Some important conversions.
UNIT - XIV
CHAPTER - 22 : BIOMOLECULES 685 - 721
22.1. Introduction, 22.2. Carbohydrates : Classification,
Monosaccharides, Oligasaccharides and Polysaccharides,
Monosaccharides - Glucose : Preparation and structure, Fructose
: Preparation and structure, Disaccharides : Sucrose, Maltose,
Lactose - their structures, Polysaccharides - Starch, Amylopectin,
Cellulose - their structures, Glycogen, 22.3. Aminoacids,
Peptides and Polypeptides, 22.4. Proteins : Classification and
structure of proteins, Biological roles of proteins, Denaturation
of proteins, 22.5. Enzymes : Nature, properties of Enzymes,
22.6. Hormones : Chemical classes, source, function and effects
of Hormones, Plant Hormones. 22.7. Vitamins : Classification
and functions of vitamins. 22.8. Nucleic Acids :
Deoxyribonucleic Acid (DNA) and Ribonucleic Acid (RNA),
Biological functions of Nucleic acids.
UNIT - XV
CHAPTER - 23 : POLYMERS 722 - 745
23.1. Introduction, 23.2. Classification of polymers,
23.3. General method of polymerization,
23.4. Copolymerization, 23.5. Some important polymers :
Polythene, Polyacrylonitrile (PAN) or Orlon,
Polytetrafluoroethylene (PTFE) or Telflon, polyamides or
Nylons, Polyesters, Bakelites; Rubber - Natural and synthetic
rubber (cis-polybutadiene, Neoprene, Buna-N, Buna-S.
UNIT - XVI
CHAPTER - 24 : CHEMISTRY IN EVERYDAY LIFE 746 - 771
24.1. Introduction, 24.2. Chemicals in Medicine - Analgesics,
Tranquilizers, Antiseptics and Disinfectants, Antimicrobials,
Antibiotics, Antifertility Drugs, Antacids, Antihistamines,
24.3. Chemicals in Food - Preservatives, Artificial sweetening
agents, Antioxidants, 24.4. Cleansing agents - Soaps and
Detergents, Cleansing action of Soaps and Detergents.
.........
UNIT - I
CHAPTER - 1
THE SOLID STATE
The study of solids is mainly the study of crystals since most of the naturally occurring
solids are crystalline in nature. Solids are characterised by definite shape, definite volume and
fixed melting point.Besides compressibility, rigidity and high-mechanical strength are the
properties of a solid. The molecules, atoms or ions that constitute a solid are closely packed
and held by strong cohesive forces. So the solids have well ordered molecular arrangement.
1.1 CHARACTERISTIC PROPERTIES OF SOLIDS :
1. Shape : A solid has a definite shape.
2. Volume : A solid possesses a definite volume. It does not depend upon the size
or shape of the container.
3. Rigidity : Solids are highly rigid. This is due to the fact that the molecules have
definite positions and they cannot slide over each other to take up different
positions. The interparticle attractions in them tend to arrange the particles in an
orderly manner.
4. Compressibility : Solids are mainly incompressible. This is because the particles

which constitute the solid are in close contact with one another.
5. Diffusion : The diffusion in case of solids is extremely small. This is due to the
fact that the intermolecular forces of attraction holding the particles are very
strong in solids which result in a close packing of particles in it. Thus movement
of particles in a solid is very limited.
6. Melting point : The process of transformation of a solid into the liquid state
at a particular temperature is called melting. The constant temperature at which
a solid is transformed into the liquid state is called the melting point of the solid.
At the melting point there is an equilibrium between the solid and liquid phases.
7. Crystalline state : Solids possess a crystalline structure. This is due to orderly

arrangement of particles in solids.
2 +2 CHEMISTRY (VOL. - II)
1.2 CLASSIFICATION OF SOLIDS :

A. Solids are broadly classified into two categories : (a) crystalline solids (b) amorphous
solids.
Crystalline solids : Crystalline solids are not only rigid and incompressible but also
possess a regular orderly arrangement of atoms or molecules or ions which constitute the
crystals. Some examples of crystalline solids are sodium chloride, sugar, alum and diamond.
A crystal of sodium chloride is cubic. In sodium chloride, Na + and Cl– ions are
arranged in the crystal lattice at alternate sites. Each Na + is surrounded octahedrally by six Cl–
ions and each Cl– is surrounded octahedrally by six Na+ ions. This arrangement exists throughout
the crystal.
There are some crystalline solids whose crystalline structure contains few molecules of
water. Such crystals are called hydrates. The water of hydration is called water of
crystallisation. Examples of such crystalline solids are Blue vitriol (CuSO 4. 5H2O), Green
vitriol (FeSO4. 7H2O), Glauber's salt (Na2SO4. 10H2O), White vitriol (ZnSO4. 7H2O), Washing
soda (Na2CO3.10 H2O). There are some crystalline solids which do not contain water of
crystallisation. Such salts are called anhydrous. Some examples of such salts are sodium
chloride (NaCl), potassium nitrate (KNO3), ammonium chloride (NH4Cl) etc.
Amorphous solids : Amorphous solids are rigid and incompressible and possess some
ordered arrangement around a particular atom or ion which lasts only upto short distances.
Examples of such solids are glass, fused silica, rubber and plastic.
DISTINCTION BETWEEN CRYSTALLINE AND AMORPHOUS SOLIDS
Crystalline Amorphous
1. Geometry : Crystalline solids have 1. Amorphous solids do not have regular
regular and definite geometry which geometry. The ordered arrangement
extends throughout the crystal. extends only upto a short distance.
2. Melting point :Crystalline solids 2. Amorphous solids do not possess sharp
possess sharp melting points. melting points.
3. Isotropy and Anisotropy : Crystalline 3. Amorphous solids are isotropic i.e.
solids are anisotropic i.e. their physical their physical properties such as
properties such as conductivity, conductivity, refractive index are the
refractive index etc. are different along same along all directions.
different directions.
4. Cleavage : When a crystalline solid is 4. When an amorphous solid is cut with a
cut with a sharp edged tool, it is readily sharp edged tool, it gives smaller pieces
cut into smaller crystals with plane with irregular surfaces.
surface.
5. Symmetry : Crystalline solids possess 5. Amorphous solids do not possess
crystal symmetry. symmetry.
THE SOLID STATE 3
Classification of Crystalline solids :

Crystalline solids may be further classified into following types according to the
nature of particles constituting them and the binding forces between them.
a. Ionic solids. b. Covalent solids.
c. Molecular solids. d. Metallic solids.
a. Ionic solids : In ionic solids, the constituent particles are ions which are held together
by electrostatic forces. The arrangement of these ions is such that cations have an ions
as their nearest neighbours and vice versa. Examples of ionic solids are salts like
Sodium chloride (NaCl), Lithium fluoride (LiF), Barium sulphate (BaSO 4), Sodium
nitrate (NaNO3), Sodium sulphate (Na2SO4) etc.
Fig. 1.1 Sodium chloride crystal

Because of stronger and non-directional electrostatic interactions the ionic
solids are hard, brittle, and possess high melting and boiling points. They are bad
conductors in the solid state but good conductors in the molten state.
b. Covalent solids : In covalent solids the constituent particles are the atoms which are
held by covalent bonds. The bonds in covalent solids extend throughout the crystal and
this results in the formation of a giant three dimensional structure. Some examples of
covalent solids are diamond, graphite, quartz (SiO 2). Covalent solids are hard, non-
volatile and possess high melting points. They are bad conductors of heat and electricity.
c. Metallic solids : In metallic solids, the constituent particles are positive ions immersed
in a sea of electrons. The positively charged metal ions are held together by the cloud
of negative electrons. The cloud of electrons belong to the entire net work of crystals.
Some examples of metallic solids are common metals like copper, silver, aluminium
and sodium and some alloys. Metallic solids are malleable and ductile. They have
metallic lustre and are good conductors of heat and electricity.
d. Molecular solids : In molecular solids, the constituent particles are small molecules
which are held together by weak van der Waals forces. Some examples of molecular
solids are solid carbon dioxide, ice, sugar, iodine etc. Molecular solids are soft and
volatile. They possess low melting points and are bad conductors.
1.3 CRYSTAL LATTICES AND UNIT CELLS :
Crystal lattice :
A crystal lattice (or space lattice) is a general term of an arrangement of points in
space representing the atoms, ions or molecules forming the crystal which if extended in all
directions throughout the crystal forms a repeating unit giving a shape of the crystal. In
otherwords, a crystal lattice is a regular arrangement of the constituent particles (atoms, ions
or molecules) of a crystalline solid in three dimensional space.
Lattice points :
The positions which are occupied by the atoms, ions or molecules in the crystal lattice
are called lattice points or lattice sites.
Unit cell :
It is the smallest repeating unit in crystal lattice which when repeated over and over
again produces the complete crystal lattice.
Such units are repeated over and over again in three dimensions and represents the
shape of the entire crystal. The collection of points in the unit cell indicate the crystal coordination
number and are in consistence with the formula of the compound.
space lattice
UNIT CELL
Fig. 1.2 Space lattice and a unit cell
Close packing in Crystalline solids :

In the formation of crystals the constituent particles (atoms, ions or molecules) get
closely packed together. The closely packed arrangement is that in which the maximum available
space is occupied. The closer the packing, the greater is the stability of the packed system.
The packing will also vary according to the shape and size of the constituent particles of
crystals.
THE SOLID STATE 5
(i) Close packing in two dimensions :

To understand the packing of constituent particles let us consider the packing of hard
spheres of equal size. The spheres can be arranged side by side touching each other in a row.
The rows can be combined in the following two ways with respect to the first row to build
a crystal plane.
1. The spheres are packed in such a way that the rows have a horizontal as well as vertical
alignment. In this arrangement the spheres are found to form squares. This type of
packing is also called square close packing. (scp)
2. The spheres are packed in such a way that the spheres in the second row are placed
in the depressions between the spheres of the first row. Similarly, the spheres in the
third row are placed in the depressions between the spheres of the second row and so
on. This gives rise to hexagonal close packing of spheres (hcp)
A B
Fig 1.3 (A) A sphere in square close packing is in contact with four spheres.
(B) A sphere in hexagonal close packing is in contact with six spheres.
Arrangement I Arrangement II
(Less closely packed) (More closely packed)
Fig. 1.4 Packing of Spheres
(ii) Close packing in three dimensions :
— A Layer
a a a a a
b b b b —B Layer
a a
b b b
Fig. 1.5 Packing of second layer (B) on first layer (A)

Consider the above arrangement. Let us mark the spheres in the first layer as A. It is
clear from the above arrangement that there are two types of voids of hollows in the first layer.
These are marked as a and b. All the hollows are equivalent but the spheres of second layer
may be placed either on hollows which are marked 'a' or on other set of hollows marked 'b'.
It is to be noted that it is not possible to place spheres on both type of hollows.
Let us place the spheres on hollows marked 'b' to make the second layer which may
be labelled as B layer. Obviously the holes marked 'a' remain unoccupied while building the
second layer. The second layer is indicated as dotted circles.
When a third layer is to be added, again there are two types of hollows available. One
type of hollows marked 'a' are unoccupied hollows of first layer. The other type of hollows are
hollows in the second layer marked 'c'. Thus two alternatives are available to build the third
layer.
1. In this case, the spheres of the third layer lie directly above those in the first layer.
This type of packing is referred to as ABABA ....... arrangement .
A
(a) (b)
Fig. 1.6 ABABA... or hcp arrangement of spheres.
It is also known as hexagonal close packing (hcp)
2. The second way to pack spheres in the third layer is to place them over hollows marked
'a'. This gives rise to a new layer labelled as 'C'. However it can be shown that the spheres
in the fourth layer will correspond to those in the first layer. This gives rise to A B C A B
C A ........type of arrangement. It also known as cubic close packing. (ccp).
A
A
C C
B B
A
(a) (b) (c)
Fig. 1.7 ABCABCA... or ccp arrangement of spheres.
THE SOLID STATE 7
1.4 TYPES OF CUBIC CRYSTALS :

It is a fact that cubic system is the simplest system. There are three common types of
cubic system.
1. Simple cubic.
2. Body centred cubic (bcc)
3. Face centred cubic (fcc) or
Cubic close packing (ccp)
1. Simple cubic : In this arrangement the points (atoms, ions or molecules) are present
at all the corners of a cube.
1
Simple cubic 8 atom
Fig. 1.8 Simple cubic arrangement and number of spheres per unit cell.
From the figure it is clear that the atom present at each corner contributes 81 to each
cube because it is shared by 8 cubes. Now there are 8 atoms at the corners. Thus the number
of atoms present in each unit cell = 8 corner atoms x 81 atoms per unit cell = 1 atom.
2. Body centred cube (bcc) : It has points at all the corners as well as at the centre of
the cube.
1
8 atom
1 atom
(a)
(b)
Fig. 1.9 Body centred cubic arrangement.

It is clear from the figure that there are eight atoms at the corners and each is shared
by 8 unit cells so that the contribution of each atom at corner is 81 . In addition there is one
atom in the body of the cube which is not shared by any other cube.
Therefore, the number of atoms present at the corners per unit cell = 8 corner atoms x 81
atom per unit cell = 1
The number of atoms present at the centre of the cube = 1
\ Total number of atoms in bcc arrangement = 1 + 1 = 2.
Thus, a body centred cube has two atoms per unit cell.
3. Face centred cube (fcc). This is also called cubic close packed arrangement. It has
points at all the corners as well as at the centre of each of the six faces.
1
(a) (b) 8 atom
Fig. 1.10 Cubic close packed or face centred cubic

arrangement and share of each atom per unit cell.
In this arrangement, there is one atom at each of the eight corners.
From the above figure it is quite clear that atom present at each corner contributes 81
to each cube because it is shared by 8 cubes. In addition, there are six atoms at the faces of
the cube and each is shared by two unit cells. Therefore the contribution of each atom at the
face per unit cell is 21 .
\ The number of atoms present at corner per unit cell = 8 corner atoms x 81 atoms
per unit cell =1
The no. of atoms present at faces per unit cell
= 6 atoms at faces x 21 atoms per unit cell = 3
\The total no of atoms in ccp or fcc arrangement = 1 + 3 = 4
The following table (1.1) depicts the total no. of atoms present per unit cell in
different types of crystals.
Table 1.1 No. of atoms per unit cell in different crystals
Unit cell No. of No. of atoms No. of Total No.
atoms at corners at faces atoms in centre of atoms
1
Simple cubic 8x 8 0 0 1
1
Body centred 8x 8 0 1 2
1 1
Face centred 8x 8 6x 2 0 4
THE SOLID STATE 9
1.5 CALCULATION OF DENSITY OF UNIT CELLS :

The density of unit cell can be calculated knowing the type of crystal structure and the
edge length of the unit cell.
Let the edge length of unit cell = x pm
Volume of unit cell = (x pm)3 = (x × 10–10 cm)3 = x3 × 10–30 cm3
Mass of unit cell

Density of unit cell = Volume of unit cell
No. of atoms in the unit cell× Mass of each atom

=
Volume of unit cell
n× M N
x × 10 30 cm3
3
nM 3
= g. cm
Nx 3 10 30
where n = No. of atoms in the unit cell

M = Atomic mass
N = Avogadro Number
Thus, knowing the density of unit cell, the atomic mass as well as number of atoms or
Avogadro number can be determined. n = 1, 2, and 4 for simple cubic lattice, bcc and fcc lattice
respectively.
1.6 INTERSTICES OR INTERSTITIAL VOIDS :

In close packing spheres, certain hollows are left vacant. These hollows or voids in the
crystals are called interstital sites, or interstitial voids or simply interstices. Two such voids
are quite important.
1. Tetrahedral 2. Octahedral.
1. Tetrahedral void :
Tetrahedral hole Tetrahedral hole
Fig. 1.11 Tetrahedral void.

The above arrangement of four spheres shows that their centres lie at the apices of a
tetrahedron. But the shape of the void is not tetrahedral. Thus the vacant space among four
spheres having tetrahedral arrangement is called tetrahedral site or tetrahedral hole.
2. Octahedral void :
Octahedral hole
Octahedral hole
Octahedral hole
Fig. 1.12 Octahedral site

This type of void is formed at the centre of six spheres. In the above arrangement, each
octahedral site is produced by two sets of equilateral triangles which point in opposite directions.
Thus the void formed by two equilateral triangles with apices in opposite direction is called
octahedral site or octahedral hole or simply octahedral void. This site is therefore surrounded
by six spheres lying at the vertices of a regular octahedron.
1.7 CO-ORDINATION NUMBER :

The number of nearest neighbours with which a given sphere is in contact is called
co-ordination number. For ionic solids, the ratio of the radius of cation to that of anion is
called radius ratio. The radius ratio for a given co-ordination number is fixed.
To understand it better, let us consider ionic solids. Each ionic solid is made up of
cations and anions which have definite arrangements. Each ion is surrounded by a number of
ions of opposite charge. For example, in A+B–, A+ ions are surrounded by a definite number
of B– ions. This number is called co-ordination number of A +. Similarly, the number of A+ions
which are surrounding a B– ion is called co-ordination number of B– ions.
Since the arrangement of ions in a crystal and the co-ordination number of ions depend
upon the ratio of its radius with respect to the radius of the ions or atoms surrounding it, the
radius ratio can be represented as :
+
Radius ratio = Radius of the cation
Radius of the anion = r
r
-
Radius ratio plays very important role in determining the structures of ionic solids. We
know that the cations and anions in the ionic compound are held together by strong electrostatic
forces. As a result, the ions try to arrange themselves in such geometrical arrangements where
the attractions between the oppositely charged ions are maximum and the repulsions between
the similar charged ions are minimum.
Example - Consider an ionic crystal AB in which a cation is surrounded octahedrally by six
anions. For simplification, let us take any four B – ions. There will be two more B–
ions, one above and the other below A+ ion which have been omitted for clarity.
The most stable arrangement is one in which anions are touching each other and
the cation simultaneously.
THE SOLID STATE 11
(a) O Anion (b)

l Cation
(c)
Fig. 1.13 Effect of change of size of anion (same cation) and the stability of structure. The cation is
octahedrally surrounded by six anions but only four are shown. The anions above and below the
cation are not shown for simplicity.
This arrangement will be most stable. However, if the size of the anion is less (cation
same) the anions will no longer touch other anions and the structure will be unstable.
(a)
s
ease r +/r –
– decr inc
r+ /r rea
ses
(b) (c)
r+
= 0.414 – 0.732
r-
–Octahedral
C.N. increases from 6 to 8

Cubic
+
+ ( rr - > 0.732)
C.N. decreases from 6 to 4
Tetrahedral ( rr - < 0 . 414 )
Fig 1.14 Effect of radius ratio on co-ordination number.

Similarly, if the size of anions is large (cation same) all the anions will not be able to
touch the cation simultaneously. The structure will be unstable.
Therefore, if we decrease or increase the radius of the anion, keeping the cation same, the
co-ordination number may increase or decrease to get stable arrangement. This means that the
co-ordination number of a compound depends upon the radius of the cations and anions.
Radius ratio versus possible co-ordination number :
The possible
+
co-ordination numbers and structural arrangements of anions around cations
r
for different r - values are given below in table 1.2.
Table 1.2 Radius ratio versus co-ordination number with examples
Radius ratio Possible Structural Examples
Co-ordination number arrangement
0.155 – 0.225 3 Trigonal planar B2O3
0.225 – 0.414 4 Tetrahedral ZnS, SiO44–
0.414 – 0.732 6 Octahedral NaCl
0.732 – 1.0 8 Cubic CsCl
Example :
The radius of Na+ ion is 95 pm and that of Cl– ion is 181 pm. Predict whether the
co-ordination number of Na+ ion is 6 or 4. (pm = picometer = 10–12m)
Solution :
Radius of Na+ = 95 pm
Radius of Cl– = 181 pm.
r+ r + (Na + ) 95
Radius ratio , r - = = 181 = 0.524
r - (Cl - )
The radius ratio lies between 0.414 – 0.732. Hence, Na+ ions prefer to occupy octahedral
holes having co-ordination number 6.
Structure of substances related to close packed lattices :
Example :
1. Structure of sodium chloride : A unit cell representation of sodium chloride is shown in
fig. 1.15
Cl–
Na+
Cl– ion octahedrally
surrounded by six
Na+ ions
Na+ ion octahedrally

surrounded by six Cl – ions
Fig. 1.15 Representation of unit cell of NaCl.

The salient features of the structure are :
i. The Cl– ions adopt cubic close packed arrangement. Therefore, Cl – ions are
present at all the corners and at the centre of each face of the cube. This
arrangement is also regarded as fcc arrangement of Cl – ions.
ii. The Na+ ions occupy all the octahedral sites.
iii. Since there is an octahedral site per atom in closed packed arrangement, there
will be one Na+ ion for every Cl– ion. Thus the ratio of Na+ and Cl– ions in this
structure is 1 : 1 and the formula of the compound is Na + Cl–.
iv. In this structure, each Na+ ion is surrounded by 6 Cl– ions which are disposed
towards the corners of a regular octahedron. (Fig 1.16 ). Similarly each Cl – ion
is surrounded by six Na+ ions. Thus the co-ordination numbers of Na+ and Cl–
in NaCl structure are 6 and 6.
THE SOLID STATE 13
2. Structure of Zinc sulphide (Zinc blend)
Zn2+ion
tetrahedrally
surrounded by S2–ion
four S2– ions tetrahedrally
surrounded by
four Zn2+ ions
Zn2+ion of
second unit cell
Fig. 1.16 Representation of zinc blend (ZnS) structure.
i. The S2– ions form cubic close packed arrangement. In this arrangement the S 2–
ions are present at the corners of the cube and at the centre of each face.
ii. The zinc ions (Zn2+) occupy half of the tetrahedral sites.
iii. There are two tetrahedral sites per atom in a closed packed lattice. That means
there are two tetrahedral sites available for every S 2– ions. In this arrangement,
any half of the tetrahedral sites is occupied by Zn 2+ ions. Therefore, there is one
Zn2+ ion for every S2– ion and the formula is ZnS.
iv. In this structure each Zn2+ ions is surrounded by four sulphide ions which are
disposed towards the corner of a regular tetrahedron. Similarly each S 2– ion is
surrounded by four Zn2+ ions which are also disposed towards the corners of a
regular tetrahedron.
3. Structure of CaF2 (Calcium fluoride) :
F– ion surrounded
by 4 Ca2+ ions F–
Ca2+
Fig. 1.17 Representation of CaF 2 structure.

i. The Ca2+ ions are arranged in ccp arrangement. In this arrangement Ca 2+ ions are
present at all the corners and at the centre of each face of the cube.
ii. The fluoride ions occupy all the tetrahedral sites.
iii. There are two tetrahedral sites per atom in a closed packed lattice. This means
there are two tetrahedral sites for every Ca 2+ ion. Since F– ions occupy all the
tetrahedral sites, there will be two F – ions for each Ca2+ ion.
Thus the formula of the substance is CaF2.
iv. In this structure, each F– ion is surrounded by four Ca2+ ions, while each Ca2+ ion is
surrounded by eight F– ions. Thus the co-ordination numbers of Ca2+ & F– ions are
8 & 4.
4. Structure of Cesium chloride (CsCl)
Cs+ ion
Cl–
surrounded by 8
Cs+
Cl– ions
(a) (b)
Cl– ion surrounded

by 8 Cs+ ions
Fig. 1.18 Representation of CsCl structure.
The salient features are :

i. The Cl– ions are arranged in a simple cubic arrangement. In this arrangement the
Cl– ions are present at all the cornes of the cube.
ii. The Cs+ ions occupy the cubic site. That is Cs+ ions are present at the body centre of
the cube.
iii. From the above figure, it is clear that there are 8 Cl – ions at the corners of the cube.
Since each ion at the corner is shared by eight unit cells, its contribution per unit
cell is 1/8. Therefore 8 Cl– ions at the corners = 8 x 1 = 1 Cl– ion per unit cell.
8
There is also one Cs+ ion in the body centre and its contribution per unit cell is 1.
Thus there is one Cl– for each Cs+ ion and the compound has the formula CsCl.
iv. In this structure, each Cs+ ion is surrounded by 8 Cl– ions which are disposed towards
the corners of a cube. (see the fig. 1.18) When the unit cell is extended, it can be
seen that each Cl– ion is also surrounded by 8 Cs+ ions.
Thus, the co-ordination number of Cs+ and Cl– ions are 8 and 8.
1.8 POINT DEFECTS :

The crystal which is made up of same unit cells and contains the same lattice points
throughout the crystal is said to be an ideally perfect crystal. Any deviation of the ideally perfect
crystal from the periodic arrangement of its constituents is known as defect or imperfection of
the crystal.
THE SOLID STATE 15
The imperfection or defect which arises due to missing atoms, displaced atom or extra
atom within the crystals in known as Point defect. Point defects are thus due to imperfect pack-
ing during original crystallisation or they may arise due to thermal vibration of atoms at elevated
temperature. The common point defects one Schotty defect and Frenkel defect. The less com-
mon point defects includes metal excess defect and metal deficiency defects.
Defects in stoichiometric solids - Stoichiometric compounds are those in which the
number of +ve and –ve ions are in the same ratio as indicated by their chemical formulae. The
defects which do not disturb the stoichiometry of the compound are known as stoichiometric
defects. These are of the following types.
(1) Schottky Defects
(i) These defects arise due to missing of equivalent number of cations and anions from
their respective positions in the crystal lattice thereby forming pair of holes.
(ii) These defects are more common in ionic compounds with high co-ordination number
and having both positive and negative ions with almost equal size.
(iii) The crystal, as a whole, is electrically neutral since the number of missing +ve and
–ve ions is the same.
(iv) Examples of ionic crystal showing Schottky defect include NaCl, KCl, KBr, CsCl
etc.
X+ Y X+ Y
X+
+
Y X Y
X+ Y X+ Y
Y X+ Y X+
Fig. 1.19 Schottky Defect

Consequences of Schottky defects.
(i) Due to Schottky defect there is an increase in volume of the crystal with no in-
crease in mass.
(ii) The density as well as the covalent character of the crystalline solid decreases.
(iii) The crystal becomes capable of conducting a small amount of electricity through
ion jump mechanism.
(iv) The movement of atoms or ions in the crystal is induced due to existence of a
vacancies. This accounts for the phenomenon of diffusion solids.
(v) The number of Schottky defects increase with increase in temperature.
(vi) The lattice energy of the crystal in lowered due to presence of holes. Thus, stability
of crystal is lowered.
(2) Frenkel Defects

(i) This defect arises due to shifting of an ion from its normal position to interstitial
site in the crystal lattice between the lattice points thereby causing a vacancy in the
original position.
(ii) This defect is more common in ionic compounds having low co-ordination number
and having large difference in size between positive and negative ions.
(iii) The crystal remains neutral since the number of +ve ions is equal to the number of
–ve ions.
(iv) In an ionic crystal generally the cation moves since it is smaller than the anion and
can easily fit into the vacant space in the lattice.
(v) Examples of ionic crystals showing Frenkel defect include ZnS, AgCl, AgBr, AgI
etc.
X+ Y X+ Y
Y X
X+ Y- X
X Y- X Y
Y X Y X
Fig. 1.20 Frenkel Defect

Consequences of Frenkel Defects
(i) The crystals are made good electrical conductors due to these defects.
(ii) These defects also account for the phenomenon of diffusion in solids.
(iii) These defects bring about closeness of similar charges which tend to increase the
dielectric constant of the crystal.
(iv) The number of Frenkel defects increase with temperature.
(v) The stability of the crystal is lowered due to presence of the holes.
Defects in Non-stoichiometric solids
Non-stoichiometric solids are those in which the ratio of +ve and –ve ions differs from
that represented by chemical formulae. These compounds do not strictly obey the law of constant
proportions. Examples include Feo.94 O or VOx , where x is between 0.6. and 1.3, In such type of
compounds the balance of +ve and –ve charge is made by having either extra electrons or extra
+ve charge. As a result the crystal structure becomes irregular and defective. These defects are of
two types.
THE SOLID STATE 17
(i) Metal excess defects

When the metal ions are in excess as compared to –vely charged ion, the solid is said to
have metal excess effect. There defect are due to two phenomena.
(a) Anion vacancies
(i) This defect arises due to removal of anions or nonmetal ions from the lattice sites
resulting in the increase in concentration of metal ion or cation.
(ii) The vacancy caused by the loss of anion is occupied by electron so that electrical
neutrality is maintained
X Y X Y
Y X e X
X Y X Y
Y X Y X
Fig. 1.21 Metal excess defect

(iii) This type of defect is observed in crystals which are likely to exhibit Schottky
defect. Alkali metal halides are heated in a medium of alkali metal vapour so that
anion vacancies are created. Alkali metals get deposited over alkal halide crystal.
The halide ions move towards the surface and combine with metal ions.
(iv) On the otherhand when metals are converted into metal ions electrons are pro-
duced and the electron diffuse into the crystal and occupy the vacant positions in
the lattice sites.
(v) The electrons occupy the holes known as F- Centres or Coloured centres (German
word ‘Farbe’ meaning colour). F-centre is responsible for colour of the compound.
For example, NaCl is yellow due to presence of excess Na+ ion. KCl is violet due to
presence of excess K+ ion.
Consequences of Metal excess deffect due to anion vacancies
(a) The solids havings metal excess deffect act as semiconductors. This is due to pres-
ence of electrons at the F-centres.
(b) The electrons present at F- centres are excited to higher energy level and when they
return to the ground state they do so by emitting certain radiation. This radiation
falls is the visible region, so a colour is visualised. For example, ZnO gets yellow
on heating.
(c) The solids having F-centres with unpaired electrons are paramagnetic.
(b) Extra cations in interstitial sites.

(i) This defect arises due to presence of extra cations in the interstitial sites.
(ii) To maintain electrical neutrality equivalent number of electrons are placed in the
interstital sites.
Fig. 1.22 Metal excess defect due to interstitial cations.

(iii) This type of defect is observed by the crystals which are likely to exhibit Frenkel
defect. For example, when ZnO is heated, oxygen is lost reversibly and the intersti-
tial sites accomodate excess metal ion. The electrons are trapped in the
neighbourhood.
(iv) The electrical conductivity and the yellow colour in hot condition are due to these
trapped electrons.
2. Metal deficiency defect
If the number of metal ions is less than the number of –vely charged ions, the solid is said
to have metal deficiency defect. These defects are of two types.
(a) Cation vacancies
(i) This arises due to loss of cations from normal lattice site.
(ii) When a cation is missing, an extra electron must be present in the crystal and the
extra negative charge in balanced by neighbouring metal ion (X +) acquiring two
+ve charges (X++) instead of one.
Fig. 1.23 Metal deficiency defect due to cation vacancy

THE SOLID STATE 19
(iii) The movement of +ve hole is caused due to apparent movement of X 2+ ions is due
to movement of an electron from X+ ion.
(iv) Transition metal compounds having metals with variable valencies exhibit this
type of defect. Some specific examples are crystals of FeO, NiO and FeS.
(b) Extra anions in the interstitial sites
(i) This effect arises due to presence of extra anions in the interstial spaces of the
crystal.
(ii) The cations carrying additional charge are helpful in maintaining electrical neutrality.
(iii) Anions are much larger than cation therefore do not fit well into interstitial sites.
Hence this defect is usually not seen.
1.9 ELECTRIC AND MAGNETIC PROPERTIES OF METALS :

Metals conduct electricity due to the movement of electrons or ions when a potential
difference is created. The conduct of electricity by metals takes place in solid as well as in molten
state. The conductivity of metals depends upon the number of valence electrons present in it and
the binding energy. The atomic orbitals of atoms linearly overlap to form molecular orbitals
which are very close to each other in energy to form a band. If this band is partially filled in it
overlaps with a higher energy unoccupied conduction band, then electrons can flow easily under
an applied electric field and metal behaves as good conductor. (Fig. 1.24a)
If the energy gap between filled valence band and the next higher unoccupied band is
large, electrons cannot jump to the unoccupied band. Such a substance cannot conduct electricity
and behaves as insulator. (Fig. 1.24b)
When the energy gap between the filled valence band and the next higher unoccupied
band is small, some electrons can jump to the conduction band and show some conductivity, such
substances are called semiconductors. Electrical conductivity of semiconductors increases with
the rise of temprerature because electrons acquire more energy and can jump to the conduction
band. Substances like silicon and germanium show this type of behaviour and are called intrinsic
semiconductors. The conductivity of these intrinsic semiconductors is too low to be of practical
use. Their conductivity is increased by adding an appropriate amount of suitable impurity. This
process is called doping.
Empty band Empty band
.................
................. Forbidden zone
.................
................. Small energy gap
................. (Large energy gap)
Energy
Filled band
Partially Overlapping
filled band bands
(a) Metal (b) Insulator (c) Semiconductor
Fig. 1.24 Electronic Bands of (a) Metal (b) Insulator and (C) Semiconductor
Such substances are called extrinsic or impurity semiconductors. Depending on the nature
of impurity added extrinsic semiconductros are of two types : (a) n-type extrinsic semiconductors
and p-type extrinsic semiconductors.
(a) n-Type extrinsic semiconductors :

These are obtained by adding impurity atoms having more external electrons than the
parent insulator atoms. Silicon and Germanium are insulators which belong to group 14 of the
periodic table and have four valence electrons each. When phophorous, arsenic and antimony
(all containing five valence electrons) atoms are added to pure silicon or germanium, we get
n-type extrinsic semiconductors. Each of these atoms occupy some of lattice stites in silicon
or germanium crystal. Four out of five electrons are engaged in formation of four covalent
bonds with the four neighbouring silicon atoms. The fifth extra electron is free to occupy the
lattice points. Such extra electrons occupy delocalised level, called donor impurity level which
remains just below the empty conduction band of silicon or germanium crystal.
These extra electrons can easily be excited to the empty conduction band by the
application of electric field or by increase in the thermal energy. Thus silicon or germanium
become semiconductors by doping. Here the increase of conductivity is due to the negatively
charged electron of the electron-rich impurity, hence the name n-type semiconductor. (Fig. 1.25a)
Empty Empty
conduction conduction
band band
Acceptor impurity
e e e e e level containing
Donor impurity Energy
positive holes
containing extra electron
ÅÅÅÅÅ
Filled conduction Filled valence

band band
(a) n-type semiconductor (b) p-type semiconductor
Fig. 1.25 (a) n-type semiconductor, (b) p-type semiconductor
(b) p-Type semiconductors :

These are obtained when an impurity atom to be added has fewer external electrons
than the parent insulator atoms. Silicon or Germanium can also be doped with a group 13
element like boron, aluminium or gallium which contains only three valence electrons. The
place where the fourth valence electron is missing is called electron hole or electron vacancy.
This electron vacancy creates a positive hole in the valence band of silicon or germanium.
THE SOLID STATE 21
There are as many positive holes as there are impurity atoms. These positive holes occupy the
level, called acceptor impurity level which exists close to the filled valence band of the
acceptor crystal. Electrons from the filled valence band can thermally be promoted to this
empty acceptor impurity level of positive holes.
Under the influence of an applied potential an electron from an adjacent atom moves
into the hole and in turn is replaced by an electron from another atom. In this way the molecule
move across the crystal in a direction which is opposite the direction of electron migration.
The conduction takes place due to the migration of the positive holes. Hence the name p-type
is given to these extrinsic semiconductors. (Fig. 1.25b)
Various combination of n-type and p-type semiconductors are used for making electronic
components. Diode is a combination of n-type and p-type semiconductors and is used as
rectifier. Transistors are made by placing one type of semiconductor between two other type,
such as npn or pnp semiconductors. These are used to detect or amplify radio or audio signals.
Solar cell is an efficient photodiode used for coversion of light energy into electrical energy.
Magnetic properties of solids :

Magnetic properties of solids generate due to the movement of electrons in an atom.
An electron has two types of motion (i) revolution around the nucleus and (ii) spinning along
its own axis. Since electron is a charged body its movement generates magnetic field. It
behaves like a tiny bar magnet and possesses magnetic moment. The magnitude of the magnetic
moment is very small and is measured in the unit called Bohr magneton. It is equal
to 9.27 × 10–24 Am2.
On the basis of the magnetic properties, substances can be classified into five categories :
(a) paramagnetic (b) diamagnetic (c) ferromagnetic (d) anti-ferromagnetic and (e) ferrimagnetic.
(a) Paramagnetism : Paramagnetism is due to presence of unpaired electrons which
are attracted by the magnetic field. They are magnetised in a magnetic field in
the same direction and lose their magnetism in the absence of the field. Some
examples of paramagnetic substances are O 2, Cu2+, Fe3+, Cr3+ etc.
(b) Diamagnetism : Diamagnetism is due to the presence of all paired electrons in
a substance. These substances are weakly repelled by magnetic field. H 2O, NaCl
and benzene are some examples of such substances. They are weekly magnetised
in a magnetic field in opposite direction. Pairing of electrons cancels their magnetic
moment and they lose their magnetic character.
(c) Ferromagnetism : Ferromagnetic substances are strongly attracted by magnetic
field. Besides strongly attracted these substances can be permanently magnetised.
In solid state, the metal ions of ferromagnetic substances are grouped together in
small regions called domains which act as tiny magnets. In an unmagnetised
ferromagnetic substance these domains remain randomly oriented and their
magnetic moments are cancelled. When the substance is placed in a magnetic
field all the domains get oriented along the direction of the magnetic field and
a strong magnetic effect is produced. This order of the domains remains as such
even after the magnetic field is withdrawn and the ferromagnetic substance
becomes permanently magnetic. Iron, cobalt, nickel, gadolinium and CrO 2 are
examples of ferromagnetic substances.
(d) Anti-ferromagnetism : Substances like MnO have their magnetic domain structure
similar to ferromagnetic substances, but their domains are oppositely oriented
and cancel out each others magnetic moment.
(e) Ferrimagnetism : Ferrimagnetism is observed when the magnetic moments of
the domains in the substance are alligned in parallel and anti-parallel directions
in unequal numbers. They are weakly attracted by magnetic field as compared to
ferromagnetic substances. Magnetite (Fe3O4) is such a substance. These substances
lose ferrimagnetism on heating and become paramagnetic.
(a) Ferromagnetic
(b) Anti-ferromagnetic
(c) Ferrimagnetic
CHAPTER (1) AT A GLANCE

1. Solids are characterised by definite shape, definite volume and fixed melting point.
Compressibility, rigidity, high mechanical strength are the properties of a solid.
2. Solids are classified as crystalline and amorphous solids.
3. Crystalline solids have definite geometry, sharp melting point and crystal symmetry.
They are anisotropic an nature.
4. Amorphous solids have neither definite geometry nor sharp melting point. They do not
possess symmetry and are isotropic in nature.
5. Crystalline solids are classified as ionic, covalent, molecular and metallic solids.
6. Ionic solids are hard, brittle, possess high melting point. Covalent solids are hard,
nonvolatile, bad conductors of heat and electricity. Metallic solids are malleable and
ductile, have metallic lusture and are good conductors. Molecular solids are soft and
volatile and bad conductors.
7. A crystal lattice is regular arrangement of the constituent particles (atoms, ions or
molecules) of a crystalline solid in three dimensional space.
8. The positions that are occupied by the atoms, ions or molecules in the crystal lattice
are called lattice points or lattice sites.
9. Unit cell is the smallest repeating unit in crystal lattice which when repeated over and
over again produces the complete crystal lattice.
THE SOLID STATE 23
10. Close packing in two dimensions in crystalline solids may be square close packing
(scp) or hexagonal close packing (hcp).
11. In three dimension close packing ABABA ... arrangement is known as Hexagonal
Close Packing (hcp), whereas ABCABCA... is known as Cubic Close Packing (ccp)
12. There are three common types of cubic systams. They are Simple Cubic, Body Centred
Cubic (bcc) and Face Centred Cubic (fcc).
13. The no. of atoms per unit cell in simple cubic, body centred cubic and face centred
cubic crystals are 1, 2 and 4 respectively.
14. The hollows or voids in the crystal are known as interstitial voids. These voids may
be tetrahedral or octahedral.
15. The number of nearest neighbours with which a given sphere is in contact is known
as the co-ordination number.
16. Radius ratio = Radius of cation

Radius of anion
17. On the basis of electrical conductivity, solids are divided into three categories :
(i) Metals (ii) Insulators (iii) Semiconductors. Free electrons in the metals are responsible
for conduction of electricity. Conductivity of semiconductors is intermediate between
metals and insulators. Semiconductors are of two types : Intrinsic and Extrinsic. Extrinsic
semiconductors are either n-type or p-type. Their combinations are used in making
electronic components.
18. On the basis of magnetic properties, solids are classified into five categories :
Paramagnetic, Diamagnetic, Ferromagnetic, Anti-ferromagnetic and Ferrimagnetic.
QUESTIONS
A. Very short answer type (One mark each) :
1. Diamond and graphite are —————. (allotropes, isomorphous)
2. Diamond is ————— solid. (co-valent, ionic, molecular)
3. What is the number of atoms present per unit cell in a face centred cubic and a body
centred cubic arrangement.
4. What is the radius ratio for an ion to occupy tetrahedral site.
5. Explain isotropy.
6. Define Anisotropy.
7. Define a unit cell of a crystal.
8. What are interstitials ?
9. What are the types of lattice imperfections found in crystals ?
10. What do you mean by crystal lattice ?

11. How many types of close packing are known in crystals ?
12. Define co-ordination number of a crystal.
13. Explain interstitial voids.
14. How many types of lattice points occur in diffrent cubic unit cells ?
15. What is the number of atoms in a body centred cubic unit cell of a monoatomic
substance ?
16. What is a polycrystalline solid ?
17. What are crystallites ?
18. Calculate the number of atoms contained in body centred cubic cell.
19. Give two examples of ionic solids.
20. Diamond, Graphite and Quartz are ————— solids.
21. Define metallic solids.
22. What is meant by molecular solids ?
23. What is meant by radius ratio ?
24. Why carbon tetrachloride is immiscible in water ?
25. The solubiltiy of a solid ————— by increase of pressure. (increased, not changed,
decreased)
26. What is the effect of pressure on the solubility of a solid ?
27. What happens to the solubility of calcium acetate if temperature increases
28. Give two examples of molecular solid.
29. Give an example of hcp and bcc crystals.
30. What is the commercial name of SiC ?
31. What are the coordination numbers of Cs+ & Cl– in CsCl lattice ?
B. Short Answer Type (Two marks each) :

1. Give two points of difference to distinguish between crystalline and amorphous solids.
2. If the radii of the cation and anion are 95 pm and 181 pm respectively, what would
be coordination number and the type of crystal geometry?
3. Explain how hcp or ccp for the some element give the same identity?
4. What should be the ideal radius of the anion in a NaCl type of structure if the radius
of the cation is r ?
+
5. Calculate the radius ratio rr– and the condition number of Li+ and F– in LiF crystal from
the given data rLi+ = 60 pm and rF– = 136 pm.

6. Silver crystallises in fcc lattice with all the atoms at the lattice points. The length of
the edge of the unit cell as determined by x-ray diffraction studies is found 408.6 pm.
the density of silver is 10.5g cm–3 . Calculate the atomic mass of silver.
THE SOLID STATE 25
7. Explain the difference between conductor and insulator.

8. Explain the difference between conductor and semiconductor.
9. Explain the following :
(i) Ferromagnetism
(ii) Paramagnetism
(iii) Antiferromagnetism
(iv) Ferrimagnetism
10. What are interstitials and interstitial voids ?
C. Short answer type (Three marks each) :

1. Write four important characteristics of solids.
2. Write two points to distinguish between Crystalline and Amorphous solids.
3. What are chief characteristics of ionic crystals ?
4. Describe a few general characteristics of covalent crystals.
5. What are molecular crystals ? How many types of molecular crystals are known ?
6. Explain metallic crystals and their properties ?
7. What do you understand by the terms space lattice and unit cell. ?
8. Define co-ordination number in crystals. Is the co-ordination number of a sphere in ccp
and hcp arrangement same or different ?
9. Discuss the following types of cubic structures :
a. Simple cubic
b. Body centred cubic.
c. Face centred cubic.
10. How does radius ratio help in determining the structures of compounds ?
11. What are interstitial sites ? Discuss tetrahedral and octahedral interstitial sites in a
closed packed arrangement.
12. Explain why diamond is hard while graphite is soft.
D. Long answer type (Seven marks each) :

1. Describe various characteristics of solids.
2. What do you understand by close packing of spheres ? Discuss briefly hexagonal close
packing and cubic close packing of spheres.
3. Describe fcc, bcc and hcp crystals of simple ionic compounds.
4. Discuss the characteristics of solids. Give the classification of solids into ionic, covalent,
molecular and metallic solids.
5. Explain the crystal defects and their origin in the crystal.
E. Multiple choice answer type (One mark each) :

1. The number of atoms in bcc arrangement is
(a) 1 (b) 4 (c) 2 (d) 6
2. In hcp mode of stacking, a sphere has co-ordination number.
(a) 4 (b) 6 (c) 8 (d) 12
3. If edge of a bcc crystal of an element is 'a' cm, M is the atomic mass and 'N' is the
Avogadro number, then density of the crystal is
(a) a43M 2N 2M
N (b) Ma 3 (c) N a 3 (d) 2N
Ma 3
4. The unit cell with crystallographic dimensions a = b F c, a = b = g = 900 is

(a) cubic (b) tetragonal (c) monoclinic (d) hexagonal
5. The structure of sodium chloride is
(a) Hexagonal (b) Octahedral (c) Rhombohedral (d) Tetrahedral.
6. The unit cell with the structure below refers to ————— crystal system.
a b
0
90 0 90 c
90 0
(a) cubic, (b) orthorhombic (c) tetragonal (d) trigonal

7. The arrangement ABC ABC...... is referred to as
(a) Octahedral close packing (b) Hexagonal close packing
(c) Tetrahedral close packing (d) Cubic close packing
8. Which among the following will show anisotropy ?
(a) glass (b) barium chloride (c) wood (d) paper.
9. For an octahedral arrangement the lowest radius ratio limit is
(a) 0.155 (b) 0.732 (c) 0.414 (d) 0.225
10. The number of octahedral voids in a unit cell of a cubic close packed structure is
(a) 2 (b) 3 (c) 4 (d) 6
ANSWER TO MULTIPLE CHOICE TYPE QUESTION
1. c 4. b 7. d 10. c
2. d 5. b 8. b
3. c 6. a 9. c
qqq
UNIT - II
CHAPTER - 2
SOLUTIONS
A solution is a homogeneous mixture of two or more substances whose composition

can be varied within certain limits. Depending upon the total components present in the
solution, it is called binary (two components), ternary (three components), quaternary solution
(four components) etc.
2.1 CHARACTERISTICS OF A SOLUTION :

1. It has no surface of separation. As a result the various constituents in it can not be
distinguished.
2. The constituents can neither be separated by filtration nor do they settle down under
the effect of gravity.
3. The constituents in it can be obtained by processes like crystallisation, distillation,
evaporation etc.
4. The various constituents in a mixture show the properties to prove their presence.
Example :
When sodium chloride dissolves in water, the solution will show the properties of both
NaCl and water .
Solute, Solvent and Solution :
Solute : It is a substance that dissolves in a solvent.
Solvent : It is a substance in which dissolution takes place.
Therefore, solute + solvent = solution.
Further, the components of a binary solution are generally referred to as solute and
the solvent.
Types of solutions :
Depending upon the physical states of the solute and the solvent the solutions can be
classified into the following nine types.
Table 2.1 Types of Solutions

Solvent Solute Example
Gas Gas Mixture of gases, air
Gas Liquid Water vapour in air (humidity)
Gas Solid Sublimation of a solid into gas, dust particles in air.
Liquid gas CO2gas dissolved in air
Liquid Liquid Mixture of miscible liquids (alcohol in water)
Liquid Solid Salt in water, sugar in water
Solid Gas Adsorption of gases over metal (H2 over palladium)
Solid liquid Mecury in copper
Solid Solid Alloys (copper in gold), zinc in copper.
The solutions in which water is a solvent are called aqueous solutions while those in
which water is not the solvent are called non-aqueous solutions.
Examples of non-aqueous solvents are ether, benzene, carbon tetrachloride etc.
Unsaturated, Saturated and Supersaturated solutions :

When the quantity of the solute is very small as compared to the solvent, it is called
dilute solution. It can dissolve more of the solute at that temperature. Such solutions are
called unsaturated solutions.
Unsaturated solution :
The solution in which more quantity of the solute can dissolve at that temperature is
called unsaturated solution.
When more solute is added it will also dissolve. If the addition of solute is continued,
a stage will reach, when the solvent refuses to dissolve the solute at that temprature. That
stage of the solution is termed as saturated solution.
Saturated solution :
The solution in which no more quantity of the solute can dissolve at room temprature
is called as saturated solution.
When a saturated solution is heated slowly, the solvent starts evaporating from it. In
other words, the quantity of solvent starts decreasing while that of the solute remains the
same. After sometime, stop heating the solution. At this stage, a solution is obtained which
contains more solute than needed for preparing a saturated solution at that temperature. This
solution is called super saturated solutions.
SOLUTIONS 29
2.2 SOLUBILITY :
Definition : The weight in grams of a substance (solute) which when dissolved in 100 gms
of a solvent forms a saturated solution at a particular temperature, is called solubility
of the substance (solute) at that temperature.
wt (in grams) of solute
Hence, solubility = 100 x
wt (in grams) of solvent
Let 'm' grams of a solid be present in M grams of its saturated solution at t 0C. Then
taking 'X' as the solubility of the solid at t 0C, we find that
100m
X= (M - m)
Solubility Rules :
It is a fact that polar solids are soluble in polar solvents while non-polar solids are
soluble in non-polar solvents. Further, the following generalisations are also true.
(i) An ionic solid is soluble in polar solvent :

Ionic solids contain oppositely charged ions and held by electrostatic force of attraction
in the crystal. Example : In NaCl, Na+ and Cl– are present. When such substance is added to
water, attraction of water molecules for the ions is greater than the electrostatic attraction.
(ii) Ionic solids are insoluble in non-polar solvents :

In non-polar solvents like CCl4, benzene etc, the attractive force between the molecules
is very weak. Hence molecules of non-polar solvents can not pull an ion form the ionic solid.
Thus ionic solids like NaCl, KCl etc are not soluble in non-polar solvents.
(iii) Non-polar covalent solids are soluble in non-polar solvents :

The molcules of both non-polar covalent solutes and solvents are held by weak attractive
forces. As the attractive forces between the molecules of non-polar solutes and solvents are
of the same order, covalent solids are readily soluble in non-polar solvents. Iodine, wax etc
are freely soluble in benzene, carbon tetrachloride etc.
Determination of solubility of a solid like common salt in water at the temperature of

the laboratory :
It involves the following steps.
(a) Preparation of a saturated solution :
Take about 100 ml of water in a beaker and warming a little, go on adding the salt
with constant stirring till some of the salt remains undissolved and settle down without going
into solution. Cool the saturated solution thus prepared to room temperature. Filter it and note
the temperature of the filtrate ( t 0 C).
(b) Estimation of the masses of the salt and solvent :

Take a clear and dry procelain basin and weigh it accurately. Take about 10 ml of the
solution in it by a pipette and weigh again. Then evaporate the solution on a water bath
carefully. When the salt is left in the basin, dry the basin with the residue in an air oven. Cool
it in a desiccator and weigh again. Repeat the process of heating cooling and weighing till the
final weight is constant.
(c) Calculation :
Room temperature = t0C
Mass of the empty porcelain basin = W1 gms.
Mass of the basin + saturated solution = W2 gms.
Mass of the basin + residue = W3 gms.
\ Mass of residue = (W3 – W1) gms.
Mass of water = (W2 – W3) gms.
(W3 - W1)
\ Solubility = (W2 - W3)
x 100 at t0C.
Problem :
28 gms of a saturated solution of a substance contain 3 gms of the solute at 300K.
Calculate the solubility of the solute at the temperature.
Solution : Mass of solution = 28 gms.
Mass of solute = 3 gms.
\ Mass of solvent = (28–3) = 25 gms.
\ Solubility = 253 x 100 = 12
\ Solubility of the solute at 300K = 12

Effect of temperature and pressure on solubility :
(a) Effect of temperature :
When the temperature of a saturated solution is raised, it is observed that more solute
can be dissolved in the same solution. Solute separates out from it on cooling. Thus, it can
be said that solubility of a substance depends on the temperature. (Fig. 2.1)
TEMPERATURE 0C 2
Fig. 2.1 Solubility versus Temperature

SOLUTIONS 31
Again solubility of a substance may increase or decrease with temperature depending

on the heat of solution. If the heat of solution is negative (m H = – ve) or heat is evolved,
the solubility decreases with increase in temperature. Similarly, if m H is +ve i.e. heat is
absorbed in solution, then the solubility increases with increase in temperature.
Salts like KNO3, KCl, NH4Cl, NH4NO3 etc show increase in solubility with increase
in temperature. In those cases, m H is +ve. A few substances like Na2SO4, calcium acetate Ca
(CH3COO)2 etc dissolve in water with evolution of heat i.e. m H is –ve. In all those cases,
the solubility decreases with the increase in temperature.
(b) Effect of pressure :
It is known that if the solute is a solid or a liquid, pressure has no effect on solubility.
But if the solute is a gas, the pressure influences solubility according to Henry's law. The law
states that the amount of gas dissolved in a given volume of liquid at constant temperature
is directly proportional to the pressure of the gas. The law is strictly applicable to slightly
soluble gases at low pressure but for highly soluble gases such as ammonia, HCl etc, the law
does not hold good.
2.3 CONCENTRATION OF A SOLUTION :

The strength of a solution also called as the concentration can be defined as the
quantity of the solute in a given quantity of the solvent or solution.
Standard solution is a solution whose strength is known. Thus, 8 g of NaOH present
in 500 ml of the solution is a standard solution.
There are various ways in which the concentration of a solution can be expressed. The
common types are :
1. Grams per litre
2. Normality (N)
3. Molarity (M)
4. Molality (m)
5. Mole fraction (X)
6. Per cent solution.
7. Formality (F)
1. Grams per litre : Here, the strength of the solution is expressed as the amount of
solute in grams present in a litre of the solution.
If 4.9 g of H2SO4 is present in one litre of the solution, then the strength is written
as 4.9 g/litre. Similarly, if 1g. of NaOH is present in 250 ml of the solution, then the
strength is written as 4g/litre. (1g/250 ml = 4g / litre).
Thus, if W g of the solute is present in V ml of the solution, the strength is written
as ( W
V
x1 0 0 0) g per litre.
2. Normal solution and normality : A normal solution of a substance (acid, base or

salt) is one which contains one gram - equivalent of the substance in one litre of the
solution. Thus, Normality is the number of gram - equivalent of the solute present
in a litre of the solution. It is denoted by N. If one gram equivalent of the solute is
present in one litre of the solution, it is called (N) solution. Thus, 1000 ml of (N)
H2SO4 shall contain 49.g. of H2SO4, 1000 ml of (N) Na2CO3 shall contain 53g of
Na2CO3 and 1000 ml of (N) BaCl2. 2H2O shall contain 122 g of BaCl2. 2H2O.
Sometimes, a normal solution becomes stronger for analytical purpose and diluted
solutions like one-half (semi), one - tenth (deci) or one - hundredth (centi) of a normal
solution are used.
Thus, 1000 ml. of (N) H2SO4 (one normal) solution shall contain 49g of H 2SO4
1000 ml of ( N 49
2 ) H2SO4 (semi - normal) solution shall contain 2 = 24.5g of H2SO4
49
1000 ml of N H2SO4 (deci - normal) solution shall contain
10 = 4.9 g of H2SO4.
10
N 49
1000 ml of ( 100 ) H2SO4 (centi - normal) solution shall contain 100 = 0.49 g of H2SO4.
and 1000 ml of 2(N) H2SO4 shall contain 2 x 49 = 98g of H2SO4 .
Therefore, the 'normality' or 'normality factor' of the above solution will be 1, 1/
2, 1/10, 1/100 and 2 respectively. Hence, if W grams of the solute with equivalent mass Z are
present in Vml of the solution, then
Grams per litre
Normality factor = W 1000
Z x V = Equivalent mass of the solute .
Therefore, Grams/litre = Normality x Equivalent mass.
It will be seen that 1000ml of (N) H2SO4 will contain 49 g of H2SO4 and 500ml of a 2(N)
H2SO4 will contain 49g of H2SO4.Therefore, both the solutions are equivalent. This is written as
1000 ml of (N) H2SO4 º 500 ml of 2(N) H2SO4.
Similarly. 250 ml of (N) H2SO4 º 1000 ml of (N/4) H2SO4.
We find that
250 ml. of (N) H2SO4 º 50 ml of 5(N)H2SO4.
º 25 ml of 10(N)H2SO4.
º 500 ml of (N/2)H2SO4.
º 1000 ml of (N/4)H2SO4.
In general. V ml of x(N) H2SO4 º (V x x) ml of (N) H2SO4.
Problem 1. How much NaOH is present in 100 ml of (N) solution ? (CHSE, 1990A)
Solution : Equivalent mass of NaOH = 40

1000 ml of (N) NaOH will contain 40g of NaOH
40
100 ml of (N) NaOH will contain 1000 x 100 = 4g of NaOH.
SOLUTIONS 33
Problem 2. Find out the weight of NaOH required to prepare 2 litres of N/10 solution.
Solution : Equivalent mass of NaOH = 40
1 litre of (N) solution of NaOH will contain 40 g of NaOH.
2 litres of (N/10) solution will contain 4010x 2 = 8 g of NaOH.

Hence, 8g of NaOH will be required to prepare 2 litre of (N/10) solution.
Problem 3. 12 g of H2SO4 is dissolved in water to make 1200 ml of solution. Find out the
normality of the solution.
Solution : Equivalent mass of H2SO4 = 49
49 g of H2SO4 in 1000 ml will give (N) solution.
12
12 g of H2SO4 in 1000 ml will give 49 (N) solution.
x 1000
12 g of H2SO4 in 1200 ml will give 12
49 x 1200 = 0.204 (N) solution.
Hence, the normality of the solution is 0.204.
3. Molar solution and Molarity : A molar solution is one which contains one gram
mole of the solute in a litre of the solution. Thus, Molarity (M) is the number of moles
of the solute present per litre of the solution.
If Wg of the solute having the molecular mass m is present in V ml of the solution,
then
No of moles of the solute
Molarity (M) = Volume of the Solution in ml
´ 1000
1
= W
m
´ V ´ 1000
(Mass of the solute / mol. mass of the solute gives the number of moles of solute)
Grams per litre
or, Molarity (M) = Molecular mass of the solute .
Molarity is extensively followed in practice since it is a convenient measure of

concentration. Molarity of the solution changes with temperature because the volume of the
solution expands or contracts with the increase or decrease in temperature.
NOTE : Grams/litre = Normality ´ Equivalent mass = Molarity ´ Molecular mass.
Hence, Normality/Molarity = Molecular mass/Equivalent mass.
Problem 1. 4g of NaOH is present in 200 ml of a solution. Find out the molarity.
Solution : Molecular mass of NaOH = 40.
40 g of NaOH in 1000 ml of the solution give 1M solution.
1 4
4 g of NaOH in 200 ml will give ( 40 ´ 200 ´ 1000) M = 0.5 (M) solution.
Hence, molarity of the solution is 0.5.
Problem 2. How many grams of Na2CO3 is required to make 600 ml. of 0.04 (M) solution ?
Solution : Molecular mass of Na2CO3 = 106
1000 ml of 1 (M) Na2CO3 will contain 106 g of Na2CO3
600 ml of 0.04 (M) Na2CO3 will contain 106 ´ 600 ´ 0.04 g = 2. 544 g of Na2CO3.
1000
Hence. 2.544 g of Na2CO3 is required.
Problem 3. What will be the molarity of sulphuric acid if 0.8 g of sulphur trioxide is
dissolved in 100 ml of water ? (At mass of S = 32)
Solution : Mol. mass of SO3 = 32 + (3 ´ 16) = 80
0.8
0.8 g of SO3 will contain 80 = 0.01 mole of SO3
SO3 + H2O ® H2SO4
1 mole of SO3 = 1 mole of H2SO4
1 mole of SO3 in 1000 ml of water will produce 1(M) H2SO4
0.01 mole of SO3 in 100 ml of water will produce 0.1 (M) H2SO4
Hence, molarity of sulphuric acid is 0.1.
Problem 4. Calculate the molarity of water in pure water. (IIT, 1976 A)
Solution : Molarity is the number of moles of H2O per litre of pure water. Since one mole
of H2O = 18g and 1 litre of pure water » 1000 g (Roughly 1 ml = 1g)
Hence, molarity of H2O in pure water = 1000
18
= 55.55.
4. Molal solution and Molality : A molal solution is one which contains one gram mole
of the solute in 1000 g of the solvent. Thus, molality (m) is the number of moles of
the solute in 1000 g of the solvent.
If W1 g of the solute having molecular mass M 1 is present in W2 g of the solvent, then
1000 W1
Molality (m) = W 1
M1 ´ W2 ´ 1000 = M ´W
1
1 2
The molality of the solution does not change with the change in temperature of
the solution.
Problem 1 . Calculate the molality of sodium carbonate solution which is formed by
dissolving 1.325 g of it in 250 g of water.
Solution : Molecular mass of Na2CO3 = 106
106 g of Na2CO3 in 1000 g of water gives 1 m solution
1325
.
1.325 g of Na2CO3 in 250 g of water will give 106 ´ 1000
250 (m) = 0.05 (m) solution.
Hence, molality of the solution = 0.05
SOLUTIONS 35
5. Molefraction : Molefraction of the solute (Xsolute) or solvent (Xsolvent) is the ratio of the
number of moles of the solute or solvent to the total number of moles of solute and
solvent in the solution.
Thus.
no. of moles of the solute
Xsolute = molefraction of the solute =
no. of moles of solute + no. of moles of solvent
no. of moles of the solvent
and Xsolvent = molefraction of the solvent =
no. of moles of solute + no. of moles of solvent
If W1 g of solute of molecular mass M1 is present in W2 g of solvent having molecular

mass M2 then molefraction of the solute,
W1 / M1 W1 / M1 W M1M 2 W1M 2
Xsolute = =
+
= 1´ =
W1 / M1 + W2 / M 2 W M
1 2 W M
2 1 M1 W1M 2 + W2 M1 W1M 2 + W2 M1
M1M 2
Smilarly, the molefraction of the solvent
W2 / M 2 W2 M1
Xsolvent = =
W1 W2 W1M 2 + W2 M1
+
M1 M 2
[Note - Molefraction of solute + Molefraction of solvent = 1]
Problem 1 : Calculate the molefraction of NaOH is an aq. NaOH solution which contains
2.0 g of it in 150 ml of solution. (Density of the solution = 1.25 g/ml)
Solution Mass of NaOH = 2 g
Molecular mass of NaOH = 40
2
\ No. of mole of NaOH = 40 = 0.05
Volume of the solution = 150 ml. and
Density of the solution = 1.25 g / ml.
\ Mass of the solution = Volume x density = (150 x 1.25)g = 187.5 g
Mass of solvent (water) = 187.5 g – 2 g = 185.5 g
185.5g
\ No. of moles of solvent = 18g = 10.3
no.of moles of NaOH
Molefraction of NaOH = no.of moles of NaOH + no.of moles of H O
2
= 0.050.+0510.3 = 4.83 x 10–3.
6. Per cent solution :
This way of expressing concentration can be of four types :
(a) Mass to mass percentage : The number of grams of solute in 100 grams of the solution
mass of solute in g
determines the percentage of a solution (w/w). = Mass of solution in g ´ 100.
(b) Mass to volume percentage :- The number of grams of solute in 100 ml of the solution
mass of solute in g
determines the percentage of a solution (w/v) = ´ 100.
volume of solution in ml
(c) Volume to volume percentage (for liquids) : - The number of ml. of solute in 100 ml of the
volume of solute in ml
solution determines the percentage of a solution (v/v) = ´ 100.
volume of solution in ml
(d) Volume to mass percentage :- The number of ml of solute in 100 g of the solution
volume of solute in ml
determines the percentage of a solution (v/w) = mass of solution in g
´ 100
Thus, 5% solution (w/w) of NaOH will mean 5 g of NaOH in 100 g of NaOH solution.
Similarly, 80% H2SO4 solution (v/v) will mean 80 ml of H2SO4 in 100 ml of H2SO4 solution
and so on.
7. Formality :
Formality (F) is defined as the number of formula mass of the solute per litre of the solution.
W ´ 1000
F= where W = mass of solute in g.
M´V
M = Formula mass of solute in g.
V = Volume of solution in ml.
5.85 ´ 1000
Thus, 5.85g of NaCl in 500 ml of the solution will give = 0.2 F solution of NaCl
58.5 ´ 500
(formula mass of NaCl is 58.5)
In most of the cases formality is same as molarity.
8. Parts per million : When a solute is present in a very small amount (trace amount) in a
solution, its concentration is expressed in terms of parts per million (ppm). It is defined
as the number of parts by mass of the solute present in one million (10 6) parts by mass of
the solution. Thus,
mass of the solute
ppm = × 106
mass of solution
Dissolved oxygen in sea water is 5.8 ppm, which means that 5.8g of oxygen is dissolved
in 106 g of sea water.
Atmospheric pollution in cities is expressed in terms of ppm by volume. It refers to the
volume of pollutant in 106 units of volume. 15 ppm SO2 in air means 15mL of SO2 is present in
106 mL of air.
Interrelations between various concentration terms
We have already found that
Grams per litre = Normality × Equivalent mass of solute
= Molarity × Molecular mass of solute
SOLUTIONS 37
Nomality Molecular mass

=
Molarity Equivalent mass
Relationship between Molality and Molarity
moles of solute
Molarity = Vol. of solution (in L)
moles of solute
Molality=
mass of solvent in kg
Molarity moles of solute mass of solvent (in kg )

= ×
Molality Vol. of solution (in L) moles of solute
mass of solvent(in kg ) mass of solvent (in g ) W

= = = 2
Vol. of solution (in L) Vol. of solution (in mL) V
where W2 = mass of solvent in grams and

V = volume of solution in mL.
If the density of the solution is d gmL–1
Mass of solution = d × V
Mass of solute = No. of moles ×mol. mass of solute = n × M1
Mass of the solvent = W2 = mass of solution – mass of solute
= d × v – n M1
Molarity M V× d nM 1
Thus, = =
Molality m V
Molarity× V molarity molarity

Hence, Molality (m) = = =
V× d nM 1 d n M d molarity× M 1
1
V
Relationship between molefraction and molality

Suppose XA = mole fraction of the solute and
XB = mole fraction of the solvent.
No. of moles of solute

XA =
No. of moles of solute+ No. of moles of solvent
No. of moles of solvent

and X B =
No. of moles of solute+ No. of moles of solvent
XA No. of moles of solute

=
X B No. of moles of solvent
If W1 = mass of solute with molecular mass M 1 and

W2 = mass of solvent with molecular mass M 2
X A W1 × M 2
=
X B W2 × M1
XA× 1000 W1× 1000

= =m
XB× M2 W2× M1
X A × 1000
or, =m
(1 X A )× M 2
Miscellaneous problems involving determination of concentration :
Problem 1 : What is the molarity and molality of a 13% solution (by mass) of H 2SO4 ? Its
density is 1.02 g / ml. To what volume should 100 ml of this acid be diluted
in order to prepare a 1.5 (N) solution ? (I.I.T., Adm. Test, 1978 B)
Solution : 13% H2SO4 (by mass) means
Mass of H2SO4 = 13 g
Mass of solution = 100 g
Molecular mass of H2SO4 = 98
mass 100g
Volume of the solution = density = 1.02g / ml = 98.04 ml.
Thus, 98.04 ml of H2SO4 contain 13 g of H2SO4

13 ´ 1000
\ 1000 ml of H2SO4 will contain g of H2SO4 =132.6 g of H2SO4
98.04
132.6
132.6 g H2SO4 = moles = 1.35 moles of H2SO4.
98
\ 1000 ml of H2SO4 will contain 1.35 moles of H2SO4.
Hence. molarity = 1.35
Mass of 1000 ml of H2SO4 soln.= 1000 ´ 1.02 = 1020 g
Mass of H2SO4 in 1000 ml of H2SO4 soln = 132.6 g
\ Mass of solvent = (1020 – 132.6) g = 887.4 g
887.4 g of solvent contain 132.6g of H2SO4 or 1.35 moles of H2SO4 .
. ´ 1000
135
\ 1000 g of solvent will contain = 1.52 moles of H2SO4 .
887.4
Hence, molality = 1.52
Equivalent mass ´ Normality = g/litre
SOLUTIONS 39
g / litre 132.6
or, Normality = Equivalent mass = 49 = 2.71
Hence, Normality of the solution = 2.71.

100 ml of 2.71(N) will be diluted to give 1.5(N) H2SO4.
Suppose V ml = Volume of the diluted acid.
Then, 100ml ´ 2.71 (N) = V ml ´ 1.5(N)
100ml ´ 2.71(N)
or, V= 1.5(N)
= 180.67 ml.
Therefore, 100 ml of this acid must be diluted to 180.67 ml or 180.7ml.

Problem 2 : Calculate the molefraction of a 90% ethyl alcohol (by mass) solution.
Solution : 100 g of ethyl alcohol solution will contain 90 g of ethyl alcohol and 10g of water.
Mol. mass of ethyl alcohol (C2H5OH) = 24 + 6 + 16 = 46
and of water (H2O) = 2 + 16 = 18.
\ No of moles of C2H5OH per 100 g of solution = 90
46 =1.96
10
and No. of moles of H2O per 100 g soln = 18 = 0.56
1.96
Hence. mole fraction of ethyl alcohol = 1.96 0.56 = 0.78
+
0.56
and mole fraction of water = 1.96 0.56 = 0.22
+
Problem 3 : Calculate the normality of the resulting solution obtained by mixing 10cc of
N/2 HCl with 30cc of N/10 H2SO4 and 40cc of N/20 HNO3.
Solution : Total volume of the acid = (10 + 30 + 40)cc = 80 cc.
10cc of N/2 HCl º 5cc of (N) HCl
30cc of N/10 H2SO4 º 3cc of (N) H2SO4
and 40cc of N/20 HNO3 º 2cc of (N) HNO3
Suppose the normality of the resulting solution = x
\ 80cc of x (N) º 10 cc of (N) acids
or, x = 10
80 = 0.125
Hence, the normality of the solution = 0.125
SVS
Alternately, N = Total volume = 10
80 = 0.125
Hence, the strength of the resulting acid solution is 0.125 (N)
2.4 SOLUBILITY OF GASES IN LIQUIDS :

Most of the gases are soluble in water as well as in other liquids to a more or less extent.
The solubility of a gas in liquids depends upon
(i) Nature of the gas

(ii) Nature of the solvent
(iii) Temperature of the gas- liquid system
(iv) Pressure of the gas
Generally, the gases which are easily liquified, are more soluble in common solvents.
Thus CO2 is more soluble in water or in any other solvent than hydrogen or oxygen. The gases
which are capable of forming ions in aqueous solutions are more soluble in water than in any
other solvent. Gases like HCl and NH3 are highly soluble in water, but not in organic solvents in
which they do not ionise.
The solubility of most of the gases decreases with increase in temperature at constant
pressure. When the temperature increases gas is expelled. However, some gaes are more soluble
at higher temperature.
The solubility of a gas in liquid is considerably influenced by presure. William Henry, in
1805 found that at a given temperature the solubility of a gas increases directly as the pressure.
This is known as Henry’s law, which states that the mass of a gas dissolved by a given volume
of liquid at constant temperature, is proportional to the pressure of the gas.
Therefore, if m be the mass of gas dissolved per unit volume of the liquid and P is the
pressure of the gas in equilibrium with the solution, then according to Henry’s law.
m a P at constant temperature.
or, m = kP where, k is the proportionality constant.
m
or, =k
P
It has been found that most of the gases obey Henry’s law provided
(i) the pressure is not too high
(ii) the temperature is not too low
(iii) the gas is not highly soluble and does not chemically combine with the solvent.
(iv) the gas does not dissociate.
Henry’s law may also be stated in terms of the volume of gas dissolved instead of mass.
Suppose m grams of a gas occupying a volume VmL is dissolved in a given volume of the
solvent at an equilibrium pressure of the gas (P). Keeping the temperature constant, if the pres-
sure is increased to 2P, the mass of gas dissolved in the same volume of solvent will be 2m,
which corresponds to a volume 2V at pressure P. But the new volume of the gas passing into the
solution at pressure 2P will be ½ ×2V = V, since according to Boyle’s law, volume varies in-
versely as the pressure. Thus the volume of the gas dissolved will remain same as before inspite
of increase in pressure. Henry’s law, therefore, may also be stated as the volume of gas dis-
solved in a solvent at a given temperature is independent of the pressure.
2.5 VAPOUR PRESSURE :

When a liquid is placed in an open vessel exposed to atmosphere, it gradually
disappears. The change of liquid into gas is known as evaporation. At constant temperature,
SOLUTIONS 41
when the evaporation of a liquid takes place in a closed container, the molecule that escape
from the surface of the liquid are trapped in the container and occupy the space above the
surface of the liquid. The molecules collide with each other and with the walls of the container.
A few of them may also hit the surface of the liquid and return to it resulting in condensation.
The rate of return of molecules in vapour state (condensation) is proportional to the concentration
of molecules in vapour state. Finally a stage reaches, when the rate of evaporation is equal
to the rate of condensation.
Liquid l Vapour
Ev
apo
ra t
i on
Equilibrium
Rate
on
e nsati
d
Con
Time
Fig. 2.2 Equilibrium curve for evaporation and condensation
Vapour pressure of the liquid at any given temperature is the pressure exerted by the
vapour of a liquid when it is in equilibrium. with the liquid.
Vapour pressure increases with the increase of temperature.
B.P. (Boiling point) : The temperature at which the vapour pressure of a liquid
becomes equal to the prevailing atmospheric pressure, bubbles begin to form through out the
liquid and finally boils. This temperature is called the boiling point of a liquid. Every liquid
has a standard or normal boiling point.
800 308 352 373

760
700
1 600
Pressure
er
eth
l
ho
500
yl
co
r
eth
a te
la l
400
W
hy
Di
Et
300
200
100
250 275 300 325 350 375 400

Temperature (K) ®
Fig. 2.3 Plot showing variation of vapour pressure of liquids with temperature
Boiling point is defined as the temperature at which the vapour pressure becomes
equal to the standard atmospheric pressure (760 mm). At a given temperature, the greater the
vapour pressure of a liquid, the lesser would be its boiling temperature. The pressure cookers
hasten the cooking process. In pressure cooker higher pressure is built up, consequently the
boiling temperature of liquid increases.
Molar heat of vapourisation is the quantity of heat supplied to one mole of a liquid
at its boiling point so as to change it into vapour state at the same temperature.
2.6 IDEAL AND NON-IDEAL SOLUTIONS :

Ideal solutions
An ideal solution of component A and B means that the force of attraction between A and
B molecules (i.e. A – B molecular interaction forces) will be the same as those for the A – A or B
– B molecules. For such a situation to occur, the component should have identical structure and
polarity. As there is no change in interaction forces between two components when they are
mixed to form ideal solution, heat change on mixing (DH mixing) will be zero. Moreover, in such
cases, the volume of the solution is the sum of the volumes of the components before mixing.
Thus volume change on mixing (DVmixing) is zero. To sum up, the conditions for an ideal solution
formation are
o
III PB
+ PB
VAP. PRES
P = PA
II
PB
o
PA
PA
I
xA = 1 mole fraction xA = 0
xB = 0 xB = 1
Fig. 2.4 Vapour pressure versus mole fraction curve of an ideal solution
(i) Raoult’s law should be obeyed.

(ii) D Hmixing should be zero
(iii) DVmixing should be zero
Examples of ideal solution are
(i) Ethyl chloride + Ethyl bromide
(ii) Benzene + Toluene
(iii) Chloro benzene + Bromobenzene
(iv) n-Hexane + n - Heptane
SOLUTIONS 43
According to Raoult’s law, a plot of PA or PB against xA and x B for a solution should give
a straight line I & II (Fig. 2.4) passing through the points PAO or PBO when xA and xB equals unity..
The total vapour pressure P exerted by the solution as a whole at any composition is given by the
sum PA + PB, indicated by the line III in Fig. 2.4 (as required by Dalton’s law of partial pressure),
joining points PAO & PBO
Vapour pressure at any point on the graph is the same as calculated from Raoult’s law,
PA = xA. PAO
and PB = xB. PBO
Non-ideal solutions
It has been found that most of the pairs of miscible liquids form non-ideal solutions.
Non-ideal solutions (i) do not obey Raoult’s law (ii) DV mixing is not equal to zero (iii) DV mixing is
not equal to zero. There is difference in the structures and polarity of the molecules of the com-
ponents. Depending upon the nature of solute and solvent, non-ideal solutions may exhibit posi-
tive or negative deviations from the ideal behaviour.
(a) Non-ideal solutions exhibiting positive deviation
Let us consider a liquid solute and a liquid solvent constituting a solution where the
solute-solvent interactions are weaker than the solute-solute or solvent-solvent interactions. In
such a solution, the total vapour pressure of the solution is greater than that corresponding to an
ideal solution of the same composition. The boiling points of such solutions are relatively lowered.
Such behaviour of solutions is said to have a positive deviation from Raoult’s law (Fig. 2.5) For
such solutions
PA > PAO x A and PB> PBO xB and DV mixing> 0 and
heat is absorbed which means DH mixing> 0
+ PB
P = PA
PBO
PAO PB
VAP. PRES
PA
xB = 0 xB = 1
Fig. 2.5 Vapour Pressure versus mole fraction curve for

non-ideal solution exhibiting positive deviation
In Fig. 2.5 the thick lines show actual behaviour whereas the dotted lines show the ideal
behaviour. The total vapour pressure of such a solution will be the highest and the boiling point
will be the lowest for one of the intermediate compositions. This solution has now the property
of boiling at a constant temperature without any change in composition. Liquid mixtures which
can distil without any change in composition are termed as azeotropes or azeotropic mixtures.
In case of positive deviations, minimum boiling point azeotropes are obtained. A few examples
of solutions showing positive deviations are
(i) Ethanol (polar) and cyclohexane (non-polar)
(ii) Benzene (non-polar) and acetone (polar)
(iii) Benzene and carbon tetrachloride
(iv) Carbon tetrachloride and chloroform.
In pure ethanol, a considerable fraction of the molecules are hydrogen bonded.
H
|
C2H5– O O – C2H5
.......
|
H H
.......
|
O–H ..... O – C2H5
|
C 2H5
When cyclohexane is added, these molecules enter into the hydrogen bonded ethanol
molecules breaking up the hydrogen bonds and reduce the ethanol-ethanol intermolecular at-
traction. The liquid pair shows a slight increase in volume and heat is absorbed.
(b) Non-ideal solutions exhibiting negative deviation

Let us consider a solution of a liquid solute and liquid solvent where the solute-solvent
interactions are stronger than solute-solute or solvent-solvent interactions. In such a solution,
the total vapour pressure of the solution is less than that corresponding to an ideal solution of the
same composition at the same temperature. These solutions are said to exhibit negative devia-
tions from Raoult’s law. They also show an increase in boiling point on adding more of the
solute.Forsuch solutions,PA < PAO xA and PB < PB x B , DH mixing< 0, DV mixing < 0
The total vapour pressure of such a solution will be the least and the boiling point will be
the highest for one of the intermediate compositions.
The solution has now the property of boiling at a constant temperature without any change
in composition and can distil over at a constant temperature without any change in composition.
Such mixture are termed as azeotropes or azeotropic mixture. In case of negative deviations,
maximum boiling point azeotropes are obtained.
SOLUTIONS 45
PBO
PB
P = PA+
PAO
VAP. PRES
PB
PA
xB = 0 xB = 1
Fig. 2.6 Vapour Pressure versus mole fraction curve
for non-ideal solution exhibiting negative deviation
A few examples of solutions showing negative deviation are

(i) Chloroform and acetone
(ii) Acetic acid and pyridine
(iii) Chloroform and benzene
(iv) Water and nitric acid
(v) Diethyl ether and chloroform
When chloroform and acetone are mixed, the hydrogen bonding occurs between the two
molecules.
Cl CH3
Cl – C – H ..... O = C
Cl CH3
This decreases the escaping tendency of the molecules from each component and results
in the increase in the boiling point of the solution. In case of negative deviation, contraction in
volume on mixing along with evolution of heat is expected.
2.7 COLLIGATIVE PROPERTIES OF DILUTE SOLUTIONS :

A dilute solution is one in which the amount of the solute is very small in comparison to the
amount of the solvent. The dilute solutions behave ideally. Dilute solutions obey Raoult’s law.
Dilute solutions containing non-volatile solute exhibit some special properties which
depend upon the number of solute particles irrespective of their nature. These properties are
known as colligative properties and since they are properties of dilute solutions, the properties
are often called colligative properties of dilute solutions. These properties are inter-related,
since if one is measured, other can be calculated. Thus the properties of the dilute solutions
which depend upon the number of solute particles irrespective of their nature are called
colligative properties. A few colligative properties are
(i) Relative lowering in vapour pressure

(ii) Elevation in the boiling point
(iii) Depression in the freezing point
(iv) Osmotic pressure
These properties provide excellent method for the determination of the molecular masses
of dissolved solutes. For best results the following conditions must be satisfied.
(a) the solution should be very dilute
(b) the solute should be non-volatile
(c) the solute should not undergo association or dissociation in solution.
Lowering of vapour pressure : Whenever we add a nonvolatile solute e.g. sodium chloride
to a solvent i.e water, the solute occupies a certain surface area of the solvent. As a result, the solvent
molecules which are more volatile than the solute molecules get lesser opportunity to change to the
vapour state. In other words, the vapour pressure of the solution. becomes lesser than that of pure
solvent i.e. there is lowering of vapour pressure.
Relative lowering of Vapour pressure : The vapour pressure of a liquid is lower when a
non-volatile solute is dissolved in it and the lowering is proportional to the amount of solute
dissolved. Suppose a pure liquid has a vapour pressure P 0 and the solution has vapour pressure P S.
Hence the lowering wiill be P0–PS. The ratio of the lowering of vapour pressure to the vapour
P 0 - Ps
pressure of pure solvent 0 is known as the relative lowering of vapour pressuree.
P
Raoult's Law states that the vapour pressure of the solution is directly proportional to the
molefraction of the solvent at a given temperature.
Mathematically, PS µ x1
where PS ® vapour pressure of solution.
x1 ® mole fraction of solvent
or, PS = P0 x1 ,
where P0 is the vapour pressure of pure solvent.
We know, x1 + x2 = 1
where x2 is the mole fraction of solute.
or, x1 = (1 – x2)
or, PS = P0(1 – x2)
Ps
or, = (1 – x2)
P0
Ps
or, – 1 = – x2
P0
SOLUTIONS 47
Ps
or, 1– = x2
P0
or, P0 - PS = x2
P0
Thus, Raoult's law may be stated in another form :
"The relative lowering of vapour pressure is equal to the mole fraction of the solute."
P0 - PS = n +nN
P0
where n and N are the number of moles of solute and solvent respectively.
Since the solution under consideration is dilute, the molar concentration of the solute
is very small as compared to the solvent and can be neglected.
P0 - PS n
= N
P0
Relative lowering in vapour pressure is a colligative (interlinked) property, since it
relates to the molar concentration of solute and solvent in the solution.
Determination of molecular mass :
We know that, P0 - PS n
= N
P0
P0 - PS w 1 / M1
or, = w /M
P0 2 2
Where w1 is the mass of the solute

M1 is the molecular mass of the solute.
w2 is the mass of the solvent.
M2 is the molecular mass of the solvent
P0 - PS w1 M 2
= w M
P0 2 1
P0 wM
or, P - PS
0 = w2 1
1M 2
P 0 w1 M 2
or, M1 =
(P 0 - PS )w2
All other values, being known, the molecular mass of the solute can be calculated.
Raoult’s Law for Volatile Solutes
Let us consider a solution of two miscible liquid components A and B having mole
fractions xA and xB respectively. Let their partial vapour pressures be P A and PB respectively. The
partial vapour pressures in the solution will be proportional to the respective mole fractions in
the solution. Therefore,
PA a xA and PB and xB
Basing on the experimental data, Raoult showed that in case of mixtures of two miscible
liquids, the above relation can be written as
PA = PAO x A and PB = PBO x B
where PAO and PBO are the vapour pressures of pure components A and B. This is Raoult’ss
law which states that for a solution of volatile liquids, the partial vapour pressure of each
component in the solution is directly proportional to its mole fraction. It may be remem-
bered that this will not hold good if a mixture of volatile liquids does not form a solution.
2.8 ELEVATION OF BOILING POINT (EBULLIOSCOPY) :

A liquid boils when its vapour pressure becomes equal to the atmospheric pressure.
But as the vapour pressure of the solvent is lowered by addition of non-volatile solute, it is
apparent that the boiling point of the solution will be higher than that of the pure solvent. In
other words the boiling point of the solvent is elevated by the addition of non-votatile solute
to it. This is known as elevation of boiling point. (DT b)
If we plot graphs between the different values of temperature and the vapour pressure
for the pure solvent as well as for its solution, the two curves that are formed may be given
as follows.
B B1
Atmospheric It 'P' represents the atmospheric pressure, then
Pressure the boiling point temperature of the pure solvent is
1 T1 and that of the solution is T2. The elevation in
Vapour Pressure
e nt boiling point, DTb may be given as,

s o lv
DTb = T2 – T1
on
A
l ut i Mathematically, DTb = Kb x m. where Kb is the
so
A1 DTb molal elevation constant obtained by dissolving one
moles of solute in 1000 gm of the solvent. As Kb is
T1 T2 constant,
Temperature ®
DTb µ m.
Fig 2.7 Plot of vapour pressure versus temperature
Since elevation of boiling point is dependent upon the molar concentration of the
solute, it is a colligative property.
Determination of molecular mass of solute : The elevation of boiling point DTb is
useful in determining the molecular mass of the solute (M).
The mass of the solute = W1 gm.
The mass of the solvent = W2 gm.
The molecular mass of the solute = M
mass of the solute per 1000gms of the solvent
\ Molality of the solution =
molecular mass of the solute
SOLUTIONS 49
W1 ´1000
= W2 ´ M
\ DTb = Kb.m
W1 ´1000
or, DTb = Kb W ´ M
2
K b .W1 ´1000
or, M =
DTb .W2
2.9 DEPRESSION OF FREEZING POINT (CRYOSCOPY) :

Freezing point of a liquid is defined as the temperature at which the solid and liquid
state of a substace have the same vapour pressure. In other words, it is that temperature at
which the solid and the liquid states of a substance coexist; the liquid and solid are in
equilibrium state.
Vapour pressure of a solution is lower than that of the pure solvent. Hence the freezing
point of a solution is lower than that of pure solvent. Hence the freeezing point of a solution
is lower than that of pure solvent.
If we plot graphs between different values of temperature and the corresponding vapour
pressure for the solid and the liquid states of pure solvent as well as for its dilute solution,
the curves formed may be represented as follows.
C E
t
ven
sol
Vapour pressure2
q u id
li
B
t io n
s ol u
D
A
mT f
T1 Tf
Temperature ®
Fig. 2.8 Plot of V.P. against temperature
According to the definition of freezing point temperature, freezing point of the solvent
is Tf and that of solution is T1. Since Tf is greater than Tl there is lowering or depression in
freezing point temperature, DTf
\ DTf = Tf – T1
Mathematically, DTf = Kf x m.
where Kf is the molal depression constant obtained by dissolving 1 mole of the solute
in 1000 gm of the solvent.
As Kf is a constant, DTf µ m.
Since the depression in freezing point is dependent upon the molal concentration of
the solute, it is a colligative property.
Determination of molecular mass of solute : The depression in freezing point value
DTf is useful in determining the molecular mass of the solute (M).
Let the mass of the solute be W1 gm.
The mass of the solvent be W2 gm.
Molecular mass of the solute be M.
mass of the solute per 1000 gm of the solvent
Molality of the solution =
molecular mass of the solute
W1 ´1000
= W2 ´ M
By substituting the value of M in the relation, DTf = Kf x m ,
Kf .W1 ´1000
we have , DTf = W2 ´ M
Kf .W1 ´1000
or M= DTf .W2
2.10 OSMOSIS :
When a solution is separated from its solvent by a semipermeable membrane, the
solvent molecules pass through it into solution to have uniform concentration of both sides
of the membrane.
"The spontaneous flow of solvent into a solution or from a more dilute to a
concentrated solution through a semipermeable membrane is known as OSMOSIS"
S
P
w
Fig 2.9 Abbe Nollet's experiment

SOLUTIONS 51
Abbe Nollet's Experiment : The passage of solvent through membranes was first
observed by Abbe Nollet (1784). He used an animal membrane (Pig's bladder) as the
semipermeable membrane, which was stretched across the mouth of a thistle funnel P. (Fig.10.5).
The funnel was filled with a strong sugar solution, S, and inverted over a trough of water, W.
The water gradually rises in the stem of the thistle funnel and position of equilibrium ultimately
reached when the hydrostatic pressure equalises the pressure of the water. This pressure
developed as a result of osmosis is the osmotic pressure of the solution and is measured by
the difference in water levels inside and outside.
Illustration of OSMOSIS : Take two eggs of equal size, whose outer shells have
been removed by dissolving in hydrochloric acid. Put one of them in distilled water and the
other in saturated salt solution. After a few hours, it will be noticed that the egg placed in
distilled water swells and the one in salt solution shrinks. It is due to the fact that in the former
case, water enters the concentrated egg fluid while in the latter water comes out of the egg in
order to have equal concentration on both sides.
Salt Solution
Distilled Water
SWELLING OF EGG SHRINKING OF EGG
Fig. 2.10 Illustration of osmosis

Difference from diffusion :
(i) In osmosis, the presence of semipermeable membrane is essential.
(ii) In osmosis it is only the solvent molecules which flow out whilst in diffusion
both the solute as well as the solvent molecules flow out in opposite direction.
Osmotic Pressure : The flow of solvent into solution may be stopped by the application
of pressure on the solution side. This extra pressure which must be applied to a solution to
stop the flow of solvent molecules through the semipermeable membrane is known as osmotic
pressure. This is represented by the symbol p.
SEMI-
PERMEABLE
MEMBRANE
SOLVENT SOLUTION
M
Fig. 2.11 Osmotic pressure
Isotonic Solution : The solutions having same osmotic pressure are known as isotonic
solutions.
Molecular mass and osmotic pressure : van't Hoff (1887) made a thorough study
of the osmotic pressure of dilute solution or ideal solution. He concluded that a dilute solution
behaves like ideal gas.
(i) Boyle-van't Hoff law of solution : According to the law for dilute solution the
product of osmotic pressure and volume is constant, provided the temperature is
constant.
1
( Since p µ V )
Mathematically, p V = Constant, at constant temperature.
(ii) Charle-van't Hoff law for solution : According to the law for a solution of fixed
composition the osmotic pressure is directly proportional to absolute temperature.
Mathematically, p µ T
(iii) van't Hoff equation for dilute solution : This equation is similar to the ideal gas
equation (PV = nRT).
According to the laws stated above,
1
pµ V p ® Osmotic pressure.
pµT
T
pµ V or, p V = KT
where K is a constant called van't Hoff constant for solution and it has the same value
for all solutions. The value of K has been found to be the same as that of R i..e. gas constant.
pV = RT (for 1 mole of the solute dissolved in V litres)
or, pV = nRT. ......... (1) (for n moles of the solute dissolved in V litres)
pV = W T W ® mass of the solute

M RT
M ® molecular mass of the solute.
WRT
or, M= ................................ (2)
pV
n
Again from equ. (l) p = V RT T or, p = CRT ....................................(3)
where C is molar concentration of solution.
For a solution, at a given temperature both R and T are constants.
Hence, p µ C.
Since osmotic pressure depends upon the molar concentration of the solution, it is a
colligative property.
SOLUTIONS 53
2.11 ABNORMAL MOLECULAR MASS :

As we have seen, the colligative properties of solutions depend on the number of solute
particles present in the solution. Various relations hold good in dilute solution only when there is
no change in molecular state of the solute. If the total number of particles of the solute changes
in solution, the colligative property will also change accordingly. For example, if a sugar solu-
tion is taken, the experimental value of the colligative property will be same as the theoretical
value, because one mole of the non-electrolyte sugar gives one mole of particle. On the other
hand, a solution containing one mole of an electrolyte like NaCl will contain 2 moles of particles
(1 mole of Na+ and 1 mole of Cl– ions). Similarly one mole of BaCl2 would produce 3 moles of
ions in solution. When benzoic acid is taken in benzene, the number of benzoic acid particles is
reduced because of the association of benzoic acid particles in benzene. Colligative properties of
the solution depend upon the number of particles, the value observed will be higher or lower
than the calculated values.
Since the molecular mass is inversely related to the colligative properties, in case of
dissociation of the solute, the observed molecular mass will be less than the calculated value and
in case of association, the observed molecular mass will be more than the calculated value.
Van’t Hoff Factor ‘i’ - In order to account for the abnormal colligative properties, van’t
Hoff introduced a factor ‘i’, known as van’t Hoff factor ‘i’ is defined as the ratio between the
observed value of the colligative property and the calculated value.
Observed value of colligative property
i=
Calculated value of colligative property
No. of particles after dissociation or association

=
No. of particles taken ideally
As we know, molecular mass is inversely proportional to colligative property. Therefore,
van’t Hoff factor ‘i’ can be written as
Theoretical molecular mass
i=
Experimental molecular mass
DP
(
Po
) (DTb )obs = (DT )
∫ obs
=
p obs M cal
=
Thus, i =
DP
= (DTb )Cal (DT )
∫ cal
p cal M obs
( )
Po
In case of association , i < 1 and in case of dissociation i > 1
Application of van’t Hoff factor
van’t Hoff factor ‘i’ can be used to calculate the degree of association and the degree of
dissociation.
(a) Degree of Association
Suppose one mole of solute A is dissolved in a definite volume of the solvent where it
has undergone association. ‘n’ molecules of solute A has formed the associated molecule (A) n,
according to the reaction
nA An
(1-a) a/n
a
Let ‘a’ be the degree of association, then the no. of associated moles = and the number
n
of unassociated moles = 1 –a
a 1
Total no. of moles in soln = + 1 – a = 1+ n 1 a
n
Thus van’t Hoff’s factor ‘i’ = 1+(1/n –1) a 1 < 1 if n = 2 or more.

1– i
a=
1
1–
n
1
As colligative property a=
mol.mass
Observed colligative property Actual mol. mass
=
Theoretical colligative property Observed mol. mass.
The degree of association a can be calculated by knowing the value of ‘i’ and ‘n’
(b) Degree of Dissociation
Suppose one mole of solute A has undergone dissociation to give ‘n’ particles according
to the reaction
A ® B + C + ............
(1- α ) α α
No. of particles before dissociation = 1

No. of particles after dissociation = (1 - α ) + nα = 1 + α (n - 1)
No. of particles after dissociation 1+ a(n 1)
Thus, van’t Hoff’s factor ‘i’ = No. of particles before dissociation = 1
i 1
or, a=
n 1
The degree of dissociation a can be calculated by knowing the value of ‘i’ and ‘n’
1. Liquids have definite volume but no definite shape. They are incompressible and they
possess the property of flowing.
2. At any given temperature the pressure exerted by the vapour of a liquid when it is in
equilibrium with the liquid is known as vapour pressure of the liquid.
3. Vapour pressure increases with increase of temperature.
4. Boiling point is the temperature at which the vapour pressure becomes equal to the
standard atmospheric pressure.
5. Greater the vapour pressure of a liquid, the lesser would be its boiling point.
SOLUTIONS 55
6. Raoult's law : The relative lowering of vapour pressure is equal to molefraction of solute.
7. Relative lowering of vapour pressure, elevation of boiling point and depression of
freezing point are the colligative properties.
8. Viscosity of a liquid is its property by virtue of which it tends to oppose the relative
motion between its different layers. It decreases with increase in temperature and increases
with increase in pressure.
9. The spontaneous flow of solvent into a solution or from a more dilute to a concentrated
solution through semipermeable membrane is known as osmosis.
10. The extra pressure which must be applied to the solution to stop the flow of solvent
molecules through the semipermeable membrane is known as osmotic pressure.
11. The solutions having the same osmotic pressure are known as isotonic solutions.
12. Surface tension is the force in dynes acting at right angles to an imaginary line of unit
length on the surface of a liquid. It decreases with increase of temperature.
13. Standard solution : A solution whose strength is known.
14. Grams per litre : Grams of solute per litre of the solution.
15. Normality : Number of gram - equivalents of the solute present per litre of the solution.
Mass of solute in grams per litre

16. (N). It is temperature independant N= Equivalent mass of the solute
17. Molarity : Number of moles of solute present per litre of the solution. (M). It is
temperature dependant.
grams per litre
M = molecular mass of the solute
Normality Molecular mass

Hence N = Molarity = Equivalent mass .
M
18. Molality : Number of moles of the solute present per 1000 g of the solvent (m). It is
independent of temperature.
Mass of the solute in grams per 1000 g of solvent
m= Molecular mass of the solvent
19. Molefraction : Ratio of the number of moles of the component to the total number of
moles of all the components (solute and solvent) in the solution.
20. Percent Solution :
(a) Mass to mass: Number of grams of the solute in 100 g of solution (w/w).
(b) Mass to volume : Number of grams of the solute in 100 ml of solution. (w/v)
(c) Volume to volume :Number of ml of the solute in 100 ml of solution. (v/v)
(d) Volume to mass : Number of ml of the solute in 100 g of solution. (v/w).
21. Formality : Number of formula mass of the solute per litre of the solution. (F)
22. Parts per million : Number of parts by mass of solute present in one million (10 6) parts
by mass of the solution
23. A solution is a homogeneous mixture of two or more substances. It may be binary,
ternary or quaternary depending upon the no. of components present.
24. The mass in grams of a substance which when dissolved in 100 gms of a solvent
forming a staturated solution at a particular temperature is called solubility.
25. Solubility Rule : The polar solids are soluble in polar solvents whereas nonpolar solids
are soluble in nonpolar solvents.
mass of solute in gms

26. Solubility = mass of solvent in gms x 100
27. If DH is +ve, the solubility inscreases with increase in temperature. If DH – ve, the
solubility decreases with increase in temperature.
28. Henry's law : The amount of gas dissolved in a given volume of liquid at constant
temperature is directly proportional to the pressure of the gas.
PROBLEMS WITH SOLUTION

1. The vapour pressures of ethanol and methanol are 44.5 and 88.7 mm Hg respectively. An
ideal solution is formed at the same temperature by mixing 60g of ethanol and 40g of
methanol. Calculate the total vapour of the solution and the molefraction of methanol in
the vapour phase.
Solution :
According to Raoult's law
Partial vapour pressure = Vapour pressure of pure liquid x mole fraction.
Now moles of ethanol = 60

46
= 1.304 (molar mass = 46)
40
Moles of methanol = 32 = 1.250 (molar mass = 32)
1.304
Mole fraction of ethanol = 1.304 + 1.250
= 0.51
Mole fraction of methanol = 1 – 0.51 = 0.49

Partial vapour pressure of ethanol in solution, P(ethanol) = 44.5 x 0.51 = 22.69 mm of Hg
Partial vapour pressure of methanol in solution, P(methanol) = 88.7 x 0.49 = 43.46 mm of Hg
Total vapour pressure = P(ethanol) + P(methanol) = 22.69 + 43.46 = 66.15 mm of Hg.
SOLUTIONS 57
P(methanol)
Mole fraction of methanol in vapour phase = Total vapour pressure = 43.46
66.15
= 0.657
2. Vapour pressure of water at 200C is 17.5 mm of Hg and lowering of vapour pressure of a

sugar solution is 0.061 mm of Hg. Calculate.
(i) relative lowering of vapour pressure
(ii) vapour pressure of the solution
(iii) mole fraction of sugar and water.
Solution :
(i) Calculation of relative lowering of vapour pressure :
Vapour pressure of water ( PA0 ) = 17.5 mm of Hg.
Lowering of vapour pressure ( PA0 – PA) = 0.061.
PA0 - PA
Relative lowering of V.P = = 0.061 = 0.00348
PA0 17.5
(ii) Calculation of V.P. of solution

P = V.P of solvent – lowering in V.P
= 17.5 – .061
= 17.439 mm of Hg
(iii) Calcutation of mole fraction of sugar and water.
Mole fraction of sugar, XB solute
PA0 - PA
= XB
PA0
PA0 - PA
Here, = 0.00348
PA0
Mole fraction of sugar. XB = 0.00348

Mole fraction of water (=XA) = 1 – XB = 1 – 0.00348 = 0.9965
3. The boiling point of pure water is 1000C. Calculate the boiling point of an aqueous solution
containing 0.6 g of urea (molar mass = 60) in 100 g of water. (K b for water = 0.52K/m)
Solution : We know that
Kb ´ WB ´ 1000
mTb = M B ´ WA
-1
Kb = 0.52 K m , WB = 0.6g, MB = 60 and WA = 100 g
´ 0.6 ´ 1000
\ mTb = 0.5260 ´ 100
= 0.0520C.
Thus, b.p of the solution
= 100 + 0.052
= 100 . 0520C.
4. 50 ml of benzene (density 0.879 g/ml) when added with 0.643 g of a compound lowers the
freezing point from 5.510C. to 5.030C. If K for benzine is 5.12 K Kg mol–1, calculate the
molar mass of the compound.
Solution : The molar mass MB is calculated as
K f ´ WB ´ 1000
MB = WA ´ DTf
Given WB = 0.643g, WA = (50ml) x (0.879 g/ml) (i.e. = 43.95 g)

-1
Kf = 5.12 K m , mTf = 5.51 – 5.03 = 0.480
´ 0.643 ´ 1000
\ MB = 5.1243.95 ´ 0.48
= 156.06
5. If 1.71 g of sugar (molar mass = 342) are dissolved in 500 ml of a solution at 300K, what
1 1
will be its osmotic pressure ? (R = 0.082 Latm. K mol )
Solution : According to van't Hoff equation

WB RT
p = CRT = n RT = M V
V B
500
WB = 1.71 g, V = 1000 L, T = 300 K
1 1
R = 0.082 L atm K mol .
´ 0.082 ´ 300
Putting all the values, p = 1.71
342 ´ 500 / 1000
= 0.246 atm.
6. Osmotic pressure of a solution containing 7g of a protein per 100 ml of solution is 25 mm

Hg at 370C. Calculate the molar mass of protein.
p = CRT
nB
= RT
T
V
WB RT
= M V
B
WB RT
\ MB =
pV
SOLUTIONS 59
Here, WB = 7g, T = 273+37 = 310K,

25
p = 760 atm., V = 100ml = 0.1 L
1 1
R = 0.082 litre. atm K mol
7 ´ 0.082 ´ 310
\ MB = 25 ´ 0.1 = 54094
760
QUESTIONS
A. Very short answer type questions (One mark each) :

1. At 730 mm pressure, the boiling point of water is .............................. (more than 100 0C,
less than 1000C)
2. The boiling point of sea water at 760 mm pressure is ........................................ ( more
than 1000C, less than 1000C).
3. The vapour pressure of a liquid is equal to the atmospheric pressure at its .....................
(boiling point, freezing point)
4. The viscosity of glycerol is more than that of water due to .......................... (hydrogen
bonding, van der Waals forces)
5. Define the term surface tension and viscosity.
6. What is the freezing point of water at 1 atm. pressure in Kelvin scale ?
7. With the increase of temperature, the vapour pressure of a liquid ......................
(a) Decreases, does not change, increases)
8. Between sea water and drinking water which will freeze at a lower temperature ?
9. What do you understand by viscosity of a liquid ?
10. Vapour pressure of a liquid ————— with rise of temperature.
11. Why is CCl4 immiscible in water ?
12. Name one factor which influences the solubility of a solid in a solvent ?
13. How does boiling point of a liquid change with decrease in atmospheric pressure ?
14. What is the effect of pressure on the boiling point of a liquid ?
15. How does viscosity of a liquid vary with temperature ?
16. Between water and ether which has a higher vapour pressure ?
17. What is the order of increasing vapour pressure of the following at room temperature ?
Water, Sugar solution in water, alcohol - water solution
18. What is the relationship between depression in freezing point of a solution and molecular
mass of the solute ?
19. Why is vapour pressure of a solution lower than that of a pure solvent ?
20. What is the SI unit of viscosity ?
21. What is the SI unit of surface tension ?
22. Which of the following has higher vapour pressure at the same temperature ?
CH3OH ( BP = 64.50C) C2H5OH ( BP = 78.30C)
B. Short answer type questions (Two marks each) :

1. Write four important characteristics of liquids.
2. Define and explain the term "vapour pressure".
3. Describe the effect of temperature on the vapour pressure of a liquid.
4. Define the term 'boiling point'.
5. Explain the term freezing point.
6. Define molality of a solution.
7. Define molarity of a solution.
8. What is the equivalent mass of sodium carbonate ?
9. Define and illustrate equivalent mass of an acid
10. Define 'Molality'.
29.25 g of NaCl is present in 529.25 g of the solution. Find out the molality.
11. What is the molality of a solution containing 40 g of NaOH in 1000 ml of water ?
12. Write down the equation that will show the relationship between normality and molarity.
13. Define surface tension.
14. (a) Define the terms (i) viscosity (ii) coefficient of viscosity.
(b) What do you understand by viscosity of a liquid ?
15. Distinguish between diffusion and osmosis.
16. Explain why ?
(a) In summer, earthen pots are used to keep water cool.
(b) Liquid drops are spherical.
(c) Egg shrinks in size when placed in sodium chloride solution.
(d) The boiling point of water is more than that of ether.
(e) Ammonia is used as a refrigerant.
17. What do you mean by osmosis ?
18. What do you understand by "osmotic pressure".
19. What do you understand by viscosity of a liquid ?
20. Calculate the vapour pressure of the solution at 100 0C containing 3gms of cane sugar
in 33 gms of water. [molecular weight of sugar = 342]
21. The relation of heat of vapourisation to the boiling point in absolute scale of liquids is
approximately 21. The relation is known as........ .
SOLUTIONS 61
22. Why surface tension of a liquid decreases with increase in temperature ?

23. Between sea water and pure water, which will boil at a higher temperature ? Give
reason.
24. Why glycerol is more viscous than water ?
25. What is reverse osmosis and how is it helpful ?
26. What is the effect of temperature on the surface tension of a liquid ? Explain with
reason.
27. Distinguish between diffusion and osmosis.
28. 0.265 gms of sodium carbonate is present in 100ml of the solution. What is its normality ?
29. Calculate the normality of the following
(a) 0.585 g NaCl / 100 cc soln.
(b) 0.49 g H2SO4 / 1000 cc soln.
30. What is van't Hoff's factor ? How is it related to the degree of association of a solute
with solvent ?
C. Short answer type questions (Three marks each) :

1. Define the term solution. How many types of solutions can be formed?
2. A solution of glucose (C6H12O6) in water is labelled as 10% W/W. What would be the
molality and mole fraction of each component of the solution?
3. A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by
mass. Calculate the mass percentage of the resulting solution.
4. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 ml. of
0.15 M solution is methanol.
5. Vapour pressure of water is 12.3 kPa at 300K. Calculate vapour pressure of 1 molal
solution of a non-volatile solute in it.
6. A solution of sucrose is prepared by dissolving 68.4 g in 1000 g of water. Calculate the
vapour pressure of solution at 20°C. The vapour pressure of water of 293K is 0.023 atm.
Assume that the solution behaves ideally. (Molar mass of sucrose = 342 g mol –1).
7. A solution containing 18 g of non-volatile solute in 200 g of water freezes at 272.07K.
Calculate the molecular mass of the solute (Water freezes at 273K and its K f = 1.86 Kg
mol–1).
8. The boiling point of a solution containing 5.0 g of of non-volatile solute in 1 Kg of a
solvent at 0.05° higher than that of pure solvent. Calculate the molecular mass of the
solute (Molecular mass and Kb for a solvent are 78 and 2.53K Kg/mol–1 respectively).
9. A 5% solution of CaCl2 at 0°C developed an osmotic pressure of 15 atmosphere.

Calculate the degree of dissociation.
10. 5.85 g of NaCl is dissloved in 90 g water. What is the mole fraction of NaCl?
11. A solution of 2.4 g of a substance in 25g water boiled at 100.8°C at 1 atm. pressure .
Calculate the molecular mass of the substance (Boiling elevation constant for water =
0.52°C per 1000g of it)
12. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in freezing point
of water observed is 1.0°C. Calculate the Van't Hoff factor and dissociation constant of
CH2FCOOH.
D. Long answer type questions (7 marks each) :

1. Describe the kinetic molecular theory of liquids.
2. Describe the characteristic properties of the liquids.
3. (a) Write a method for measuring the vapour pressure of a liquid.
(b) Write a note on boiling point.
4. Explain the term surface tension. What are the factors on which surface tension depends ?
5. Write short notes on :
(a) Viscosity (b) Osmosis (c) Osmotic pressure.
6. Describe briefly about osmosis and osmotic pressure.
(a) Osmotic pressure
(b) Viscosity
(c) Surface tension.
(d) Osmosis.
(e) Boiling point and freezing point.
8. Describe the characteristic properties of liquids and explain the following ;
(i) Evaporation causes cooling.
(ii) A drop of liquid assumes spherical shape.
(iii) The vapour pressure of a liquid increases with the increase in temperature.
(iv) 'Like dissolves like.'
(v) "Liquid state" lies between solid and gaseous state."
(vi) Boiling point of a liquid depends on temperature.
9. Explain the effect on the boiling point and freezing point when a non-volatile solute is
dissolved in a volatile solvent.
10. What is viscosity ? How does it vary with rise of temperature ? Mention some applications
of viscosity in eveyday life.
SOLUTIONS 63
11. Discuss briefly the effect of temperature on,

(a) Surface tension and (b) Viscosity.
12. State Raoult's law. A solution of 2.4 g of a substance in 25g of water boiled at 100.8 0C
at 1 atm. pressure. Calculate the molecular mass of the substance (Boiling elevation
constant for water = 0.520C per 1000 g of it)
13. What is osmotic pressure ? How will you determine the molecular mass of a substance
by this method ?
The osmotic presure of 200ml of aqueous solution containing 1gm protein at 27 0C in
2.0 x 10–1 atm. Calculate the molecular mass of protein (R = 0.082 L atm. mol –1 K–1)
14. Define molality of a solution.
15. Define molarity of a solution.
16. Define 'Molality'.
29.25 g of NaCl is present in 529.25 g of the solution. Find out the molality.
17. What is the molality of a solution containing 40 g of NaOH in 1000 ml of water ?
18. Write down the equation that will show the relationship between normality and molarity.
19. Four solutions A, B, C, and D contain 1g each of HCl, HNO3, H2SO4 and H3PO4
respectively per 100 ml. Arrange the solutions in the increasing order of their molarity
and normality.
20. (a) Calculate the molarity when 73g of HCl is dissolved in water to make 1500 ml
solution.
(b) Calculate the molarity of seminornal Na 2CO3 solution. Na = 23, C = 12
(c) 5.85 g of NaCl is dissolved in 90 g of water. What is the mole fraction of NaCl?
21. What is the molality of a solution containing 0.25 mole of the solute in 250 g of the
solvent ?
22. Sp. gr of HCl solution is 1.17. 100 g of HCl solution contains 36.5 g of acid. Calculate
the normality of the solution.
23. 200 ml of 0.2 M NaOH and 300 ml of 0.3 M NaOH are mixed. Find out the molarity
of the resulting solution.
E. Multiple choice type (One marks each) :

1. When KCl is dissolved in water, the
(a) Boiling point is raised.
(b) Boiling point is lowered.
(c) Boiling point remains unchanged.
2. An aqueous solution of methanol in water has vapour pressure,

(a) Equal to that of water.
(b) Equal to that of methanol.
(c) More than that of water.
(d) Less than that of water.
3. Compared to Jalandhar, the vapour pressure of water at Simla is,
(a) Lower
(b) More
(c) Equal.
4. Dissolution of a solid in a solvent.
(a) Increases its vapour pressure.
(b) Lowers the vapour pressure.
(c) Does not change its vapour pressure.
(d) Decreases boiling point
5. Viscosity of a liquid
(a) Increases with increase in temperature.
(b) Decreases with decrease in temperature.
(c) Independent of temperature.
(d) Decreases with decrease in pressure
6. With increase in temperature, the vapour pressure of a liquid.
(a) Decreases
(b) Does not change.
(c) Increases
7. Cleaning action of soap is due to.
(a) Viscosity of water.
(b) Surface tension of water.
(c) Polarity of water.
(d) high boiling point of water.
8. When an egg is placed in concentrated sodium chloride solution, it shrinks due to
(a) Osmosis
(b) Diffusion
(c) Decomposition
9. The unit of viscosity is poise which means
(a) Dyne Cm–2
(b) dyne
(c) dyne cm–2 sec–1
(d) dyne cm
SOLUTIONS 65
10. The internal resistance to flow possessed by liquid is called its

(a) Surface tension
(b) Fuidity
(c) (n)
(d) Viscosity
11. A liquid in capillary tube rises due to
(a) Surface tension
(b) Vapour pressure
(c) Osmosis
(d) Viscosity
12. When salt water is slowly frozen the first solid which separates is
(a) ice
(b) salt
(c) a compound formed from water and salt
(d) solid solution of salt and ice
13. The vapour pressure of a liquid
(a) is directly proportional to the temperature.
(b) is inversely proportional to the temperature.
(c) increases only up to the boiling point.
(d) vary from liquid to liquid.
14. At high altitudes the water boils at low temperature because
(a) water molecules are bound with strong hydrogen bonds.
(b) low atmospheric pressure.
(c) high atmospheric pressure.
(d) at low altitude the fuel does not give sufficient energy.
15. When temperature increases, the surface tension of a liquid is
(a) increased
(b) decreased
(c) neither increased nor decreased
(d) depends on the nature of the liquid
16. When a dry grape or raisin is placed in water, it swells due to
(a) Difflusion
(b) Osmosis
(c) Absorption
(d) Surface tension
17. Dissolution of solute in a solvent

(a) lowers its vapour pressure
(b) increases its vapour pressure
(c) increases its freezing point
(d) lowers its boiling point
18. Egg when placed in a concentrated solution of common salt gets shrinked due to
(a) diffusion
(b) surface tension
(c) decomposition
(d) osmosis
19. Which of the following solution shows highest osmotic pressure ?
(a) 0.1 M glucose
(b) 1 % urea
(c) 0.1 M common salt
(d) all show equal osmotic pressure
20. The boiling point of water in a pressure cooker is
(a) below 1000C.
(b) above 1000C.
(c) 1000C.
(d) depends upon the size of pressure cooker.
21. The osmotic pressure of a dilute solution is directly proportional to the
(a) Diffusion rate of the solute.
(b) Concentration of the solute.
(c) Elevation of boiling point.
(d) Flow of solvent from a concentrated solution to a dilute solution.
22. Which of the following 0.1 M aqueous solutions will have the lowest freezing point ?
(a) Potassium sulphate
(b) Sodium chloride
(c) Urea
(d) Glucose
23. One of the following is not affected by the change in temperature
(a) Normality
(b) Molarity
(c) Molality
(d) none of these.
SOLUTIONS 67
24. 10ml of conc. H2SO4 (18 molar) is diluted to 1 litre. The approximate strength of dilute
acid would be
(a) 0.18 N (b) 0.09 N
(c) 0.36 N (d) 18.O N
25. 12g of H2SO4 is dissolved in water to make 1200 ml of the solution. The concentration
in normality is
(a) 0.051 (b) 0.102
(c) 0.122 (d) 0.204
26. The molarity of pure water is
(a) 55.6 (b) 50
(c) 100 (d) 18
27. 5.85 g of NaCl is dissolved in 90 g of water. The molefraction of the solute is
(a) 0.01 (b) 0.1
(c) 0.2 (d) 0.0196.
28. The normality of 26.5 g of Na2CO3 present in one kilolitre solution is
(i) 0.25 N (ii) 0.05 N
(iii) 0.5 N (iv) none of these.
ANSWERS TO MULTIPLE CHOICE TYPE QUESTIONS
1. (a) 5. (b) 9. (c) 13. (c) 17. (a) 21. (b) 25. (iv)
2. (c) 6. (c) 10. (d) 14. (b) 18. (d) 22. (a) 26. (i)
3. (b) 7. (b) 11. (a) 15. (b) 19. (c) 23. (iii) 27. (iv)
4. (b) 8. (a) 12. (a) 16. (b) 20. (a) 24. (iii) 28. (iv)
qqq
UNIT - III
CHAPTER - 3
ELECTROCHEMISTRY
3.1 INTRODUCTION :
Electrochemistry deals with the interaction of electrical energy with chemical species. It
is divided into two categories : (i) Electrical energy performing chemical change (electrolysis)
and (ii) Conversion of chemical energy to electrical energy i.e. producing electricity by redox
reactions. All electrochemical reactions involve transfer of electrons and therefore, they are redox
reactions.
Substances are divided into two types on the basis of conduction of electricity through
them. Substances which conduct electric current are called conductors and substances which do
not conduct electricity are called non-conductors or insulators.
Conductors are again divided into two types i.e.
(i) Metallic or electronic conductors (ii) Electrolytes or electrolytic conductors.
Metallic Conductors - These are metals through which electric current can pass without
any transfer or change in chemical properties of matter. Metals are best conductors, e.g., copper,
aluminium etc. This property is not restricted to pure metals, it is also possessed by most of the
alloys of metals, carbon, certain solid salts and oxides.
Electrolytic conductors or Electrolytes - Substances which allow the passage of
electricity through their aqueous solution or fused state are called electrolytes. Passage of electric
current results in transfer of matter and changes in concentration.
Examples : Fused salts, acids, bases and their aqueous solutions.
Non-electrolytes - Substances which do not conduct electric current through their aqueous
solutions are called non-electrocytes. Examples are - cane sugar, urea, glycerol, benzene etc.
Distinction between metallic and electrolytic conduction
Metallic conduction Electrolytic conduction
1. It occurs due to flow of electrons. 1. It occurs due to movement of ions
in solution or a fused electrolyte
2. No change in chemical properties of 2. It involves chemical reactions at
conductor takes place. the electrodes.
3. Does not involve transfer of matter. 3. It involves transfer of matter in form of ions.
4. It shows an increase in resistance as 4. It shows a decrease in resistance as
temperature increases. temperature is increased.
ELECTROCHEMISTRY 69
Properties of electrolytes
1. Electrolytes conduct electricity in molten of fused state or in aqueous solutions.
2. Chemical reaction takes place at the electrodes and electrolytes are chemically
decomposed.
3. Electrolytes on being dissolved, positive and negative ions are formed in solution.
4. All electrolytes do not conduct electricity to the same extent. Some electrolytes
provide greater number of ions, these are called strong electrolytes. Examples
are hydrochloric acid, sodium hydroxide etc. (strong acids and strong bases, also
strongly ionic salts). Some other electrolytes conduct electricity to lesser extent,
because these provide lesser number of ions. These are weak electrolytes.
Examples are acetic acid, oxalic acid etc.
3.2 ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION :
(1) When an electrolyte is dissolved in water, it splits up into ions. The process of
splitting up of an electrolyte into positive and negative ions (cations and anions
respectively) is called ionisation or electrolytic dissociation.
For examples : NaCl Na+ + Cl-

unionised Cation Anion
molecule
(2) Properties of the electrolytes in solution are due to the properties of the ions
produced on dissociation.
(3) Electrical conductivity of an electrolyte is due to the movement of ions towards

the oppositely charged electrodes. Conductivity depends upon the number of ions
in the solution. Greater the number of ions, greater is the conductivity.
(4) Electrolytes in solution split up into ions. Ions reunite to form the original
molecules. Thus, there is dynamic equilibrium between the ions and unionised
molecules.
(5) The extent to which an electrolyte undergoes dissociation into ions is called degree
of dissociation or ionisation.
Number of molecules dissociated into ions
Degree of ionisation =
Total number molecules dissolved.
Degree of ionisation is different for different electrolytes. Electrolytes having high degree
of inisation are called strong electrolytes and electrolytes having low degree of ionisation are
called weak electrolytes.
3.3 STRONG AND WEAK ELECTROLYTES :
All ionic compounds (such as KCl, NaCl, KNO3 etc.), strong acids (such as HCl, H2SO4,
HNO3 etc.) and strong bases (such as KOH, NaOH, etc.) ionise almost completely in aqueous
solution. A very small fraction of these substances remain as unionised molecules. Such substances
are called strong electrolytes. Law of ionic equilibrium can not be applied to such substances.
Examples : KCl ® K+ + Cl- (almost completely ionised)
NaOH ® Na+ + OH- (almost completely ionised)

KNO3 ® K+ + NO3- (almost completely ionised)
Certain other acids like acetic acid, carbonic acid (H2CO3) and bases likeNH4OH, Ca(OH)2
etc. ionise slightly in solution. Large fraction of these substances remian as unionised molecules
in solution. These are called weak electrolytes.
Examples :- CH3COOH H+ + CH3COO- (very slightly ionised)
NH4OH NH4+ + OH- (very slightly ionised)
A faction of the total number of molecules which exist as ions in solution is called its
degree of dissociation.
Degree of dissociation Number of molecules dissociated into ions.

=
Total number molecules dissolved
Ostwald's dilution law

When a weak electrolyte is dissolved in water, a very small fraction of it dissociates into
ions in solution. An equilibrium exists between the ions and unionised molecules. Let us take the
case of a weak acid. HA, of which 1 mole is dissolved in 'V' litres of water. Let 'x' moles of HA
dissociate into ions at equilibrium.
HA H+ + A-
Initial Conc. 0 0 0
Conc. at equilibrium (1-x) x x
1-x , [H+] = x and [A-] = x
At equilibrium [HA] =
V V V
ELECTROCHEMISTRY 71
x´ x
[ H + ][ A - ] V V = x2
Applying law of equilibrium, K a = =
[ HA ] (1- x ) V(1 - x )
V
where K a is the dissociation constant of acid. Greater the value of K a, stronger is the acid.
1 = C moles per litre

V litres
For a very weak electrolyte, 'x' is extremely small and can be neglected in the denominator.
2 Ka
Thus, Ka = x = Cx2 or, x =
V C
Kb
Similarly, for a weak base, x = —— , where Kb is the dissociation constant of base.
C
Problems :
1. Calculate the amount of acetic acid present in one litre of its solution, having a =
1% and Ka = 1.8 ´ 10-5
CH3COOH CH3COO- + H+
Initially 1 0 0
After dissociation, 1-a a a
where 'a ' is the degree dissociation, if concentration of acetic acid is C mol. litre -1
[CH3COO-] [H+] aC. aC a2C2
Ka = = =
[CH COOH] C (1-a) C(1-a)
3
2 2
If 'a' is very small, 1 - a = 1,K a = a C = a 2 C
C
-5 1 2 -1
Then 1.8 ´ 10 = C ´ 100 or C = 0.18 mol. litre .
Therefore, 1 litre solution contains 0.18 moles = 0.18 ´ 60g = 10.8g.

(Mol. mass of CH3COOH = 60)
2. Calculate the concentration of H+ and degree of dissociation of 0.2M acetic acid
solution, having Ka = 1.8 ´ 10-5
CH3COOH CH3COO- + H+
Initially, 1 0 0
After dissociation, 1- a a a
-1
Let initial concentration of acid be C moles. litre and a be the degree of dissociation.
Ka
So, [H+] = aC = C —— = KaC = (1.8 ´ 10-5 ´ 0.2) = 1.9 ´ 10-3 mol. litre-1
C
Ka 1.8 ´ 10-5
Also, a = —— = ————— = 0.0095 or 0.95%
C 0.2
3.4 ELECTROLYSIS :
The process of decomposition of an electrolyte in solution or in the fused state by passing
electric current is known as electrolysis.
Aqueous solution of an electrolyte is taken in a glass vessel. Two metal plates are dipped
in the solution and upper end of the plates are connected to the two poles of a battery. These metal
plates are called electrodes. The electrode connected to the positive pole of the battery is called
anode and that connected to the negative pole of the battery is called cathode. Electric current
enters the electrolyte through the anode and leave the electrolyte through the cathode. Electrolyte
is dissociated into positive and negative ions and move to the oppositely charged electrodes on
passing the current. Cations (Positive ions) are liberated at cathode and anions (negative ions)
are liberated at anode.
+ -
BATTERY
ANODE ANION CATHODE

SOLUTION OF
ELECTROLYTE
ELECTROLYTIC
CATION
TANK
Fig. 3.1 Electrolysis
The process of electrolysis can be described in the following manner.

(i) Electrolyte dissociates into positive and negative ions.
(ii) At anode - Anions being liberated at anode lose electrons and get converted to
neutral atom (primary process). Neutral atom may combine with another atom to
form molecule or may react with water. (secondary process).
(iii) At cathode - Cations being liberated at cathode, gain electrons and form neutral
atoms which get deposited on cathode (Primary process) or may react with water
(secondary process)
ELECTROCHEMISTRY 73
Examples -
electrolysis of fused NaCl
NaCl ® Na+ + Cl-
At cathode Na+ + e ® Na liberated at cathode
At anode Cl- - e ® Cl (primary process)
Cl + Cl ® Cl2(g) (secondary process) - liberated at anode.
Electrolysis of aqueous solution of NaCI

NaCl ® Na+ + Cl-
At cathode Na+ + e ® Na (primary process)
2Na + 2H2O ® 2NaOH + H2 (g) (secondary process)
Hydrogen is liberated at cathode.
At anode Cl- - e ® Cl (primary process)
Cl + Cl ® Cl2(g) (secondary process) - liberated at anode.
Electrolysis of aqueous solution copper sulphate

Using copper electrodes -
CuSO4 ® Cu2+ + SO42-
H2O ® H+ + OH-
At cathode Cu2+ + 2e- ® Cu, deposited on cathode.
At anode Cu - anode goes into solution forming Cu2+ ions
Cu ® Cu2+ + 2e, equivalent amount of copper goes into the solution.
Using platinum electrodes -

CuSO4 ® Cu2+ + SO4 2-
H2O ® H+ + OH-
At cathode Cu2+ + 2e ® Cu, deposited on cathode.
At anode OH- -e ® OH
2OH ® H2O + O
O + O ® O2, liberated at anode.
3.5 FARADAY'S LAWS OF ELECTROLYSIS :
Michael Faraday studied the quantitative relationship between the amount of chemical
change observed at the electrodes and the quantity of electricity passed through the solution. The
result of his investigation is expressed in the form of two laws.
1. First law - The mass of the substance liberated at the electrode during the process of
electrolysis is directly proportional to the quantity of electricity passed
through the electrolyte.
If 'W' is the mass of substance liberated at the electrode and 'Q' is the quanitity of electricity
(in Coulombs) passed through the electrolyte, then
W µQ But, Q = C. t
where C = current in amperes and t = time in seconds.
W
then, W µ C.t or W = Z.C.t. or Z =—
C.t
where 'Z' is a constant known as Electrochemical equivalent.
If C = 1 ampere and t = 1 second, then W = Z.
Therefore, electrochemical equivalent of a substance is defined as the the mass of the
substance liberated when one ampere of current is passed through the electrolyte for one second.
It can also be defined as the mass of substance liberated by the passage of one coulomb of
electricity.
1 coulomb = 1 ampere ´ 1 second
(unit of electricity)
Faraday (F) is a bigger unit of electricity.
1 Faraday = 96500 coulombs.
It has been found that by passing one Faraday (96500 coulombs) of electricity through the
electrolyte, 1 gm equivalent of the substance is liberated.
For example, on passing 1 Faraday or 96500 coulombs of electricity through silver nitrate
solution, 108 gm ( 1gm. equiv. of silver) of silver is deposited at the cathode.
Mass of substance liberated by passing 96500 coulombs of electricity = 1 gm. equiv.
When one coulomb of electricity is passed,
1 gm. equivalent
= Electrochemical equivalent of substance is deposited.
96500
Chemical equivalent
Therefore, electrochemical equivalent (E.C.E.) =
96500
Hence, E.C.E. or Z for silver = 108 = 0.0011181
96500
2. Second law - When the same quantity of electricity is passed through different electrolytes
connected in series, the masses of different substances liberated at the
electrodes are proportional to their equivalent masses.
Let there be three voltameters containing solutions of copper sulphate, silver nitrate and
acidulated water and these are connected in series, so that same amount of electricity is passed
through the electrolytes for a given time. It is found that the masses of copper, silver and hydrogen
liberated at the respective electrodes are in the ratio of their equivalent masses or chemical equivalents.
ELECTROCHEMISTRY 75
Mass of copper deposited Equivalent mass of copper

Thus, =
Mass of silver deposited Equivalent mass of silver
This law becomes useful in determining equivalent mass of substances.
Mass of copper deposited
Mass of copper deposited 96500 E.C.E. of copper
= =
Mass of silver deposited Mass of silver deposited E.C.E of silver
96500
Equivalent mass of copper
=
Equivalent mass of silver
Problems based on Faraday's Laws

1. What current strength in amperes will be required to liberate 10gm. of iodine
from KI solution in one hour (Eq. mass of KI = 127)
W = 10 gm. Z= 127 , t = 3600 seconds

W = Z.C.t. 96500
or, C = W = 10 ´ 96500 = 2.11 ampere.

Z.t 127 ´ 3600
2. A current of 3 amp. passing through AgNO3 solution for 20 minutes deposited 4g.
of silver. What is the E.C.E. of silver ?
Here, C = 3 amp. t = 20 x 60 seconds
W = 4g.
W = Z.C.t.
or, Z = W = 4 = 0.00111
C.t. 3 ´ 20 ´ 60
3. 0.2964 g. of copper was deposited on passage of a current of 0.5 amp. for 30
minutes through a solution of copper sulphate. Calculate atomic mass of copper.
Cu++ + 2e ® Cu
For the deposit of at.mass or 1 mole of Cu-atoms 2 Faraday of electricity are required.
Here, W = 0.2964g. Q = C.t = 0.5 ´ 30 ´ 60 = 900 coulombs.
900 coulombs deposit 0.2964g of Cu.
\ 193,000 will deposit = 0.2964 ´ 193000 = 63.56g of Cu

900
Hence, at. mass. of copper = 63.56
4. Calculate the E.C.E. of Cu. and Ag when that of H2 is 0.0000104

(At. mass of Ag = 107.88 and that of Cu. = 63.54)
E.C.E of H2 Eq. mass. of H2
=
E.C.E. of Ag Eq. mass. of Ag.
Thus, E.C.E. of Ag = 0.0000104 ´ 107.88 = 0.01112
1
E.C.E. of Cu = 0.0000104 ´ 31.77 = 0.00033

1
(Q Eq. mass. of copper = At. mass = 63.54 = 31.77)
2 2
5. (a) What is the charge in coulomb on a CO32- ion ?
(b) Calculate approximately, how much current is necessary to produce
oxygen gas at the rate of 1 ml. per socond ?
(a) 6.02 ´ 1023 electrons correspond to 96,500 coulombs (1 Faraday)
96,500 ´ 2 -19
2 electrons present on CO32- ion correspond to = 3.2 ´ 10
23 Coulombs
6.02 ´ 10
(b) 1 Faraday = 96,500 coulombs.
1g. equiv (8g) of oxygen = 22.4 litres = 5,600 ml at N.T.P.
4
Hence, for the production 1 ml. of oxygen,

coulombs required = 96, 500 = 17.23.
5,600
Current in amp/sec. = 17.23 = 17.23

1
3.6 APPLICATIONS OF ELECTROLYSIS :
(a) Electroplating : This is done for decoration by depositing gold, silver etc. on
baser metals and protection of metals by depositing nickel, chromium etc. on baser
metals. Also broken parts of metals are repaired by depositing the metals
electrolytically.
The article to be electroplated is cleaned mechanically by sand paper, washed with NaOH
and excess of water. This article is made the cathode. The metal to be deposited is made the
anode. The electrodes are suspended in a tank made of glass, wood or cement. Electrolyte taken
in the tank is a soluble salt of the metal which is to be deposited. Electrolyte used should be
highly soluble, a good conductor and should not undergo oxidation, reduction or hydrolysis. For
best electroplating, low current density, low temperature and high metal concentration in the
ELECTROCHEMISTRY 77
electrolyte is essential. Anode and cathode are connected to the positive and negative pole of
battery respectively.
Examples of some common electrolytes used :
(i) Copper sulphate solution with dilute sulphuric acid - Copper plating.
(ii) Potassium argentocyanide K[Ag(CN)2] -Silver plating.
(iii) Nickel ammonium sulphate - Nickel plating.
(b) Electrorefining : Metals obtained in the extraction process contain impurities. To
purify the metals like copper, silver, lead etc electrorefining process is used. In this
process a sheet of impure metal is made anode. If copper metal is to be refined, a
sheet of pure copper is made the cathode. Electrolyte used is a solution of copper
sulphate mixed with dilute sulphuric acid. Anode and cathode are connected to the
positive and negative pole of battery respectively. On passing the current copper
from the impure anode goes into the solution as Cu++ ions and from the electrolytic
solution pure copper is deposited on the cathode.
CuSO4 ® Cu2+ + SO42-

At cathode Cu2+ + 2e ® Cu (deposited on cathode)
(c) Electrotyping : Reproduction of objects of art on wood carvings are concerted to

printing plates by the electrodeposit method. Impression of the object of art is
taken on the block of wax. The impression of wax is coated with graphite (a good
conductor). This plate is made the cathode. Anode is made of copper and both are
suspended in a tank of copper sulphate. On passing electric current copper metal is
deposited on the impression on wax. After depositing the metal, wax is melted and
the metal plate so obtained is used in printing.
(d) Electrolytic extraction of metals : Certain active metals like sodium, potassium,
magnesium, calcium etc. are extracted by the electrolysis of their fused salts. For
example, when fused sodium chloride is electrolysed sodium metal is liberated at
the cathode.
3.7 ELECTROLYTIC CONDUCTANCE :
Ohm's law which is valid for metallic conductors is also applicable to electrolytic
conductors. It states that :
The strength of the current (I) passing through a conductor is (i) directly proportional
to the potential difference (E) applied across the conductors and (ii) inversely proportional
to the resistance (R) of the conductor.
Hence, I = E
R
where 'I' is in amperes, 'E' in volts and 'R' is measured in ohms.
Resistance (R) of any conductor varies (i) directly as the length of the conductor (l) and
(ii) inversely as the area of cross section of the conductor (a).
Thus, R µ l ............................................... (i)
and R µ 1 ........................................... (ii)
a
Combining (i) and (ii), we have R a l

a
or, R = r l where 'r' (rho) is a constant which depends upon the nature of material and
a
is called specific resistance.
When l = 1 cm, a = 1sq.cm, then R = specific resistance (r)
Therefore, specific resistance is equal to the resistance in ohms of a material which is 1

cm in length and 1 sq. cm in area of cross-section. Thus, specific resistance is the resistance of
one cm cube of the material.
Conductance (C) — In electrochemistry the term conductance is used instead of

resistance. Conductance is the reciprocal of resistance. C = 1
R
As the unit of resistance is ohm, the unit of conductance is ohm--1 or mho.
Specific Conductance k (Kappa) :- It is the reciprocal of specific resistance i.e.
k = 1 = 1 ´ 1 = 1 ´ conductance (C)
r R a a
If l = 1 cm and a = 1 sq. cm., then, k = C

Thus, specific conductance is defined as the conductance of a solution in a cell in
which the electrodes are 1 cm apart and have unit (1 sq. cm) area.
The term l is called cell constant.

a
Therefore, specific conductance (k) = cell constant ´ conductance.

specific conductance
or cell constant =
conductance
The unit of specific conductance is ohm-1 cm-1

ELECTROCHEMISTRY 79
Equivalent conductance ( L ) : Specific conductance is a property of the conducting

medium. But while dealing with electrolytic solutions a quantity of greater significance known
as equivalent conductance is more commonly used. In these cases, conductance also depends
upon the concentration of electrolyte or the number of ions present in the solution.
Equivalent conductance is defined as the conducting power of all the ions produced
by one gram equivalent of an electrolyte in a given solution. It is denoted by ' L ' (lambda)
Equivalent conductance is related to specific conductance by the following relation.
Equivalent conductance = specific conductance ´ V
where V is the volume in c.c. containing one gram equivalent of the electrolyte.
Therefore, L = k ´ V = 1000 ´ k
C
where C is the concentration of the electrolyte in gram. equivalent per litre.
Unit of equivalent conductance is ohm-1 . cm2 / gm. equiv.
Molar conductance (m) : Molar conductance of a solution is the conducting power of

all the ions provided by one gram mole of electrolytic solution. It is denoted by "m" (Mu)
Molar conductance is related to specific conductance by the relation :
m = k ´ V = k ´ 1000
C
where 'k' is the specific conductance 'V' is the volume of the electrolytic solution containing one
mole of the electrolyte and 'C' is the molar concentration (number of moles of electrolyte per litre
of the solution)
The unit of molar conductance is ohm-1 . cm2 mole-1.
3.8 MEASUREMENT OF CONDUCTANCE :
The Wheatstone bridge method is generally employed for this purpose. This method
measures the resistance of solution, the reciprocal of which gives the conductance. A schematic
diagram of the apparatus is shown in fig 3.2.
Unknown solution of electrolyte is taken in a suitable conductivity cell placed in a
thermostat. Resistance of the electrolyte can not be measured by applying direct current because
of the following reasons.
(i) Electrode reactions change the concentration of electrolyte about the electrode.
(ii) The products of electrolysis produce an opposing potential. In order to avoid these
TEST SOLUTION
RESISTANCE R
BOX
Z
A R B
TELEPHONE HEAD
INDUCTION COIL
THERMOSTAT
Fig. 3.2 Conductivity determination
difficulties, the resistance of electrolyte is measured by applying an alternating

current with a frequency of the order of kilo Hertz from an induction coil. 'R' is
the resistance box and a telephone head is used to detect the current. AB is a
uniform wire and sliding contact point 'Z' moves over it
When current flows, a known resistance R is introduced through the resistance box. The
resistance should be about the same order as that of the solution. The sliding contact Z is moved
along the wire AB until no sound (or minimum sound) is heard in the detector. At this null point,
Resistance of the solution length ZB
=
Resistance R length ZA
Since 'R' is known and length ZB and ZA can be read from the scale fixed below the wire
AB, the resistance of the solution can be calculated. Reciprocal of resistance gives the conductance.
Problems on Conductance
1. A decinormal solution of sodium acetate when placed between two electrodes
each 1.5 cm square and placed at a distance of 0.72cm has a resistance of 52.4
ohms. Calculate its specific conductance and equivalent conductance.
l
R=r Here, l = 0.72 cm, a = 1.5 sq. cm, R = 52.4 ohm.
a
r = R.a = 52.4 ´ 1.5 = 163.8 ohm cm

l 0.72
ELECTROCHEMISTRY 81
Specific conductance (k) = 1 = 1 = 0.0061 mhos.cm-1

r 163.8
Equivalent conductance = k ´ V = 0.0061 ´ 10, 000 = 61 mhos.cm2 /g.eq.
2. In a conductivity cell, 0.01 N KCl solution gave a resistance of 225.0 ohms while
a 0.01N solution of HCl gave a resistance of 77.1 ohms. Specific conductance of
KCl solution is 0.00141 mhos.cm-1. Calculate the specific and equivalent
conductance of HCl solution.
a l
Specific resistance (r) = R ´ , where = cell constant
l a
Specific conductance
Cell constant =
Observed conductance of KCl solution
= 0.00141 = 0.00141 ´ 225 = 0.317 cm-1

1/225
specific conductance of HCl solution = conductance ´ cell constant.
= 1 ´ 0.317 = 4.11 ´ 10-3 mhos.cm-1
77.1
Equivalent conductance ( L ) = k x V
= 4.11 ´ 10-3 ´ 100,000 = 4.11 ´ 10-3 ´ 105 = 4.11 ´ 102 mhos.cm2/g.equiv.
3. Electrolytic conductance of 0.20 mol. l-1 solution of KCl at 298K is 2.48 ´ 10-2
ohm-1. cm-1. Calculate its molar conductance.
specific conductance (k) = 2.48 ´ 10-2 ohm-1 cm-1
\ 0.2 mol KCl will be present in
1000 cm3 = 5000 cm3 solution.
0.2
Thus, V = 5000 cm3 mol-1 solution
Molar conductivity = m = k ´ V
= 2.48 ´ 10-2 ´ 5000 = 124 ohm-1 cm2 mol-1
4. N/10 solution of NaCl has specific conductance of 0.001119 ohm-1 cm-1. Find
out equivalent conductivity.
Equivalent conductance ( L ) = 1000k
C
N
Here, solution means C = 0.1
10
\ L = 0.001119 ´ 1000 = 11.19 ohm-1 cm2 g.equiv.-1

0.1
Factors affecting equivalent conductance

(1) It increases with increase in temperature of solution.
(2) Increase in ionic interaction decreases equivalent conductance.
(3) It is more or less inversely proportional to viscosity of the solvent.
(4) Association of ions leads to decrease in equivalent conductance.
(5) Strong ion-solvent interaction can increase the size of the ions leading to decrease
in equivalent conductance.
But the most important factor is the concentration of the electrolyte or its dilution, which
is discussed below.
3.9 EFFECT OF DILUTION ON EQUIVALENT CONDUCTANCE :
Conductance of the solution depends upon -

(i) Nature of electrolyte (ii) Dilution (iii) Temperature
Electrolytes are divided into two types :- (a) strong electrolytes.
(b) weak electrolytes.
Strong electrolytes : Acids such as HCl, H2SO4 etc, alkalies such as NaOH, KOH etc.
and most of the salts ionise completely in solution and thus have high values of conductance even
at high concentrations, are known as strong electrolytes.
Weak electrolytes : Some acids like acetic acid and bases like ammonium hydroxide
do not ionise completely in solution and have low values of conductance are known as weak
electrolytes.
Effect of dilution : Equivalent conductance of any electrolyte increases with increasing

dilution i.e., decreasing concentration of the solution. Results of conductance measurement of
many electrolytes shows that variation of equivalent conductance with concentration depends
upon the type of electrolyte (fig 4.3). A solution which contains larger number of ions compared
to another solution of same concentration at the same temperature, is said to be strong electrolyte
and the other having low degree of ionisation is called weak electrolyte. Increase in equivalent
conductance with dilution is not so large in case of strong electrolytes, as in the case of weak
electrolytes.
ELECTROCHEMISTRY 83
On plotting equivalent conductance of some electrolytes against concentration the curves

obtained are shown in fig 3.3 below.
EQUIVALENT CONDUCTIVITY ®
KCl
BaCl2
NiSO4
CH3COOH
CONCENTRATION ®
Fig. 3.3 Change in equivalent conductivity with dilution
It is observed that for strong electrolytes, there is a tendency for equivalent conductance
to approach a certain limiting value when concentration approaches zero. This limiting value is
called equivalent conductance at infinite dilution or zero concentration denoted by L 0. In case of
strong electrolytes it is found by extrapolating the equivalent conductance graph to zero
concentration.
In case of weak electrolytes, it is observed that at the higher concentrations the equivalent
conductance is very low but in the more dilute solutions the values rise rapidly. In such cases
(like acetic acid) the limiting value can not be attained by extrapolating the graph to zero
concentration. However, for weak electrolytes the value may be obtained indirectly by using
Kohlrausch's law.
With increase in degree of dissociation due to dilution more number of ions are furnished
and equivalent conductance increases. When limiting value of equivalent conductance is
approached, the degree of dissociation is unity. At any other concentration degree of dissociation
is calculated from the conductance ratio. i.e. the ratio opf equivalent conductance at any
concentration ( L c) to that at infinite dilution ( L 0)
Lc
a=
L0
Equivalent conductance at a given concentration

Degree of dissociation =
Equivalent conductance at infinite dilution.
3.10 KOHLRAUSCH'S LAW :
It has already been observed that equivalent conductance of solution increases with dilution
until it becomes constant. This limiting value, L 0 is known as equivalent conductance at infinite
dilution.
Kohlrausch (1875) studied the equivalent conductances at infinite dilution ( L0) for a
number of pairs of strong electrolytes having the same cation or anion. The values are recorded in
Table - 4.1 below.
Table - 3.1
L 0 values of some pairs of electrolytes at 298K.
Electrolyte L0 Difference Electrolyte L0 Difference
KCl 149.86 KBr 151.92
23.41 2.06
NaCl 126.92 KCl 149.86
KBr 151.92 LiBr 117.09

23.41 2.06
NaBr 128.51 LiCl 115.03
From the table it is found that replacement of potassium ion in any of electrolytes
having a common anion produces the same difference (23.41 ohm -1cm-2 g. equiv-1) in L 0,
irrespective of the chloride ion in any of the electrolytes, having a common cation produces the
same difference (2.06 ohm-1 cm2 g.equiv-1) in L 0.
Thus he concluded that the difference in conductances of any two cations or anions appears
to be the same, irrespective of the nature of the other ions with which they are associated.
Kohlrausch concluded that at infinite dilution, where dissociation of all electrolytes is complete,
each ion migrates independently and contributes to the total equivalent conductance of an
electrolyte a definite share, which depends only on its nature and not at all on that of the ion with
which it is associated. He put forward the law of independent migration of ions which states
that :
At infinite dilution, each ion makes a definite contribution towards equivalent conductance
of the electrolyte irrespective of the nature of the other ion with which it is associated and that
the value of equivalent conductance at inifinite dilution for any electrolyte is given by the sum of
the contributions of the two ions.
So, L 0 = l0a + l0c
ELECTROCHEMISTRY 85
where l0a and l0c are called the ionic conductances at infinite dilution of the anion and
cation respectively.
Application: Equivalent conductance at infinite dilution can be obtained graphically by
extrapolation for strong electrolytes. But this method can not be applied for weak electrolytes.
However, conductance of weak electrolytes can be evaluated by the application of Kohlrausch
law. For example, equivalent conductance of acetic acid at infinite dilution can be evaluated
from the equivalent conductance at infinite dilution of hydrochloric acid, sodium chloride and
sodium acetate by the following procedure.
l0CH3COO- + l0H+ = (l0H+ +l0Cl-) + (l0CH3COO- + l0Na+) - (l0Na+ l0Cl-)
or, L 0CH3COOH = L 0HCl + L 0CH3COONa - L 0NaCl
Putting the conductance value of L 0HCl, L 0CH3COONa and L 0NaCl in the above
equation L 0CH3COOH can be calculated.
Problem
(1) Equivalent conductance of sodium propionate, hydrochloric acid and sodium
chloride at infinite dilution are 85.9, 426.1, 126.4 mhos.cm2eq-1 respectively at
298 K. Calculate equivalent conductance at infinite diulation for propionic acid.
(i) L0C2H5COONa = l0C2H5COO- + Na+
(ii) L 0HCl = l0H+ + l0Cl-
(iii) L 0NaCl = l0Na+ + l0Cl-
Adding (i) and (ii) and subtracting (iii) from it, L0C2H5COOH can be obtained.
L 0C2H5COOH = L 0C2H5COONa + L 0HCl - L 0NaCl
= 85.9 + 426.1 - 126.4 = 385.6 mhos cm2eq-1
(2) Calculate the degree of dissociation of sodium chloride in 0.1N solution. The
equivlaent conductance at this dilution is 98.4 mhos cm 2 eq-1 and ionic of sodium and chloride
ions are 43.4 and 65.5 mhos. cm2 respectively.
L cNaCl = 98.4 mhos.cm2eq-1
L0NaCl = l0Na+ + l0Cl- = 43.4 + 65.5 = 108.9
Lc 98.4
a = = = 0.9036
L0 108.9
Hence degree of dissociation is 0.9036
3.11 ELECTROCHEMICAL CELLS :
Electrochemical cells can be grouped into two categories :

(i) Electrolytic cells (ii) Galvanic cells
An electrolytic cell is a device in which the external supply of electrical energy is necessary
in order to bring about a physical or chemical change in the cell.
On the other hand in a galvanic cell the energy released by a physical or chemical change
is transformed into electrical energy. Examples are Daniell cell, Laclanche cell, dry cell, storage
battery etc.
Chemical reactions often result in energy changes. In an electrochemical cell, the energy
change appears in form of electricity as a result of chemical reactions called redox reactions
(reduction and oxidation). Electrical energy is produced in the cell due to oxidation at one electrode
and reduction at the other electrode of the cell.
Oxidation involves loss of electrons.

For example : Zn ® Zn2+ + 2e
Fe ® Fe2+ + 2e
Fe2+ ® Fe3+ + e etc.
Reduction involves the gain of electrons.
For example : Fe3+ + e ® Fe2+
Cu2+ + 2e ® Cu
A reaction in which oxidation and reduction take place simultaneously is called redox
reaction.
For example : Zn(s) + CuSO4(aq) ® ZnSO4(aq) + Cu(s)
Zn ® Zn2+ + 2e (oxidation half reaction)
Cu2+ + 2e ® Cu (reduction half reaction)
Galvanic cell
Materials : Let us consider an electrochemical cell of the type Zn-CuSO 4. In this case two
beakers are used. Zinc and copper rods are used as electrodes and a salt bridge is
used to have continuity between the two solutions in beakers.
In one of the beakers 0.1 M ZnSO4 solution is taken in which a zinc rod is dipped. It is
called zinc-half cell. In another beaker 0.1M CuSO4 solution is taken in which a copper rod is
dipped. It is called copper-half cell. Solutions in the two beakers are connected by an inverted
U-tube containing an electrolyte. Two ends of the U-tube have porous plugs. Zinc rod which
serves as anode is connected to the copper rod which serves as cathode by copper wires having
a galvanometer in the circuit.
ELECTROCHEMISTRY 87
The arrangement is shown

The arrangement is in Fig. 3.4
shown below:
in Fig. 4.4 below:
e- e-
GALVANOMETER
Cu WIRE Cu WIRE
ANODE CATHODE
SALT BRIDGE
Zn Cu
0.1M 0.1M
ZnSO4 ZnSO4
Fig. 3.4 Electrochemical cell
Working
(i) On connecting the two rods, zinc rod dissolves to from Zn 2+ ion which goes into
solution.
Thus, oxidation takes place at the Zn-anode (loss of electron)
Zn. (s) ® Zn2+ (aq) + 2e
This constitutes the Zn-ZnSO4 half cell (oxidation half cell)
(ii) Electrons produced at the zinc-electrode flow through the copper wire and the
Cu-electrode into CuSO4 solution. Copper ions in the solution are reduced and
copper is deposited on the cathode. Thus, reduction takes place at the copper
electrode. (gain of electron).
Cu2+(aq) + 2e ® Cu(s).
This constitutes the Cu-CuSO4 half cell (reduction half cell)
In the outer circuit electron flows from Zn-rod (anode) to Cu-rod (cathode). The
conventional current flow is in opposite direction to that of flow of electrons.
(iii) Salt bridge is the device containing an electrolyte like KCl, KNO 3 etc. (in agar
gel) in the U-tube which maintains continuity between the two half cells.
To sum up the functions in an electrochemical cell the following points are to be remembered.
(a) Electrochemical cell converts the energy produced in a chemical reaction to

electrical energy.
(b) Anode is the electrode at which oxidation half reaction takes place.
(c) Cathode is the electrode at which reducation half reaction takes place.
(d) Electrons flow in the external circuit from anode to cathode.
(e) Current flows in opposite direction to the flow of electrons.
(f) Salt bridge maintains continuity between the solution in two half cells.
(g) The cell is represented by writing the oxidation half cell in the left hand side and
reducation half cell in the right hand side with salt bridge in the middle indicated
by two vertical lines.
Zn | Zn2+ (0.1 M) | Salt bridge | Cu2+ , | Cu. (0.1M)
or, simply, Zn | Zn2+ || Cu2+ | Cu.
Daniell cell
The galvanic cell in which Zn - CuSO4 reaction occurs is known as Daniell cell. Working
principle of the cell has been described under galvanic cell. In the Daniell cell the salt bridge is
replaced by porous pot, so that the two electrolytes remain separated but the ions diffuse through
the pot. The arrangement is shown in Fig. 3.5.
POROUS POT
COPPER VESSEL
CuSO4 SOLUTION
ZnSO4 SOLUTION
Fig. 3.5 Daniell cell
In this case copper sulphate solution is taken in a copper vessel which serves as cathode.
Zinc sulphate solution is taken inside the porous pot in which zinc rod is dipped which serves as
anode. Porous pot is placed in the copper sulphate solution. Working of the cell is similar to that
described under galvanic cell.
ELECTROCHEMISTRY 89
3.12 CELL REACTIONS :
(i) Zn, | ZnSO4 | KCl | Hg2 Cl2 (s), | Hg.

Zinc rod dipped in ZnSO4 solution. Salt bridge consists of KCl and the calomel
electrode consitsts of Hg2 Cl2 (s), Hg (l)
At anode Zn (s) ® Zn2+ + 2e
At cathode Hg2Cl2(s) + 2e ® 2Hg(l) + 2Cl-
electron flows from znic-anode to mercury-cathode.
(ii) Zn, | ZnSO4 | K2SO4 | HCl, | H2, Pt
Here zinc rod is dipped in zinc sulphate solution Salt bridge consists of potassium
sulphate. Hydrogen gas at one atomospheric pressure is passed through platinum
electrode dipped in hydrochloric acid. Zinc rod serves as the anode and platinum
electrode serves as cathode.
At anode Zn (s) ® Zn2+ (aq) + 2e
At cathode 2H+(aq)+2e ® H2(g)
Electron flows from zinc electrode to hydrogen electrode.
(iii) Cu, | Cu(NO3)2 || AgNO3 |Ag with KNO3 solution as salt bridge.
At anode, Cu(s) ® Cu2+ (aq) + 2e
At cathode, Ag+(aq) + e ® Ag(s)
Copper rod dipped in Cu(NO3)2 solution serves as anode and silver rod dipped in AgNO3
solution serves as cathode. Election flows from copper to silver electrode.
(iv) Zn, Zn(NO3)2 || KNO3 || AgNO3, Ag with KNO3, salt bridge
Similarly, at anode, Zn ® Zn2+ + 2e
At cathode Cu2+ (aq) + 2e ® Cu(s)
Electrons flow from zinc to silver electrode.
(v) Pt, H2, HCl | K2SO4 || CuSO4, Cu
Platinum electrode is dipped in hydrochloric acid. Hydrogen gas under one atmospheric
pressure is bubbled through it. Copper electrode is dipped in CuSO 4 solution. K2SO4 solution
serves as the salt bridge.
At anode, H2(g) ® 2H+(aq) + 2e
At cathode Cu2+ (aq) + 2e ® Cu(s)
Electrons flow from hydrogen to copper electrode.
3.13 ELECTRODE POTENTIAL :
In the electrochemical cell one electrode loses electrons (oxidation) and the other electrode
gains electron (reduction). The tendency of an electrode to lose or gain electrons is called
electrode potential. It is called oxidation potential, where oxidation takes place at the electrode
and reduction potential where reduction takes place at the electrode.
In the half cell, if the metal rod is suspended in a solution of one molar concentration and
temperature is 298K, the electrode potential is called standrad electrode potential (E0). If a gas
is involved, instead of solution the standard conditions are 298K and one atmospheric pressure.
(i) Absolute electrode potential can not be determined (as no half cell works
independently). Therefore , electrode potential is measured with respect to a
standard electrode, (Electrode potential of standard hydrogen electrode is zero).
(ii) Electrode potential of an electrode changes with change in the concentration of
ions in solution in contact with the electrode.
Reduction potential of an electode µ Concentration of ions
1
Oxidation potential of an electrode µ
Concentration of ions
(iii) Electrode potential is expressed in volts.
Standard hydrogen electrode is used as reference electrode to determine electrode
potentials of other electrodes.
3.14 SINGLE ELECTRODE POTENTIAL :
When the two half cells constituting an electrochemical cell is connected through a
voltmeter to measure the potential difference between the two electrodes, this is called the e.m.f.
of the cell. The contribution of each electrode to the cell potential is called single electrode
potential. But the potential of a single electrode cannot be measured. Therefore, one electrode is
chosen arbitrarily as a standard electrode (whose potential is known) to measure the potential
difference between the standard electrode and any other electrode. A standard (normal) hydrogen
electrode is taken as the standard reference electrode and its standard electrode potentail is taken
to be zero volt.
Standard hydrogen electrode : It consists of a platinum foil coated with finely divided
platinum black and dipped in an acid solution of one molar concentration. Hydrogen gas at a
pressure of one atmosphere is continuously bubbled into the solution and temperature is maintained
at 298 K. The reaction taking place at the electrode is
H2(g) ® 2H+(aq) + 2e
2H+(aq) + 2e ® H2(g)
ELECTROCHEMISTRY 91
Depending upon the type of

reaction, hydrogen electrode can act as an
anode or cathode in the electrochemical cell.
Potential of all other electrodes are found
by coupling it with a standard hydrogen H2 gas at
1 atm. pressure
electrode.
Thus, single electrode potential of

an electrode is measured by joining it with 1M
HCl Pt plate
standard hydrogen electrode (using salt
bridge) and measuring the e.m.f. of the
galvanic cell.
Fig. 3.6 Standard Hydrogen electrode
3.15 NERNST EQUATION :
Nernst gave a relationship between reduction of an electrode and concentration of ions

in the electrode reaction.
Mn+ (aq) + ne ® M(s)
2.303RT M
E = E0 - log
nF [Mn+]
As the concentrations of pure solids and liquids are taken as unity, the equation can be
written as-
2.303RT
E = E0 + log (Mn+)
nF
where, R = 8.31 JK-1 mol-1
T = Temperature in Kelvin, usually 298 K
n = Number of moles of electrons
F = Faraday = 96,500 coulombs.
Equilibrium constant from Nernst Equation
Consider the redox reaction in a cell at equilibrium
Zn (s) + Cu2+ (aq) Zn2+(aq) + Cu(s)
[Zn2+(aq)]
Equilibrium constant, Kc = . From Nernst equation, we have
[Cu2+(aq)]
0.0591 [Zn2+] 0.0591
Ecell = E0cell - log = E0- log Kc
2 [Cu2+] 2
0.0591
or, E0cell = log Kc at 298 K.
2
2.303RT
or, E0cell = log Kc (General equation)
nF
Free Energy Change in Electrochemical cell
In electrochemical cell, chemical energy is converted into electrical energy. Electrical
energy is produced due to the work done in the cell and electrical work done is equal to the
decrease in free energy. Change in free energy of the system ( DG) is negative which indicates
that electrical work is done in the system on the surroundings.
Electrical work done = Quantity of electricity flowing ´ E.m.f. of the cell.
In a cell reaction, if 'n' moles of electrons are transferred, the quantity of electricity following
= nF Faradays
Suppose Ecell = E.m.f. of the cell.
\ Electrical work done = nF ´ E.m.f. of cell = nF.Ecell
For a spontaneous reaction, DG is negative.
Under standard condition, i.e. molar Conc. = 1M, T = 298 K,
DG0 = -nF E0 cell where DG0 is the standard free energy change.
Then, DG0 = - RT ln Kc where 'Kc' is the equlibrium constant of cell reaction.
Therefore, DG0 = - 2.303 RT log Kc
Using this equation either DG0 or Kc can be calculated.
3.16 ELECTROMOTIVE FORCE (E.M.F.) OF A CELL :

Electrochemical cell is made of two half cells containing two electrodes. One of the
electrodes must have a higher electode potential than the other electode. Due to this potential
difference between the two electodes electrons flow from electrode of higher potential to the
electrode at lower potential. The difference between the electrode potentials of two half cells is
called as electromotive force (e.m.f.) of the cell or cell potential or voltage.
E.m.f. of a cell is measured by connecting the voltmeter between the two electrodes of a
cell. Magnitude of e.m.f. depends upon the nature of the electrodes and concentration of solutions
of the two half cells.
Example - Daniell cell Zn, ZnSO4 (1M) | CuSO4 (1M), Cu.
Concentration of the solutions is 1M and temperature 298 K
E.m.f. of the cell = 1.10 volts.
Therefore, Ecell = Eanode -Ecathode (in terms of oxidation potential)
and Ecell = Ecathode - Eanode (in terms of reduction potential)
An electrode with higher oxidation potential (lower reduction potential) is called
anode and an electrode with lower oxidation potential (higher reduction potential) is called
cathode.
ELECTROCHEMISTRY 93
3.17 ELECTROCHEMICAL CELLS :
Types of Electrochemical cells

As discussed earlier, electrochemical cells are those in which the chemical energy is
converted to electrical energy. Mainly, there are two types of electrochemical cells which produce
electricity from a chemical reaction. They are
(i) Primary cells or Dry cells or Primary batteries
(ii) Secondary voltaic cells or Reversible cells.
(i) Primary cells (Dry cells)
Any battery or dry cell used for production of electrical energy is a voltaic cell or galvanic
cell where chemical energy of the redox reaction is converted to electrical energy. In this type of
cell, once the chemicals are consumed, further reaction is not possible and the cell stops producing
electricity. Any attempt to regenerate by reversing the current flow through the cell from an
external source of electrical energy fails. The household batteries like Eveready, Panasonic, Nippo
etc are all primary batteries. They are named as ‘‘dry cells’’ or ‘‘dry batteries’’ because they do not
use any solution. Dry cells are light, compact and their voltage do not vary appreciably during
use. A single cell has a potential of nearly 1.5V.
Other such cells include ‘‘Mercury cells’’ also called ‘‘botton cells’’ suitable for low current
devices like watches, hearing aids etc and the cell potential of each units is around 1.3 volts.
Alkaline dry cells are similar to ordinary dry cells, but use concentrated KOH instead of NH 4Cl
as in dry cells. The cell potential is around 1.5 volts.
(ii) Secondary voltaic cells or Reversible cells »:
Secondary voltaic cells or Reversible cells are those in which the original reactants of the
cell are regenerated by passing direct current from an external source in the opposite direction i.e.
they can be recharged. A good secondary cell can be discharged (while supplying electric current)
and recharged several times for reuse.
Lead accumulator or Lead storage battery :
Lead accumulator or Lead storage battery is the most important secondary cell commonly
used in automobiles and inverters.
It consists of a lead anode and a grid of lead packed with lead dioxide (PbO 2) as cathode.
The electrolyte is a 38% solution of sulphuric acid ( » 4M). The whole container is made of either
glass or a polymeric material like bakelite (Fig. 3.7). The oxidation half cell is Pb/H 2SO4 and the
reduction half cell is PbO2 / H2SO4. Since H2SO4 is common to both the electrodes, the cell can be
represented as Pb | H2SO4 | PbO2
Glass vessel or Bakelite vessel
Lead dioxide
Lead
Dilute H2SO4
Separators
Fig. 3.7 Lead accumulator

When the battery is in use, it is said to be in discharging mode. While in discharging

mode, the half cell reaction is as follows.
Oxidation half cell (at anode) : Pb(s) + SO4(aq) PbSO4(s) + 2e–
Reduction half cell (at cathode) : PbO2(s) + SO42–(aq) + 4H+ + 2e– PbSO4(s) +2H2O(l)
The overall cell reaction is Pb(s) + PbO2(s) + 2H2SO4 (aq) 2PbSO4(s) +2H2O(l)
When the battery is re-charged i.e. while in recharging mode, the opposite reaction takes
place. At the oxidation half cell, reduction takes place
PbSO4(s) +2e42– Pb(s) + SO4(aq) and at the reduction half cell, oxidation takes place.
PbSO4(s) +2H2O(l) PbO2(s) +SO42–(aq) + 4H + + 2e–
Thus, the over all reaction in recharging mode is
2PbSO4(s) + 2H2O(l) Pb(s) + PbO2(s) + 2H2SO4(aq)
Water is consumed and H2SO4 is formed thus raising the specific gravity of the electrolyte.
In the recharging process the positive electrode is coated with dark brown lead dioxide and the
negative electrode with grey spongy lead. The emf of the cell rise and the electrical energy supplied
is converted into chemical energy which is stored in the cell.
The charging process is monitored by measuring the specific gravity of the electrolyte. It
varies from 1.28 when fully charged (H2SO4 and H2O) to 1.2 when discharged (mostly water).
The potential of a fully charged cell is 2.1 volts. It should not be discharged below 1.8V. This
secondary cell has a low internal resistance i.e. it can deliver a high current. It can be recharged a
very large number of times without deterioration.
Since each cell has a potential of about 2.1V, six such cells connected in series make up a
12 volt car battery.
Nickel -Cadmium Rechargeable cells (NiCad)
Now a days electronic gadgets like telephone, mobile phone, portable CD players,
calculators, pagers, digital cameras etc use these type of secondary rechargeable cells. Though
these are dry cells, they are rechargeable. The cell can be represented as
Cd | OH– || NiO2
At the anode, Cd + 2OH– Cd (OH)2 +2e–
At the cathode, NiO2 +2H2O+2e– Ni(OH)2 +2OH–
The over all cell reaction is Cd + NiO2 + 2H2O Cd (OH)2 + Ni (OH)2 during discharging
mode i.e. while in use.
The potential of such a battery is around 1.2 volt.
Fuel Cells
Fuel cells are galvanic cells which convert the energy produced during combustion of fuels
like hydrogen, methane, carbon monoxide, methanol etc. directly into electrical energy Electricity
produced by thermal plants create a lot of pollution. Again, the primary cells can produce electricity
for a short period since the quantity of the oxidising and reducing agent is limited. But in fuel
cells, electrical energy can be obtained indefinitely as long as fuel supply is maintained for outside
ELECTROCHEMISTRY 95
source. The most successful fuel cell is the hydrogen-oxygen fuel cell and was used in Apollo
space programme to generate power and the water produced as byproduct was used as drinking
water for the astronauts.
A hydrogen-oxygen fuel cell consists of three compartments separated by porous graphite
electrodes (anode and cathode) impregnated with finely divided platinum or palladium as catalyst.
The electrolyte in the central compartment is a resin containing concentrated aqueous sodium
hydroxide solution. A schematic diagram of a H2–O2 fuel cell is given in Fig.3.8. Hydrogen as is
fed into one compartment and oxygen gas, into another. The gases diffuse slowly through porous
electrodes and so does the electrosyte. Chemical reactions take place. Hydrogen is oxidised at the
anode and oxygen is reduced at the cathode in presence of electrolyte.
e– e–
e– e–
Fuel in H2 O2 (Fuel in)

e–
e–
e–
O2
H2
H2O
unused gas, water out

Excess H2 Gas out
Anode Electrolyte Cathode
Fig. 3.8 Schematic diagram of H2– O2 Fuel cell

At the anode, hydrogen is oxidised to H+ ions, which are neutralised by OH– ions of the
electrolyte.
2H2 4H+ + 4e–
4H + 4OH–
+
4H2O
Thus, at the anode, 2H2(g) + 4OH–(aq) 4H2O (l) + 4e–
At the cathode, oxygen is reduced to OH– ions
O2(g) + 2H2O(l) + 4e– 4OH– (aq)
The net cell reaction is 2H2(g) + O2(g) 2H2O(l)
The water produced vapourises off as the cell is operated at a temperature above 100 0C.
This is then condensed and used. The electrolyte allows only charged particles to move through
it from anode to cathode and not electrons which move through the external circuit producing
current.
An individual fuel cell produces a very small amount of direct current (DC) of about 1 volt.
So several such fuel cells are stacked or placed in series to increase the current output. The main
advantages of the fuel cells are
(a) they are non-polluting.
(b) like secondary cells, they do not need to recharge.
(c) the efficiency of fuel cells is about 70% compared to thermal plants where efficiency is
about 40%
Recently, fuel cell technology has advanced a lot. Modified electrodes, catalysts and
electrolytes have increased the efficiency of such cells considerably. They are used in automobiles,
buses, air planes, boats, motor cycles and submarines.
3.18 ELECTROCHEMICAL SERIES :

When the potential of the electrode is measured by dipping the electrode in normal solution
of one of its salts with normal hydrogen electrode, it is known as the normal electrode potential
or standard electrode potential (E0). for example, the standard electrode potential of Zn/Zn 2+
electrode can be determined by setting up a cell of the type.
Zn | Zn2+ || H+ (a= 1) | H2 (1atm) | Pt
Ecell = EZn, Zn2+ - EH2, H+ = EZn, Zn2+ -0) (since EH , H = 0)
= EZn, Zn2+ 2 +
The e.m.f. of the cell was found to be 0.763 volt, hence EZn, Zn2+ is 0.763 volt. Similarly,
standard electrode potential of several other elements can be determined. When the metals are
arranged in the order of their standard electrode potentials on hydrogen scale, a series is obtained
which is known as electrochemical series or electromotive potential series.
Table 3.2 below gives the standard electrode potential E 0 of a number of electrodes at
298K. In this series, a negetive potential indicates the tendency greater than hydrogen to go into
the solution in the ionic from. Therefore the metal having more negative potential displaces
those with more positive potentials from their solutions.
Table 3.2 Standard electrode potentials (Reduction) at 298K

Electrode Electrode reaction E0 (volts)
Li+, Li Li+ + e Li (s) - 3.04
K+, K K+ + e K (s) - 2.92
2+
Ba , Ba 2+
Ba + 2e Ba - 2.906
Ca2+, Ca Ca2+ 2e Ca (s) - 2.87
+
Na , Na +
Na + e Na(s) - 2.71
Mg+2, Mg Mg2+ + 2e Mg (s) - 2.370
3+
Al , Al 3+
Al + 3e Al(s) -1.660
Zn2+, Zn Zn2+ + 2e Zn (s) - 0.76
2+
Fe , Fe 2+
Fe + 2e Fe (s) -0.44
Cd2+, Cd Cd2++2e Cd (s) - 0.40
2+
Co , Co 2+
Co + 2e Co (s) - 0.28
Ni2+, Ni Ni2+ + 2e Ni (s) -0.24
2+
Sn , Sn 2+
Sn + 2e Sn (s) -0.14
Pb2+, Pb Pb2+ + 2e Pb (s) -0.13
+
2H , H2 (g), Pt +
2H + 2e H2(g, 1 atm) + 0.00
Cu2+, Cu Cu+ + 2e Cu + 0.337
+
Ag , Ag +
Ag + e Ag + 0.791
ELECTROCHEMISTRY 97
Application of Electrochemical series
(1) To Calculate e.m.f. of a cell: Standard e.m.f. (E0) of a cell can be calculated by the
following procedure.
(i) Write the half cell reactions with their electrode potentials.
(ii) Balance each half cell reaction to equate number of atoms and change.
(iii) Balance the electrons in both the half cell reactions.
(iv) Subtract equation with lower value of E0 from the equation with higher value of E0
E0cell = Redn. potential of Redn. half cell - Redn. potential of oxdn. half cell.
Example - To calculate e.m.f. of the cell Zn, Zn2+ | | Ag+, Ag.
Zn(s) - 2e ® Zn2+, E0 = - 0.76v (i)
(Redn. potential)
Ag+ + e ® Ag, E0 = 0.79v. (ii)
(Redn. potential)
Multiply eqn (ii) with 2 and subtract eqn (i) from it
Then, we have Zn(s) + 2Ag+ ® 2Ag + Zn2+
Thus, Zn- electrode acts as anode and Ag - electrode as cathode.
E0cell = E0cathode - E0anode = 0.79 - (- 0.76) = 1.55 volt.
(2) To predict the anode or cathode in a cell.

An electrode with higher oxidation potential (lower reduction potential) is taken as anode.
The electrode with lower oxidation potential (higher reduction potential) is taken as cathode.
For example, in the cell, Zn l Zn2+ || Cu2+ | Cu.
E0 for zinc = -0.763 volt, E0 for copper = +0.337volts
(Redn. potential) (Redn. potential)
Therefore, Cu-electrode is the cathode and Zn-electrode is anode.
(3) To predict whether a particular redox reaction can occur or not.

For example, reaction Cu + Zn2+ ® Cu2+ + Zn
Reducation potential of Cu = + 0.337volt and that of Zn = - 0.763volt
Thererfore, the above reaction can not occur. Cu-can not displace zinc as zinc has a
higher position in the E.C. series.
But the reaction, Cu2+ + Zn ® Zn2+ Cu.
can occur and znic can displace copper from its salt solution.
(4) To predict reactivity of elements.

On the basis of electrode potentials, a given set of elements can be arranged in the order
of their reactivity. An element whose oxidation potential is more (or reduction potential
is less) is said to be more active. A more reactive metal can displace a less reactive metal
from its solution, but not the vice-versa. For example, zinc can displace copper from its
salt solution. In order of reduction potential the series can be arranged as follows.
Increasing order of Reactivity
Li < K < Ba < Ca < Na < Mg < Al < Zn < Co < Fe < Cd < Ni < Sn < Pb < H2 < Cu < Ag
Decreasing order of
Reduction potential
The metals which are above hydrogen in electrochemical series can displace hydrogen
from mineral acids, but the metals which are below hydrogen (Cu, Ag etc.) can not liberate
hydrogen from mineral acids.
Problems on E.m.f. (1) Calculate the e.m.f. of the galvanic cells having following reactions.
(i) 2Cr (s) + 3Cd2+ (aq) ® 2Cr3+(aq) + 3 Cd (s)
(ii) Fe2+(aq) + Ag+ (aq) ® Fe3+ (aq) + Ag (s)
E0Cr3+/Cr = - 0.73v, E0Cd2+/Cd = - 0.40v, E0 Fe2+/Fe3+ = 0.77v
E0Ag+/Ag = +0.80v
Solution
(i) Cell is represented as Cr/Cr3+(aq) || Cd2+ (aq) | Cd.
E0cell = E0 cathode - E0anode = -0.40 - (-0.73) = -0.40 + 0.73 = 0.33 volt
(ii) Cell is represented by Fe2+ | Fe3+(aq) || Ag+ | Ag
E0cell = 0.80 - (0.77) = 0.03 volt.
3.19 CORROSION :
The slow coating of surfaces of metallic objects with oxides or other salt of the metal is
called corrosion. In corrosion, a metal is oxidised by loss of electrons to oxygen by which the
metal is positively charged and oxygen is negatively charged. Thus the metal oxide is formed.
Corrosion of metal iron takes place in presence of water and air. Though the chemistry of corrosion
is quite complex, it may be considered essentially as an electrochemical phenomenon. At the
place of corrosion oxidation takes place and that spot behaves as anode. The anodic reaction can
be written as:
Anode : 2Fe(s) ® 2Fe2+ + 4e– ........... (1)
E0Fe2+/Fe = – 0.44 V
ELECTROCHEMISTRY 99
Electrons released at the anode move through the metal and go to another spot on the
metal and reduce oxygen in presence H+ ion. The H+ ion is supposed to be generated from carbonic
acid (H2CO3) formed due to dissolution of carbon dioxide in air with water (CO 2 + H2O ®
H2CO3). At this cathodic spot the following reaction takes place
Cathode : O2(g) + 4H+ (aq) + 4e– ® 2H2O (l) ............... (2)
E0H+ | O | H O = 1.23 V
2 2
By adding equation (1) and (2), the overall reaction is obtained.
2Fe(s) + O2(g) + 4H+ (aq) ® 2Fe2+ (aq) + 2H2O (l)
E0cell = 1.23 V – ( –0.44V) = 1.67 V ............... (3)
The Fe2+ ions are further oxidised by the atomspheric oxygen to Fe 3+ ions which come out
as a rust in the form of hydrated ferric oxide (Fe 2O3 × x H2O) and with further production of
hydrogen ions. Like iron, silver, copper, bronze articles also get corroded by developing oxides
or other salts on their surfaces. Prevention of corrosion is of great importance because of damage
of structures, buildings, bridges etc. by it. Corrosion can be prevented by coating the surface with
paints, by some other chemicals or by covering the sufaces of corrosion prone metals with inert
metals like Zn, Sn, Pt etc. An electrochemical method is to provide a sacrificial electrode of
another metal (like Zn, Mg, Sn etc.) which corrodes itself but keep the object intact.
1. Electrolytic dissociation The process of splitting up of an electrolyte into positively and

negatively charged ions is called electrolytic dissociation.
2. Degree of dissociation (a ) The fraction of the total substance which exists as ions in
solution is called its degree of dissociation.
3. Electrolysis The process of chemical decomposition of an electrolyte in solution or in

fused state by the passage of electric current is known as electrolysis.
4. Faraday's laws of electrolysis: 1st law -- The mass of substance liberated at the electrode
as a result of electrolysis is directly proportional to the quantity of electricity passed
through the electrolyte. (W = z.c.t)
2nd law: When the same quantity of electricity is passed through different electrolytes
connected in series, then the mass of different substances liberated at the electrodes are
proportional to their chemical equivalents.
5. Electrochemical equivalent It is defined as the mass of substance liberated when one

ampere of current is passed through the electrolyte for one second (or one coulomb of
electricity passed)
Chemical equivalent
1Faraday = 96, 500 coulombs. E.C.E. (z) =
96,500
6. Specific conductance (k) Specific resistance is defined as equal to the resistance in ohms
of a material of 1 cm length and the 1 sq. cm in area of the cross section. Reciprocal of
specific resistance is specific conductance. Unit = ohm -1cm-1.
7. Equivalent conductance ( L ) is defined as the conducting power of all the ions produced
by one gram equivalent of an electrolyte in a given solution.
Unit = ohm-1cm2/g.equiv
8. Molar conductance(m ) is defined as the conducting power of all the ions furnished by
one gram mole of electrolyte in a given solution.
Unit = ohm-1. cm2mole-1
9. Kohlrausch law Equivalent conductance at infinite dilution for any electrolyte is given
by the sum of the contributions of the two ions. L0 = l0c + l0a
10. Electrochemical cell It is a device in which redox reaction takes place indirectly and the
chemical energy is converted to electrical energy. Lead accumulator is a secondary
reversible voltaic cell used in automobiles, inverters etc.
11. Electrode potential Tendency of an electrode to lose or gain electrons is called its
electrode potential. Electrode potential at 298K and in one molar concentration is called
standard electrode potential.
12. E.m.f. of cell Ecell = Ecathode - Eanode (in terms of reduction potential).
13. Electrochemical series Arrangements of elements in the increasing order of their standard
electrode potentials (reduction potentials)
QUESTIONS
A. Very Short answer type questions (One mark each) :
1. Give the correct answer
(i) What happens to equivalent conductance when solution is diluted ?
(ii) What is the amount of substance liberated by the passage of 1 Faraday of electricity ?
(iii) Define specific conductance.
(iv) Define equivalent conductance.
(v) Define molar conductance.
ELECTROCHEMISTRY 101
(vi) State Kohlrausch law.

(vii) What is electrode potential ?
(viii) What is the unit of equivalent conductance ?
(ix) Define electrochemical equivalent.
(x) What is the unit of molar conductance ?
(xi) What is cell constant ?
(xii) What is electromotive force ?
(xiii) In the outside circuit of a cell electron flows from which electrode ?
(xiv) Which gas is liberated at anode due to electrolysis of molten sodium hydride ?
(xv) Which gas is liberated at cathode due to the electrolysis of aqueous solution of
sodium chloride ?
(xvi) What is the unit of e.m.f. ?
(xvii) What is an electrochemical cell ?
(xviii) Define degree of dissociation of an electrolyte ?
(xix) What is the unit of specific conductance ?
(xx) What is the basis on which anode or cathode is identified in a cell ?
(xxi) What is the relationship between chemical equivalent and electrochemical equivalent ?
(xxii) What is the function of a salt bridge ?
(xxiii) What happens to the conductance of a solution when temperature is increased ?
(xxiv) Oxidation and reduction take place at which of the electrodes in a cell ?
(xxv) What is the e.m.f. of a standard hydrogen electrode ?
(xxvi) What do you mean by strong electrolyte ?
(xxvii) During electrolysis of aqueous solution of NaCl at which electrode chlorine is
liberated.
(xxviii) What is the charge in coulombs on CO32- ion ?
(xxix) How many coulombs of electricity are required to produce 20 gram of calcium
form molten CaCl2 ?
(xxx) Write the cell representation when Zn electrode is connected to standard hydrogen
electrode :
(xxxi) What is the charge in coulombs on Cu+2 ion?
(xxxii) In an electrochemical cell, reduction taken place at ______.
(xxxiii) What is the relation between standard e.m.f. of a cell and equilibrium constant?
(xxxiv) One faraday of electricity will deposit __________ weight of a metal.
(xxxv) What is the unit of equivalent conductance? How does the equivalent conductance
vary with dilution?
(xxxvi) What is the basis on which anode or cathode is identified in a chemical cell?
(xxxvii) What do you understand by strong and weak electrolytes?
(xxxviii) How many coulombs of electricity are required to produce 20g of calcium from
molten CaCl2?
(xxxix) Represent the cell and the standard emf of the cell having the following reaction.
2+
2Cr(s) + 3Cd (aq) 2Cr3+(aq) + 3Cd(s)
E° Cr3+ / Cr = 0.73V and E° Cd2+ / Cd = -0.40V
(xl) State and explain Kohlrausch's law.
(xli) How many moles of aluminium can be prepared by the electrolysis of molten
alumina with a current of six Faradays.
(xlii) Explain why copper sulphate solution cannot be stored in zinc vessel?
2. Fill in the blanks :

(a) Conductance of a solution __________ with dillution.
(b) Amount of substance liberated by the passage of one coulomb of electricity through
an electrolyte is called ___________
(c) The more _________ the standard reduction potential, the ____________ is the
ability to displace hydrogen from acids.
(d) Conduction of electricity in solution is due to ____________
(e) At __________ electrode in a cell oxidation takes place.
(f) At ______ electrode in a cell reduction takes place.
(g) In electrochemical cell ________ energy is concerted to ________ energy.
(h) E.m.f. of a standard hydrogen electrode is __________.
(i) Zinc has a ____________ tendency to lose electrons than copper.
(j) In a galvanic cell electron flows from _________ to _________ through the
connecting wires.
(k) In a galvanic cell the difference between reducation potential of cathode and anode
is called ___________
(l) An aqueous solution of silver nitrate ___________ be stored in a copper vessel.
(m) According to electrochemical series zinc is __________ active than iron.
(n) Electrolysis of molten sodium hydride liberates ________ gas at the _______.
(o) Electrochemical equivalents of two metals are in the ratio of their _________
(p) E.C.E. ´ ___________ = Chemical equivalent.
(q) Mass of substance liberated at the electrode is directly proportional to ________
(r) On electrolysis of aqueous solution of sodium chloride _________ is liberated at
cathode.
(s) The unit of cell constant is ___________
(t) The unit of equivalent conductance is ______________ .
(u) The unit of specific conductance is ____________

(v) In a Daniell cell copper vessel serves as ____________
(w) In electrochemical series the elements are arranged in order of ________reduction
potentials.
(x) Standard electrode potential of hydrogen electrode is _______________
(y) Specific conductance ´ ____________ = Equivalent conductance.
(z) Conductance of a solution __________ with increase in temperature.
(z1) In an electrochemical cell reduction takes place at _________
(z2) One Faraday of electricitys will deposit _________ weight of a metal.
(z3) A current of 0.5 ampere flowing for 30 minutes deposits 0.2964g of a metal at the
cathode. Calculate the equivalent mass of the metal.
3. Give reasons :
(a) Sodium can not be extracted by the electrolysis of aqueous solution of sodium
chloride.
(b) Silver nitrate solution can not be stored in a copper vessel.
(c) Copper sulphate solution can be stored in a zinc vessel.
(d) Blue colour of copper sulphate solution is dishcharged by dipping an iron rod
in it.
4. Answar the following :

(a) What is the difference between a galvanic cell and electrolytic cell ?
(b) What is the difference between electrode potential and cell potential ?
(c) How electrochemical series predicts the feasibility of a reaction ?
(d) What is the function of a salt bridge ?
(e) What is the relation between standard e.m.f. of a cell and equilibrium constant ?
5. The molar conductance of a solution of AlCl3 in found to be 130 mho cm2 mol-1 at 298K.
What would be its equivalent conductance at the same temperature ?
B. Short answer type questions (Two marks each) :

1. Distinguish between strong electrolytes and weak electrolytes.
2. Define conductance, specific conductance and equivalent conductance.
3. What are the electrolytic products of fused NaCl? Write equations.
4. What is the difference between electrochemical equivalent and chemical equivalent?
5. What is electroplating?
6. What are the main difference between electromotive force of cells and cell potential?
7. Write down the notations of representing cathode, anode, and galvanic cell.
8. What are reference electrodes? What is the electrode potential?

9. What are fuel cells? What are its advantages?
10. Write the reasons of corrosion.
11. How metal corrosion is prevented?
12. Calculate the time required for a current of 2 amp. to decompose one gram mole of water.
13. When a current strength of 965 amp. can deposit 0.9g of Al metal in 20 sec. What is the
efficiency of electrolysis?
14. Standard oxidation potential of iron electrode is + 0.44V. Calculate the potential of Fe,
FeSO4 (1M) at 25°C.
15. What is lead storage battery?
16. Write down Nerst equation. How is it useful in calculating the potential of a cell?
17. 1N salt solution surrounding two platinum electrodes, 2.1 cm apart and 6.3 cm 2 in area was
found to offer a resistance of 50 ohm. Calculate the equivalent conductance of the solution.
18. Ag+ + e– ® Ag; E0 = + 0.8 V and Zn2+ + 2e ® Zn; E0 = – 0.76 V.
Calculate the cell potential for the reaction, 2Ag + Zn 2+ ® Zn + 2Ag+(aq)
19. Write down the working of mercury dry cell.
20. Write down the working of nickel-cadmium cell.
C. Short answer type questions (Three marks each) :

1. What happens to the pH of NaCl solution after electrolysis and why ?
2. Specific conductance of a 0.12 N solution of electrolyte is 2.4 × 10 –2 ohm–1 cm–1. Calculate
its equivalent conductance.
3. What is electrochemical series ? What is its significance ?
4. The equivalent coductance of 0.001N KCl solution is 147 ohm–1 cm2 gm eq–1 at 25°C. Find
the specific conductance.
5. The specific conductance of 0.12N solution of an electrolyte is 0.024 ohm –1 cm–1. Find its
equivalent conductance.
6. Explain why rusting of iron is faster in saline water than in ordinary water. Write equations.
7. An electronic current is passed through two solutions (a) AgNO 3 and (b) a solution of 10g
of blue vitriol in 500 ml of water using platinum electrodes separately. After 30 min. it was
found that 1.307g Ag was deposited. What is the concentration of Cu 2+ after electrolysis?
8. A current of 1.7 amp is passed through 300 mL of 0.16 M ZnSO4 solution for 230 seconds
with a current efficiency of 90%. Find the concentration of divalent zinc in solution.
9. The standard potential of Ni2+/ Ni is – 0.236 V. If this electrode is coupled with a hydrogen
electrode, the emf of the cell becomes zero. Calculate the pH of the acid used in electrode.
10. E0 values for Fe3+ + 3e ® Fe and Fe2+ + 2e ® Fe are – 0.036 V and –0.44 V respectively.
Calculate E0 nnd DG0 for the cell reaction Fe + 2Fe3+ ® 3Fe2+.
11. When salt spread on road to melt ice and snow during winter, corrosion of motor cars is a
major problem, justify.
12. E° of Ag electrode is 0.8V and solubility product of AgI is 1 × 10 –16. Calculate the potential
of Ag electrode at 25°C in a saturated AgI solution in water.

1. State and explain Faraday's laws of electrolysis. How many grams of Aluminium can be
produced by the elctrolysis of molten alumina with a current of 3 amperes for 10 minutes.
2. Define and explain equivalent conductance and specific conductance. A 0.1N solution of
NaCl has a specific conductance of 0.00119 mhos cm-1. Find its equivalent conductance.
3. Explain the terms :
(a) Conductance (b) Specific conductance.
(c) Equivalent conductance (d) Molar conductance
4. State and explain Kohlrausch law. How can this law be used to find equivalent conductance
of acetic acid at infinite dilution ?
5. State and explain Faraday's second law of electrolysis. How does this help in determining
equivalent mass of the metal ?
6. Write notes on :
(a) Electroplating (b) Electrorefining (c) Galvanic cell
(d) Electrotyping (e) Electrochemical series
7. What is meant by electrode potential ? Explain in the half cell reactions of
Zn (s) + Cu2+ (aq) ® Zn2+ (aq) + Cu(s)
8. Discuss the applications of electrochemical series.
9. A current of 0.5 amperes was passed through a solution of silver nitrate for six minutes.
Find the mass of silver deposited (At. mass of Ag = 108)
10. The resistance of N/5 solution of an electrolyte in a cell was found to be 45 ohm. Calculate
the equivalent conductance of the solution if the electroldes in a cell are 2.2 cm apart and
have an area of 3.8 sq.cm.
11. State and explain Faraday's laws of electrolysis. 0.2015gm of copper were deposited by a
current of 0.25 ampere in 45 minutes. What is the E.C.E. of the copper ?
12. Describe the construction and working of Daniell cell.
13. The following reaction occurs in a cell Zn(s) + Co 2+ Co (s) + Zn2+.
Write the elctrode reaction and findout the e.m.f. cell, given
Zn ® Zn2+, E0 = 0.76v Co ® Co2+, E0 = 0.28v.
14. What are the difference between ionisation and electrolysis ? What are strong and weak
electrolytes, discuss with examples.
15. What is the difference between e.m.f. and potential difference ?
16. Give two applications of electrolysis.
17. Define equivalent and molar conductance. Give their relationship with specific conductance.
How does equivalent conductance vary with increase in temperature ?
How many atoms of calcium will be deposited from fused CaCl 2 by a current of 25
milliamperes passes for 60 seconds ?
18. State and explain equivalent conductance and specific conductance. Calculate the mass of
silver deposited when a current of one ampere is passed through AgNO 3 solution for 1
hour. The electrolchemical equivalent of silver is 1.21´10-3
19. Define and explain specific conductance and equivalent conductance. Why on dilution the
specific conductance decreases and equivalent conductance increases ?
A 0.1 N solution of sodium acetate has a specific conductance 0.0061 ohm-1 cm-1. Calculate
the equivalent conductance of the solution.
20. What is a galvanic cell ? Explain with an example. Calculate the half cell potential at 298K
for the reaction Cu2+ (aq) + 2e ® Cu (s), where [Cu2+] is 5.0 M and E0 is + 0.34 volt.
21. State and explain Faraday's laws of electrolysis. 0.2015g of copper was deposited by a
current of 0.25 amp in 45 min. Find out the electrochemical equivalent of copper.
22. Define equivalent and molar conductnce. Give their relationship with specific conductance.
How does equivalent conductance vary with increase in temperature? How many atoms of
calcium will be deposited from fused CaCl2 by a current of 25 milliamperes passed for 60
secs?
23. State and explain equivalent conductance. Calculate the mass of silver deposited when a
current of one ampere is passed through AgNO3 solution for 1 hour. The electrochemical
equivalent of silver is 1.21x10-3.
24. State and explain Faraday's laws of electrolysis.
When a current of 1.5 amp. strength is passed through a solution of salt of a metal (at mass
= 112) for 15 min, 0.783g of the metal is deposited. Find out the valency of the metal.
25. Describe specific and equivalent conductance. How are they related? What is the effect of
dilution on them?
The specific conductivity of an N / 20 solution of KCl at 25°C is 0.002765 mhos. If the
resistance of the same solution placed in the cell is 2000 ohms, what is the cell constant?
26. Define and explain specific conductance and equivalent conductance.
A 0.01 N solution of NaCl has a specific conductance of 0.001112 ohm-1 cm-1. Find its
equivalent conductance.
27. State and explain Faraday's laws of electrolysis.
How many grams of chlorine will be produced by the electrolysis of molten sodium chloride
with a current of 5.5 amperes for 25 minutes?
E. Multiple choice questions (One mark each) :

(i) The electric charge for electrode deposition of the gram equivalent of a substance is–
(a) one ampere for one second (b) 96500 coulombs
(b) charge on one mole of electrons (d) one ampere for one hour
(ii) Which is the strongest reducing agent ?
(a) Zn(s) (b) Cr (s)
(c) H2(g) (d) Fe2+(aq)
(iii) Faraday's law of electrolysis are retated to
(a) atomic number of cation (b) atomic number of anion
(c) equivalent mass of electrolyte (d) speed of the cation
(iv) Molten sodium chloride conducts electricity due to the presence of ______
(a) free electrons (b) free ions
(c) free molecules (d) atoms of sodium and
chlorine
(v) The unit of specific conductance is ________
(a) Ohm (b) Ohm-1cm-1
(c) Coulomb (d) Faraday
(vi) The electrode at which the electrons flow into an electrolyte is ___________
(a) anode (b) metal
(c) cathode (d) solid
(vii) The charge (in coulomb) on the Na+ ion (oxide) is __________
(a) 96500 (b) 4.8 ´ 10+19
(c) 4.8 ´ 10-19 (d) 1.6 ´ 10-19
(viii) 96500 Coulomb will deposit __________ of metal.
(a) one electrochemical equivalent (b) one gm
(c) one gm. equivalent (d) One gm. molecular mass.
(ix) Which one of the following is a weak electrolyte ?
(a) sodium chloride (b) copper sulphate
(c) acetic acid (d) Sodium chloride.
(x) ____________ is an example of strong electrolyte.
(a) Ammonium hydroxide (b) Acetic acid
(c) Sodium acetate (d) Sodium chloride
(xi) Which is the strongest reducing agent ?
(a) Zn(s) (b) Cu(s)
(c) H2(g) (d) Fe2+(aq)
(xii) The unit of cell constant is ___________
(a) ohm-1cm2 (b) cm-1
(c) ohm-1cm-1 (d) ohm-1cm2/gm.equiv.
(xiii) For a redox reaction to proceed in a cell, the e.m.f must be

(a) positive (b) negative
(c) zero (d) fixed
(xiv) Moles of aluminium produced by passing six Faraday of electricity is __________
(a) 2 moles (b) 6 moles
(c) 3 moles (d) 1 moles.
(xv) __________ grams of chlorine can be prepared by the electrolysis of molten sodium
chloride with 10 amperes current passed for 10 minutes.
(a) 2.2 (b) 4.4
(c) 3.8 (d) 5
(xvi) Which of the following type of reactions occur at the anode during electrolysis ?
(a) Dissociation (b) Substitution
(c) Reduction (d) Oxidation
ANSWERS
A.1. (i) increases (ii) 1 gm equivalent (viii) ohm-1cm2 equiv-1 (x) ohm-1cm2mol-1
(xiv) hydrogen (xv) hydrogen (xvi) volt (xix) ohm-1cm-1 (xxiii) increases
(xxiv) anode-oxdn, cathode-redn (xxv) zero (xxvii) anode (xxviii) 3.2´10-19 coulombs
2. (a) increases (b) Electrochemical equivalent (c) negative, greater (d) ions
(e) anode (f) cathode (g) chemical, electrical (h) zero (i) greater (j) anode, cathode
(k) cell potential (l) can not (m) less (n) hydrogen, anode (o) chemical equivalent
(p) 96500 (q) chemical equivalents (r) hydrogen (s) cm -1 (t) ohm-1cm2 gm. equiv-1
(u) ohm-1 cm-1 (v) cathode (w) decreasing (x) zero (y) V (z) increases.
E. Multiple Choice Type :

(i) b (v) b (ix) c (xiii) a
(ii) a (vi) c (x) d (xiv) a
(iii) c (vii) d (xi) a (xv) a
(iv) b (viii) c (xii) b (xvi) d
qqq
CHEMICAL KINETICS 109
UNIT - IV
CHAPTER - 4
CHEMICAL KINETICS
Chemical kinetics is that branch of physical chemistry, which deals with the study of the
rate of chemical reactions and the mechanism by which they occur. In other words, it deals with
how fast or slow the reaction is and through what mechanism a particular chemical reaction
occurs. The rate of a chemical reaction depends upon the experimental conditions such as nature
of reactants temperature, catalysts, the concentration of the reactants and certain energy
radiations.
4.1 TYPES OF CHEMICAL REACTIONS :
On the basis of the speed, the chemical reactions can be classified into the following
categories.
(a) Fast or Instantaneous reactions : These are reactions which are completed immediately.
These reactions occur so fast that, it is practically impossible to measure the exact speed
of such reactions.
For example, (i) the precipitation of silver chloride, and (ii) the decolourisation of acidified
potassium permanganate with ferrous sulphate solutions are instantaneous reactions.
NaCl(aq) + AgNO3(aq) ® AgCl(s) ¯ + NaNO3(aq)
2KMnO4 + 8H2SO4 +10 FeSO4 ® K2SO4 + 2MnSO4+ 5Fe2(SO4)3 + 8H2O
(b) Moderate reactions : There are many reactions which proceed at measurable speed. The
rates of such reactions can be conveniently measured. Some common examples of such
reactions are,
(i) Hydrolysis of ethyl acetate in presence of sodium hydroxide (Saponification of ester)
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
(ethyl acetate) (sodium acetate)
(ii) Hydrolysis of the aqueous solution of sucrose in presence of HCI. (Inversion of
cane sugar)
C H O +H O H+ C H O + C H O
12 22 11 2 6 12 6 6 12 6
(Sucrose) (Glucose) (Fructose)
(c) Extremely slow reactions : These are reactions which take a long time to complete.
These reactions proceed with very slow speed and it is not possible to measure the exact
speed of such reactions.
Rusting of iron is an example of extremely slow reaction.
Fe + H2O + CO2 ® Fe(OH) (HCO3)

(Rust)
4.2 THE RATE OF A REACTION :
The quantity of a reactant species consumed or the quantity of a product species formed
in unit time in a chemical reaction is termed the rate of that reaction. As the reaction proceeds the
concentration of the reactants gradually decrease, while that of products gradually increase, with
time. This can be illustrated in the following figure. But the concentration does not increase or
decrease uniformly.
( s)
Concentration®
cts
du
Pro
(mol/L)
Re
act
ant
(s)
Time (Sec)®
Fig. 4.1 Plot of concentration Versus time
Consider a reaction, A ®B
D[A] D[B]
\ Rate of the reaction = - =+
Dt Dt
Here, the -ve sign is due to that fact that the molar concentration of reactant A decreases
with time and the +ve sign is due to that fact that concentration of B increases with time. Since
rate of reaction is never uniform, it changes with time. Since rate of reaction is directly propertional
to the concentration of the reactants, it can be concluded that the rate of the reaction gradually
falls with time. Thus we can not measure the velocity or rate of the reaction simply by dividing
the amount of reactant transformed by the time taken for such a transformation.
It is essential, therefore, to consider an infinitesimally small interval of time dt, an interval

so small that it may be assumed that the velocity is constant throughout the interval and if dx is
the amount of substance transformed in this interval, then the velocity of reaction at that instant
is given by dx
dt
dx d[A] d[B]
Thus rate of the reaction = - =
dt dt dt
The rate of the reaction is also represented by - dc, where dc is the concentration of
dt
reactant left behind after a short interval of time dt.
\ Rate of the reaction = - dc = + dx
dt
dt
Determination of rate of a reaction :

We know that the rate of a reaction is directly proportional to the molar concentration of
the reacting species. The molar concentration decreases progressively but not uniformly. Hence,
the change in concentration with time does not indicate the rate of a reaction.
0.08
0.07
0.06
0.05
- A
Concentration 0.04
(mol/L)
0.03
X
0.02
D x = 0.042
0.01
q B
0 5 10 15 20 25
DT = 20 MINUTES
Time (min) ®
Fig. 4.2 Determination of rate of reaction
Suppose we are to determine the rate of the reaction after ten minutes. Draw a perpendicular
at the point on X-axis corresponding to 10min. Locate the point 'x' where it touches the curve.
Draw a tangent at point 'x' and extend it on both sides. Let it cut this X and Y axis at points B and
A respectively.
The slope of the tangent = tanq = Rate of the reaction at 10 min.
\ Rate of the reaction = tanq = OA = - dc = dx
OB dt dt
-5
\ Rate of the reaction = dx = 0.042 = 3.50 ´ 10 moles/litre/sec.
dt 1200 sec
The unit of rate of the reaction = moles/litre/sec
Instantaneous and Average Rate of reaction

As stated earlier, the rate of a reaction is defined as the change in concentration of a
reactant or product per unit time. It is expressed as (a) Rate of decrease of concentration of any of
the reactants or (b) Rate of increase of concentration of any of the products.
Consider a hypothetical reaction.
A B
where A is the reactant and B is the product.
Let us suppose that [A1] and [B1] be the concentrations of A and B respectively at time t 1
and [A2] and [B2] be the concentration of A and B respectively at time t 2.
So, Dt = t2 – t1
D[A] = [A2] – [A1]
D[B] = [B2] – [B1]
(the square brackets are used to express molar concentration)
Decrease in Conc n of A D[ A ]
Rate = Rate of disappearance of A = = ............... (1)
Time taken Dt
Increase in Conc n of B + D [B ]
Also, Rate = Rate of appearance of B = = ............... (2)
Time taken Dt
Equation (1) and (2) represent the average rate of the reaction, rav.
[A]0 rinat = –d[B] = slope

dt
[B]
Concentration of products
Concentration of reactants
[A]1 –D[A] –[A2]– [A1] d[B]

rav= = dt
Dt (t2– t1) [B]1
d[A]
[A]2 D[B]
rinat = –d[A] = – slope [B]2 D[B] D[B2]–[B1]
rinat =
dt Dt (t2– t1)
t1 t2 t t1 t2 t
Time Time
(a) (b)
Fig. 4.3 Instantaneous and average rate of a reaction

To predict the rate of reaction at a particular instant of time average rate can not be used.
This is because the average rate would be constant for the time interval for which it is calculated.
So to express the rate at a particular moment of time we have to determine the instantaneous rate.
For this we have to consider the average rate at the smallest time interval ‘dt’ (i.e. when Dt 0)
D[A] D [B]
So, rav = =
Dt Dt
d[A] d[B]
As Dt 0, or Rinst = =
dt dt
Graphically rinst can be determined by drawing a tangent at time ‘t’ on either of the curves
for concentration of A and B versus time ‘t’ and calculating its slope (Fig.3.3)
Rate constant : Consider a simple reaction,
A ®B
According to law of mass action,
dx µ [A]
dt
or, dx = k [A] ............................ (1)

dt
where, k = proportionality constant known as rate constant or velocity constant or specific
reaction rate. It is a constant only at constant temperature.
Units of rate constant :The unit of rate constant for a given reaction is Mol 1-n lit.n-1 time-1
where n is the order of reaction. (M1-n Ln-1 T-1)
(i) For a first order reaction,
A ® Product (s)
Rate of the reaction, dx = k [A]
dx
-1 -1
or, k = dx/dt = moles/L/sec = moles lit. sec = sec-1
[A] mol/L mol.lit.-1
Unit of Rate constant in first order reaction is time -1 or sec-1.
(ii) For a second order reaction,
A + B ® Product (s)
dx = k [A] [B]
dt
or, k = dx/dt = moles lit.-1 sec-1 = lit.mol.sec-1

[A] [B] moles lit.-1. moles lit.-1
(iii) For a third order reaction,

3 A ® Product(s)
\ dx = k [A]3
dt -1 -1
or, k = dx/dt = moles. lit sec = lit2 mol-2 sec-1
[A]3 (moles.lit-1)3
(iv) For a zero order reaction, A ® Product, dx = k[A]0
dt
or, k = rate0 = mol. lit.-1 sec-1

[A]
Rate of the reaction and Rate constant :
Consider a general reaction
aA + bB + ...................® lL + mM +.........................
where a,b,I,m be the number of moles of A,B,L,M respectively. Rate of such reaction
decrease in concentration of a reactant per mole or increase in concentration of a product per
mole.
Rate of reaction (r) = -d [A] ´ 1 = k [A]a [B]b
dt a
where k = Rate constant or velocity constant
or, r = -d[B] ´ 1 = d[L] ´ 1 = d[M] ´ 1
dt b dt l dt m
If concentration of the reactants are taken as unit i.e. if [A] = [B] = 1 then
r = k [A]a [B]b = k.1.1. = k
i.e rate of the reaction = rate constant
So, when the reactants involved in a reaction are at their unit concentrations,the rate of
the reaction is equal to rate constant.
Difference between rate of reaction and rate constant :
Rate of reaction Rate constant
1. It is the rate of change of concentration 1. It is the proportionality constant in the

of any of the reactants or products at a rate law.
particular instant.
2. Rate of the reaction depends upon 2. Rate constant depends upon

temperature and also on concentration temperature but is independent
of reactants. of the concentration of reactants.
Factors influencing the rate of a reaction :

Rate of a reaction is greatly influenced by the following factors:
(a) Nature of the reactants.
(b) Effect of concentration.
(c) Presence of catalyst.
(d) Temperature.
(e) Surface area of the reactants.
and (f) Radiations.
(a) Nature of the reactants : A chemical reaction involves the rearrangement of atoms
between the reacting molecules to form the product. If such arrangement involves lesser
number of bond, the reaction proceeds faster. If the reactant is a single element, then the
rate of a reaction depends upon its electronic structure. The rate of a reaction is fast, if it
involves ionic species. On the other hand, rates of moleculars reactions and oxidation -
reduction reactions are quite slow.
Examples : (i)Sodium and calcium both react with water. But the former reacts very rapidly and
the latter, moderately. This is because, sodium is an active metal because of the electronic
configuration of its atom i.e, 1s2 2s22p63s1
Rapid
2Na + 2H2O 2NaOH + H2
Ca + 2H2O Moderate Ca(OH)2 + H2
(ii) The reaction between sodium sulphate and barium chloride is instantaneous
Na2SO4 + BaCl2 ® BaSO4 + 2NaCl (ionic reaction)
(iii) The hydrolysis of cane sugar proceeds at a slower rate.
C12H22O11 + H2O ® C6H12O6 + C6H12O6 (molecular reaction)
(sucrose) (glucose) (fructose)
(iv) It has been observed that even if the concentration and temperature of the reactants
are constant, the reaction rate is widely influenced by the internal structure of the
molecule.
0
Thus, NO + 12 O 25 NO2 (very fast)
2
CO + 12 O2 250 CO2 (very slow)
(b) Effect of concentration : The effect of concentration on reaction velocity can be explained
on the basis of kinetic theory. According to this theory, the rate of chemical reaction is
determined by the number of collisions per second between the reacting molecules. If the
number of molecules of a reactant is increased, the number of collisions will also increase.
Therefore, the rate of reaction will become higher with the rise of concentration. Also
according to law of mass action,the rate of a chemical reaction is proportional to the
product of molar concentration of reactants.
(c) Presence of catalyst : The presence of catalyst influences the rate of chemical reaction.
The catalyst itself does not undergo any change in the chemical composition at the end of
the reaction.
For example, the rate of decomposition of KClO3 is considerably increased by the addition
of MnO2. In this reaction MnO2 acts as a catalyst.
MnO2
2KClO3 2KCl + 3O2
The role of catalyst is most specific. It may be consumed in one step, but finally it is
regenerated after the end of the reaction. A substance whose presence slows down the
rate of the chemical reaction is called an inhibitor.
(d) Effect of temperature : Temperature plays a vital role in influencing the rate of a reaction.
A reaction which does not start at ordinary temperature, proceeds at a faster rate, if the
reactants are slightly warmed. On warming, heat energy is supplied which increases the
kinetic energy of the reacting species. With this, the number of collisions between the
reacting molecules increases. At this stage, the kinetic energy possessed by the molecules
exceeds the energy barrier and thus the products are formed.
The effect of temperature is generally represented in terms of temperature coefficients.
The temperature coefficient is defined as the ratio of the rate constants of a reaction at
two temperatures separated by 10 degree centigrade, usually 25 0C and 350 C. For most of
the reactions, the value of temperature coefficient is 2 to 3.
Kt +10
Temperature coefficient = » 2 or 3
Kt
where,kt = rate constant at t C and k(t +10) , at 10o higher.
0
This shows that, the rate of a reaction is increased considerably with the increase of
temperature.
For example, when copper turnings are added to conc. H2SO4, no reaction takes place
between them. But on heating the reaction proceeds at a faster rate.
Cu + 2H2SO4 heat CuSO4 + 2H2O + SO2
(e) Surface area of the reactants : With increase in surface area, the rate of reaction increases
Examples are :
(i) Coal dust burns brilliantly in air than a lump of it.
(ii) Wood chips burn rapidly than a log of wood.
(iii) Rate of dissolution of powdered sugar is more than that of sugar crystals.
Thus, decrease in particle size increases the surface area. Consider a cube of size
(5cm ´ 5cm ´ 5cm).
Total surface area = 6a2 = 6 ´ 5 ´ 5 = 150 cm2 (where 'a' is side of the cube = 5cm)
Total volume = a3 = 5 ´ 5 ´ 5 = 125 cm3

If the same cube is divided into 125 small cubes each having dimension (1cm ´ 1cm ´
1cm) then total surface area = 125 ´ 6 = 750 cm2
Total volume = 1cm3 ´ 125 = 125 cm3
(f) Effect of radiations : The rate of certain reactions increases when light radiations fall on
the reacting species. Generally, ultraviolet rays, X-rays and g-rays are characterised by
shorter wavelength and greater frequency. When they fall on the reacting molecules, h u
amount of energy is transferred to the reacting species. Consequently, the reacting
molecules acquire sufficient energy to cross the energy barrier and the products are easily
formed.
For example, H2(g) + Cl2(g) slow 2HCl (dark)

H2(g) + Cl2(g) hu 2HCl (fast)
4.3 MOLECULARITY OF A REACTION :
Molecularity of a reaction may be defined as the number of reacting

species(molecules,atoms or ions) which take part in rate determining step of a chemical
reaction.The rate determining step in the slowest of all the steps involved in a chemical
reaction. If a reaction involves the decomposition of a single species, it is called unimolecular.
Similarly, if the reaction involves the collision of two species, it is bimolecular and if three
species take part in a collision leading to the formation of a product, it is called termolecular.
For example :
(i) Decomposition of nitrogen pentoxide
N2O5 ® N2O4 + 1 O (unimolecular)
2 2
(ii) Decomposition of ammonium nitrite in aqueous solution
NH4NO2 ® N2 + 2H2O (unimolecular)
(iii) Hydrolysis of ester in acid medium
CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH (bimolecular)
(iv) Dissociation of HI
2HI ® H2 + l2 (bimolecular)
(v) Oxidation of sulphur dioxide to sulphur trioxide
2SO2 + O2 ® 2SO3(termolecular)
Consider a reaction which takes place in more than one step. Formation of nitrosyl fluoride
takes place in two steps
2NO + F2 ® 2ONF
Rate of such reaction = k[NO] [F2]

Step I : NO + F2 slow ONF + F (rate = k1[No] [F2])
Step II : NO + F fast ONF (rate = k2 [NO] [F])
Step I is slower than step II, therefore rate determining. Hence rate of equation for step I
is the rate equation for the overall change. This is a bimolecular reaction since only two
molecules participate in the rate determining step. Moleculartiy of a reaction is always a
whole number. Reactions having molecularity more than three are rare.
4.4 ORDER OF A REACTION :

Order of a reaction may be defined in a number of ways; (i) "The total number of molecules
or atoms whose concentration actually change as a result of chemical change", (ii) "The total
number of molecules or atoms whose concentration determine the rate of reaction" and (iii) The
sum of the power or powers of concentration terms that occur in rate equation. Order of reaction
is an experimentally determined quantity and can not be written from a balanced chemical equation.
Consider a general reaction,
nA + mB ® Product (s)
where, A and B are the reactants having n and m as the number of moles, respectively.
Thus, dx = k [A]n [B]m
dt
The sum (n+m) represents the order of the reaction.

A few examples are given below.
(a) Reaction of first order : In these reactions, only one reactant molecule undergoes chemical
change.
Thus, N2O5 ® N2O4 + 1 O2
2
or, dx = k[N2O5]1
dt
Also, in case of first order reaction, the concentration of one reacting substance changes
during a chemical change.
But hydrolysis of ester in acid medium, although a bimoecular reaction, is of first order.
Since water is present in large excess, the change in concentration of water does not influence the
rate of reaction. The rate of reaction is determined by the help of change in concentration of ester
only.
So, CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH

dx = k [CH COOC H ]
dt 3 2 5
This type of reaction is known as pseudounimolecular reaction.

(b) Reaction of second order : A reaction is said to be of the second order, if its rate is
determined by the variation of two concentration terms or the rate of the reaction is
proportional to the second power of the concentration of a single reacting substance.
In general, the second order reaction may be of two types.
(i) When the concentration of both the reactants are same.
2A ® Products.
For example, dissociation of HI.
2HI ® H2 + I2
dx
= k [HI]2
dt
(ii) When the concentration of both the reactants are different.
A + B ®Products
For example, H2 + I2 ® 2HI
dx = k [H ] [I ]
dt 2 2
(c) Reaction of third order : In these reactions, the sum of the exponents of the concentrations
of the reactant species is 3. Generally, they are represented as follows:
2A + B ® Products
or, A + 2B ® Products
For example, 2NO + O2 ®2NO2
Since, dx = k [NO]2 [O2]1

dt
\ Order of the reaction will be = 2 + 1 = 3
(d) Reaction of zero order : Besides the reactions of first, second, and third order, there are
certain reaction styled as zero order reaction.
In these reactions, the concentration of any of the reactants does not influence the rate of
the reaction. The rate of the reaction is thus proportional to the zero th power of the concentration
of the reactants, that is, the reaction speed is constant.
For example, the reaction between hydrogen and chlorine in presence of sunlight to give
hydrogen chloride.
hu
H 2 ( g ) + Cl 2 ( g ) ¾ ¾® 2HCl (g)
dx
Since, = k[H 2 ]0 or k[Cl 2 ]0 , the order of reaction will be zero.
dt
(e) Reactions of fractional order : Besides there are a few reactions of fractional order. e.g.
CH3 CHO ® CH4 + CO. Here, rate = k[CH3CHO]3/2 and order = 3/2.
Comparision of molecularity and order of reaction :

The distinction between molecularity and order of a reaction are given below :
Molecularity Order of reaction
Common points.
1. The molecularity is dependent upon 1. The order of a reaction also depends on the
conditions of a reaction. on the conditions of a reaction.
2. Reactions of higher molecularity 2. Reactions of higher order (higher than third

(more than three) are rare. order) are also rare.
Molecularity Order of reaction
Differences :
3. Molecularity is given by the total 3. Order of a reaction is given by the number of
number of molecules of the reacting molecules whose concentrations change as a
species which take part in the rate result of the reaction.
determining step of the reaction.
4. The molecularity of each step of a 4. Order of a reaction, as determined by the

reaction is separately determined. slowest step of a reaction refers to the order
of the whole reaction.
5. Molecularity of a reaction is always 5. Order of reaction can be a whole number, a

a whole number. fraction or zero.
6. Molecularity of a reaction can 6. Order of a reaction is always determined by

be theoretically predicted by studing experimental methods.
the balanced equation for the
reaction.
7. Molecularity refers to mechanism 7. It does not refer to mechanism through which

of the reaction. the reaction proceeds.
4.5 RATE EQUATIONS :
4.5.1 Rate Equation of the First order Reaction

A first order reaction is that, in which the concentration of only one reactant changes or in
which the rate of reaction is proportional to the first power of the concentration of the reactant.
In general, such a reaction is represented as,
A ® Product (s)
'a' 0 (Initially, t = 0)
(a - x) x (after time 't' sec.)
Let the initial concentration of A = 'a' mol/L
After time 't', let x mol/L of A have decomposed.
So concentration of A after time 't' becomes (a - x) mol/L
\ According to law of mass action,
rate of the reaction, dx µ (a- x)
dt
or, dx = k (a- x) ................................... (1)

dt
k = Proportionality constant, called rate constant or velocity constant or specific reaction
rate. It has definite value at a definite temperature.
Eqn. (1) can be written as,
dx
a-x = k.dt. ....................... (2)
on integrating eqn (2) we get,

dx
ò a - x = ò k.dt
or, - ln (a-x) = k.t + I ............................... (3)
where I = Integration constant.
When t = 0, x = 0.
Substituting these values in eqn. (3) we get,
- ln a = I ........................... (4)
From eqn. (3) and (4), we get,
- ln (a-x) = k.t - ln a
or, ln a - ln (a - x) = k.t
or, k.t = ln a/a-x
or, k.t = 2.303. log a
a-x
or, k = 2.303 log a ...................... (5)

t a-x
Eqn. (5) is known as the rate equation for first order reaction.
Characteristics of 1st order reaction :

1. The unit of constant in first order reaction is time -1 or sec-1 .
2. The time taken for the completion of same fraction of change or any fraction of
change is independent of the initial concentration of the reactant.
Let t1/2= the time taken for the completion of half of the reaction. (Initial concentration 'a'
becomes half i.e. 'a' becomes a/2)
t1/2 is also known as half-life time.
At t1/2, x = a
2
2.303 a
Putting these values in eqn (5), we get, k = log
t 1/ 2 a
a-
2
2.303 2.303 0.693
or, k = log 2 or, k = ´ 0.301 or, t 1/2 =
t 1/2 t 1/2 k
or, t 1/ 2 = Constant. Similarly, we can find t1/3 = Constant and t1/4 = Constant.
3. A change in concentration unit does not affect the rate constant. Let the new concentration
be 'm' times the first one. That is, when 'a' is made ma, (a - x) changes to m(a-x).
and k = 2.303 log ma
t m (a- x)
or, k = 2.303 log a

t (a- x)
Thus, expression for k remains unaltered.
If a graph plotted between log (a -x) and 't' from the experimental values is found to be
linear, the reaction is of the first order.
4. Evaluation of k : k can be evaluated by using the rate equation (5). By determining the
concentration of reactants at different time intervals and knowing the initial concentration,
'k' can be calculated.
Alternately, k can be evaluated by graphical method. Rearranging eqn. (5)
t = 2.303
k
log a a- x
= 2.303 log a - 2.303 log (a - x)

k k
-k
or, log (a - x) = 2.303 t + log a
Thus, by plotting log( a-x) at different time intervals aginst the corresponding time intervals
we get a straight line having a -ve slope, the intercept being log a.
-
log (a - x)
q
t ®
Fig. 4.4 Plot of log (a - x) against time 't' in 1st order reaction
Slope = tan q = - k
2.303
or, k = - 2.303 ´ slope
Examples of 1st order reaction.
(i) Dissociation of PCl5

PCl5 ® PCl3 + Cl2
(ii) Decomposition of nitrogen pentoxide :

Nitrogen pentoxide is a volalite crystalline solid, which decomposes in gaseous
state or when dissolved in some organic solvents like CCl 4. The reaction is
represented by the equation, N2O5 ® N2O4 + 1/2 O2
2NO2
(iii) Decomposition of hydrogen peroxide :

The decomposition of hydrogen peroxide in aqueous solution is catalysed by the
presence of finely divided platinum and the reaction is represented by the equation.
H2O2 ® H2O +1/2 O2
(iv) Decomposition of ammonium nitrite in aqueous solution :

NH4NO2 ® N2 + 2H2O
(iv) Hydrolysis of ester in presence of acid.

CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH
The reaction can be studied by titrating a known volume of reaction mixture with
standard alkali at regular intervals.
If V0 ® Volume of alkali used initially equivalent to mineral acid alone.
Vt ® Volume of alkali used after interval 't'
V¥ ® Volume of alkali used when the reaction is complete (i.e. after 24 hours)
Then, a = (V¥ - V0)
x = (Vt - V0)
So, a - x = V¥ - V0- Vt + V0 = (V¥ - Vt)
a
and k = 2.303 log
t (a- x)
V¥ -V0
= 2.303 log
t V¥- Vt
Example : 5 ml of methyl acetate was added to a flask containing 100 ml of 0.1 NHCl maintained
at temperature of 250C . 5 ml of reaction mixture was drawn at different intervals of
time and titrated against standard alkali. The following data were obtained.
Time (min) - 0 75 119 183 ¥
ml. alkali used - 4.81 6.05 6.55 7.37 10.52
From the above data show that the reaction is of first order.
Solution :
(V¥ - V0) = 10.52 - 4.81 = 5.71
Time (V¥ - Vt) k= 2.303 log V¥ - V0

min. t V¥ - Vt
75 4.47 k= 2.303 log 5.71 = 3.263 min-1

75 4.47
k= 2.303 log 5.71 = 3.047 min-1

119 3.97
119 3.97
k= 2.303 log 5.71 = 3.228 min-1

183 3.15 183 3.15
The velocity constant k in all the cases are almost constant. Hence, the reaction is of first order.
4.5.2 Rate Equation of the Zero order Reaction

Reactions in which the concentrations of the reactants do not change with time and
therefore, the rate of the reactions remains constant throughout, are termed as zero order reactions.
The rate of the reaction for zero order can be expressed as,
dx
= k ........................... (1)
dt
or, dx = k.dt ..................... (2)
On integration with proper limits, it gives,
x=x t
dx = k ò dt
0
x = x0
or, x - x0 = k.t
k=x-x
0
or,
t
Since at the start of a reaction when t = 0, no product is formed i.e. x 0 = 0, Hence
k = x ............................... (3)
t
This is the rate equation for a zero order reaction. It suggests that the rate of zero order
reactions are independent of the amount or concentration of reactant present.
Characteristics of Zero order reaction :
1. The unit of rate constant in zero order reaction is mol. L -1 s-1
2. A graph of concentration of product (x) against time (t) for such a reaction gives a straight
line passing through the origin.
3. Half life is defined as the time required to reduce the concentration to half of its original value.
For a zero order reaction, half life is proportional to the initial concentration of the reactant.
t = t when x = a/2, where 'a' is the initial concentration of the reactant.
1/2
we get, a = k t1/2
or, t1/2 µ a
Examples : (i) A well known photochemical reaction between hydrogen and chlorine is a
zero order reaction.
H (g) + Cl (g) hu 2HCl(g)
2 2
If the gases are confined in a long tube, dipping in water, the HCl will be dissolve as soon as
it is formed. Since here pressure remains constant, the volumes of the two gases H 2 and Cl2 are
reduced. This keeps the concentrations of [H2] and [Cl2] unaltered. That is, the change in the
concentrations is zero and the rate of reaction is independent of the concentration of the reactants.
Hence the order of reaction is zero.
(ii) Some heterogeneous reactions of zero order taking place on the surfaces are given below :
2N2O hot Pt wire 2N2 + O2

catalyst
2NH3 Tungsten N2 + 3H2

catalyst
2HI Gold H2 + I2
catalyst
In the above cases, the reactions occur on the surface of the catalyst. When the surface
becomes saturated, the amount of absorbed gas is constant. Further increase in pressure can not
change the surface concentration. Therefore, the rate of reaction is independent of the concentration
of the reactant in gas phase.
4.5.3 Fractional Life Period

It is the time required to complete a particular fraction of a reaction. For example,
Half life period - It is the time required by the reaction to undergo 50% conversion into
products. It is represented by T50 or t½
(1) For a zero order reaction, the rate of reaction is
x
ko = where x = amount of product formed after time interval ‘t’
t
ko = rate constant
a
At T50, x = where a = initial concentration of the reactant.
2
x a
Hence, T50 = k = 2k
o o
3a
At t = T75, x = (T75 is the time required by the reactant to decompose 75%)
4
x 3a 3 a
Hence, T75 = k = 4k = 2 . 2k = 1.5 T50
0 0 0
Thus, T50 a a
(ii) For a 1st order reaction, the rate equation is
2.303 a
k1 = log
t a x
a
If t = T50, x =
2
2.303 a
k1 = log
T50 a
a
2
2.303 a 2.303 0.693

or, T50 = log = log 2 = k
k1 a k1 1
a
2
3a 2.303 a 2.303
If t = T75 , x = and k1 = log = log 2 2
4 T75 3a T75
a
4
2.303 2.303
T75= log 2 2 = 2. log 2= 2× T50
k1 k1
Similarly, T87.5 = 3 × T50
and T99.9 = 10 × T50
So, the time for undergoing a definite fraction of reactant in 1st order rection is
independent of concentration.
4.6 ACTIVATION ENERGY :
The concept of activation energy is important to understand why a mixture of oxygen and
hydrogen (1:2 by volume) remains unreacted at room temperature but undergoes a vigorous
change if an electric spark is passed through it.
2H + O at 200 C No reaction
2 2
2H2 + O2 Electric spark 2H O

2
From this we can conclude that, the molecules undergoing a chemical reaction must possess
a minmum amount of energy, so that the collisions between themselves result in a reaction. This
minimum amount of energy is called threshold energy (Eth). Prior to their collision, molecules
of the reactants in their normal state do possess their respective internal energy. Let the average
energy of the reactants be Er, which is less than the threshold energy. Now the excess energy that
the reactant molecules (having energy less than the threshold energy) must acquire in order to
yield products is called activation energy. Thus,
Activation energy (Ea) = Threshold energy(Eth) - Average energy possessed by the
molecules of the reactants (Er)
or, Ea = Eth - Er
Definition of Activation energy : The extra energy supplied to the reactant molecules to attain
threshold energy for undergoing chemical reaction is called activation energy.
Ep
Ea
Eth
Energy Products
Reactants
Er
Progress of reaction
Fig. 4.5 Plot of energy versus progress of reaction
Ea = Energy of activation of reactants

Ep = Energy of activation of products.
When Ep > Ea, the reaction is exothermic. When Ep < Ea, the reaction is endothermic.
The reactant molecules must acquire a certain amount of energy before they can react
upon collisions to yield the products. That is to say, they must overcome the energy barrier in
order to yield the products. The barrier determines the magnitude of the threshold energy that they
require to yield the products. As a matter of fact, reactions proceeding at a faster rate have low
value of activation energy and those which proceed slowly possess comparatively high value of
the activation energy.
Determination of Activation energy :

Arrhenius pointed out that a reasonable equation for the variation of rate constant with
temperature can be derived on the basis of the van't Hoff's equation. According to an equation
= DE .......................... (1)
suggested by van't Hoff, dlnKc
dT RT2
where, Kc = Equilibrium constant = k1/k2 (k1 and k2 are rate constant for forward and
backward reaction respectively.)
dlnk1 dlnk2 E1 E2
= ( where, D E = E1 - E2)
dT dT RT2 RT2
This may split into,
dlnk1 E1 and dlnk2 E2
= =
dT RT2 dT RT2
or, In general,
dlnk = E ............................... (2)
dT RT2
On integrating equation (2), we get,
dlink E E
dTò =ò
RT 2
or, ò dlink = ò
RT 2
. dT
or, ln k = - E + constant ............................. (3)

RT
or, log k = -E + constant .............................. (4)

2.303RT
Plot of log k vs 1/T gives a straight line with slope = - E/2.303R

where, E = Activation energy.
-
log k
1/T ®
Fig. 4.6 Plot of log k versus 1/T
From equation (3), we can get,
k = Ae-E/RT ................................ (5)
This equation is known as Arrhenius equation. Here A is a constant known as frequency
factor or collision number.
4.7 COLLISION THEORY FOR UNIMOLECULAR REACTION :
This theory was developed by Arrhenius and van’t Hoff. According to this theory, a
chemical reaction occurs by the collision between the reacting molecules. So, for a chemical
reaction to occur
(a) the reactant molecules are brought closer to each other and collide amongst themselves.
(b) the reactant molecules must possess certain amount of minimum energy before they
react upon collision.
(c) the reactant molecules must be properly oriented.
Collision between the molecules

The molecules are always in a state of motion. During their motion they collide with each
other. As a result of these collisions the chemical reaction takes place. But all the collisions do
not lead to chemical reaction. Only some effective collisions are taken into account.
The collision theory postulates that only the reactants which possess certain minimum
amount of energy known as threshold energy collide amongst themselves giving some effective
collisions leading to a chemical reaction.
As a result of collisions there is redistribution of energy among the molecules. Consequently
the number of molecules having energys more than the threshlod energy is low and the number of
molecules having lower energy is very high. Hence a small fraction of total moleules acquire
energy which is equal to or greater than the threshold energy. These molecules are said to be
activated molecules. The difference between the threshold energy and the average energy possessed
by the molecules is known as Energy of activation or Activation energy. Thus,
Activation energy (A.E) = Threshold energy (ETh) - Average energy of reactants (ER).
Orientation of colliding molecules
For a chemical reaction to occur the colliding molecules should be properly oriented. The
following figure clearly depicts the proper orientation of colliding molecules.
A A A A A A
+
+
B B
B B B B
Reactants Products
The energy required for effective collisions between the reactant molecules that are poorly
oriented is much higher than that required for properly oriented ones.
4.8 SOLVED NUMERICAL PROBLEMS :
Example 1 What is the rate of reaction and the order of reaction if the mechanism of the
reaction as,
2 NO + H2 ® N2 + H2O2 (slow reaction)
H2O2 +H2 ® 2H2O (fast reaction)
Solution : We know, the slowest step is the rate determining step.

Hence, the rate of the reaction = k [NO]2 [H2]1
\ Order of the reaction = 2 + 1 = 3
Example 2. For the following reactions, state the order with respect to each reactant and the
overall order.
(a) 3 NO(g) ® N2O(g) + NO2(g)

Rate = k [NO]2
(b) H2O2 + 3I- + 2H+ ® 2H2O + I3(aq)

Rate = k [H2O2] [I-]
(c) CH3CHO(g) ® CH4(g) + CO(g)

Rate = k [CH2 CHO]3/2
(d) CHCl3(g) + Cl2(g) ® CCl4(g) + HCl(g)

Rate = k [CHCl3] [Cl2]1/2
(e) C2H5Cl(g) ® C2H4(g) + HCl(g)

Rate = k [C2H5Cl]
What are the dimensions of rate constant in each case.
Solution :
(a) Rate = k [NO]2
Since, here only one reactant is present, the order with respect to NO or overall
order is same. It is equal to 2.
Dimension or unit of k, k= Rate = mol.L-1s-1 = mol-1L. s-1

[NO]2 (mol.L-1)2
(b) Rate = k [H2O2][I-]

Here, the order of the reaction with respect to H2O2 is one and also with respect to I- is one.
\ The overall order of the reaction = 1 + 1 = 2
Unit of k, Rate mol.L-1 s-1 = mol-1 L.s-1
k= - = -1 -1
[H2O2][I ] (mol.L )(mol.L )
(c) Rate = k [CH3CHO]3/2

Since only one reactart involves, the order of the reaction is some always.
The order of the reaction = 3/2 = 1.5
Unit of k, k= Rate = mol.L-1s-1 = mol-1/2 L1/2 s-1
3/2 -1 -1 3/2
[CH3CHO] (mol.L ) (mol.L )
(d) Rate = k [CHCl3] [Cl2]1/2

Order of the reaction with respect to CHCl3 = 1
and order of the reaction with respect to Cl 2 = 1/2
\ Overall order of the reaction = 1 + 1/2 = 3/2 = 1.5
Unit of k = mol-1/2 L1/2 s-1
(e) Rate = k [C2H5Cl]
\ The order of the reaction = 1
Unit of k , k = Rate = mol.L-1s-1 = Sec-1
[C2H5Cl] (mol.L-1)
Example 3. For the decomposition of N2O5 given as,

N2O5(g) ® N2O4(g) + 1/2O2 (g)
If the rate law = k [N2O5] and k = 1.68 ´10-2 sec-1, starting with 2.5 moles of N2O5(g)
in a 5.0 litre container at 298 K, how many moles of N2O5 would remain after 1.0 minutes ?
Solution : Initial concertation of N2O5 = [N]0 = 2.5 = 0.5 mol/litre
Let [N] = final concentration
t = 1 minutes = 60 seconds.
The first order rate equation can be represented as,
[N]o
k.t = 2.303 log
[N]
or, 1.68 ´ 10-2 ´ 60 = 2.303 log 0.5
N
1.68 ´10-2 ´ 60 -2
or, log 0.5 - log [N] = 2.303 = 43.76 ´ 10
or, log [N] = log 0.5 - 43.76 ´ 10-2

= - 0.301 - 0.4376 = -0.738
= 1.262
[N] = antilog 1.262 = 0.182 mol/lit.
Example 4. The rate constant for a first order reaction involving a compound A was found to
be 0.082 min-1. When the initial concentration of A is 0.15 mol/litre, how long will it take for the
concentration of A to drop to 0.03 mol/litre.
Solution : k = 0.082 min-1 k = 2.303 log a
t a-x
or, t = 2.303 log 0.15 = 2.303 log5

0.082 0.03 0.082
2.303
= 0.082 ´ 0.6990 = 19.6 min.
Example 5 : What percentage of the initial concentration of reactant is left in 2.0 hours for a
reaction whose rate constant is 4.25 ´ 10-5 sec-1 ?
Solution : Let the initial concentration of the reactant, a = 100 mol/L

Let, the concentration of the product after 2 hours be 'x' mol/L.
\ The concentration of the reactant left after 2 hours = (100 - x) mol/L
we know, k = 4.25 ´ 10-5 sec-1
and t = 2 hour = 60 ´ 60 ´ 2 = 7200 sec.
According to first order rate expression
k = 2.303 log a-x a
t
or, 4.25 ´ 10-5 = 2.303 log 100

7200 100 -x
or, log 100 = 0.1328

100-x
or, 100 = antilog 0.1328 = 1.358

100-x
or, 100 = 1.358

100-x
or, 100 - x = 100 = 73.64

1-358
or, x = 100 - 73.64 = 26.36%
Example 6 : A first order reaction is 20% completed in 10 minutes. Calculate (i) k for the
reaction and (ii) time taken for the reaction to go 75% completion.
Solution : (i) Let, initial concentration of the reactant, a = 100 mol/L

\ Concentration of the product formed in 10 minutes, x = 20 mol/L
Hence, concentration of the reactant left after 10 minutes, (a -x) = 80 mol/L
We know, the rate eqn. for first order reaction is,
k = 2303 log a = 2303 log 100
t a-x 10 100-20
= 2303 [log 10-log 8]

10
= 0.2303 ´ (1-0.9031)
= 0.2303 0.0969 = 0.0223 min-1
(ii) Let, t = time taken for 75% completion.
so, in time t, x = 75 mol/L
and a - x = 25 mol/L
\ t = 2303 log a
k a-x
or, t = 2.303 log 100

0.0223 25
= 2.303 log 4 = 2.303 ´ 0.6021

0.0223 0.0223
= 62.15 min
Example 7 The half life period (t1/2) of a first order reaction is 100 sec. Calculate the time
required for 80% completion.
Solution : We know, for a first order reaction,
t1/2 = 0.693
k
\ k = 0.693 = 0.693 = 0.00693 sec-1

t1/2 100 sec
Now time required for 80% completion is given by,
a
t = 2.303 . log a-x
k
= 2.303 . log 100

0.00693 sec-1 (100 - 80)
= 332.32 [log 100 - log 20] sec.

= 332.32 [2 -1.3010] sec.
= 332.32 ´ 0.6990 sec. = 232 sec.
Example 8. Concentration of a reactant A changed from 0.044M to 0.032M in 25 minutes.

What was the average rate of the reaction during this interval ?
D[A] 0.044 - 0.032 0.012

Solution : Rate = - = - = -
Dt 25 25
= 1.00048 mole/litre/min
= 4.8 ´10-4 mole litre-1 min-1
Example 9 : Calculate the half-life of a first order reaction, where the specific rate constant is
(a) 200 sec-1, (b) 2 min-1, (c) 5 year-1
Solution : The half-life of a first order reaction is represented by,

t1/2 = 0.693
k
(a), When k = 200 sec-1,

t1/2 = 0.693 = 0.0035 sec = 3.5 ´ 10-3 sec.
200 sec-1
(b) When, k = 2 min-1,

0.693
t1/2 = = 0.3465 min
2 min-1
(c) When, k = 5 year

t1/2 = 0.693 = 0.1386 year.
5 year-1
Example 10. The half life period of a reaction of first order is 100 sec. Calculate its rate constant.
Solution : We know, for a first order reaction,

t1/2= 0.693
k
or, k = 0.693
t1/2
Now, t1/2 = 100 sec.

-3 -1
\ k = 0.693 = 6.93 ´ 10 sec
100 sec
Example 11. A first order reaction takes 69.3 minutes for 50% completion. How much time
will be needed for 80% completion ?
Solution : The rate equation for first order is,

k = 2.303 ´ log a
t a-x
2.303 log a
or, t= k a-x
100
\ t50% = 2.303 log
k 100-50
2.303. log 2 ............................. (i)

=
t
and t80% = 2.303 . log 100 = 2.303 log 5 ........................ (ii)

k 100-80 k
Dividing eqn (ii) by (i) we get,

t80% log5
=
t log2
50%
We know, the time for 50% change = 693 minutes.
\ Time for 80% change,
t80% = 69.3 ´ log5 = 69.3 ´ 0.699
log2 0.301
= 160.9 min
Example 12. If the half life of a first order reaction, 'A ® product' is 2 minutes, how long will
it take [A] to reach 25% of its initial concentration ?
Solution : t1/2 = 2 minutes

0.693
\ k= t = 0.346 min-1
1/2
If initial concentration of A = [N0]
[N0]
and final concentration of A will be,
4
Hence, for a first order reaction,
[N0]
t = 2.303 log
k [N0]/4
= 2.303 log 4
0.346 min-1
2.303
= × 0.6021 = 4 minutes.
0.346 min 1
Hence, it will take 4 minutes.
Example 13. Show that the time required for the completion of 3/4th of reaction of first order is
twice the time required for the completion of half of the reaction. [CHSE, 1991]
Solution : The rate requation for first order reaction is,
k = 2.303
t
. log a
a-x
or, t = 2.303 . log a

k a-x
Let t1/2 = half-life time

Hence, at t1/2, x = a/2
When, t3/4 = time required for the completion of 3/4th of the reaction.
at t3/4, x = 3a/4
2.303 a
\ t 1/ 2 = . log
k a- a
2
= 2.303 log 2 .............................. (i)
k
2.303 a
Since, t 3/4 = .log
k a - 3a
4
2.303 . log 4 ........................... (ii)
or, t3/4 =
k
t3/4
Dividing eqn (ii) by (i), we get, t =2
1/2
or, t3/4 = 2 ´ t1/2
Example 14. A first order gas reaction has k = 1.5 ´ 10-6 per second at 2000c. If the reaction is
allowed to run for 10 hours, what percentage of the intial concentration would
have changed into the product ? What is the half life of the reaction ?
Solution : We know, k = 1.5 ´ 10-6 sec-1.

t = 10 hours = 36000 sec
Let the percentage of initial concentration changed into product = x.
If N0 = initial concentration = 100
N = final concentration = (100 - x)
2.303 . log N0
\ k=
t N
-6 2.303 100
or, 1.5 ´ 10 sec-1 = 36000 sec log 100-x
-6
or, log 100 = 1.5 ´ 10 ´ 36000 = 0.0234
100-x 2.303
Taking antilog, we get,

100
100 - x = 1.055
or, 105.5 - 1.055 x = 100

or, x = 5.2
\ The percentage of initial concentration which is changed into product = 5.2%.
Then, the half life of the reaction,
t1/2 = 0.693 = 0.693 -5
-6 -1 = 4.62 ´ 10 sec.
k 1.5 ´ 10 sec
Example 15. The value of rate constant for the decomposition of nitrogen pentoxide
(N O ®N O + 1 O ) is 3.46 ´ 10-5at 250C and 4.87 ´ 10-3 at 650C. Calculate
2 5 2 4 2 2
the energy of activation for the reaction. (R = 1.987 calories)
Solution : Here, k1 = 3.46 ´105 T1 = 273 + 25 = 298 K

k2 = 4.87 ´ 10-3 T2 = 273 + 65 = 338 K
k2 Ea T2 - T1
\log =
k1 2.303 R T2. T1
Putting the values in the above equation,
We get, Ea = 24,800 calories = 24.8 kcals.
Example 16. The specific rate constant for a reaction increases by a factor of 4 if the temperature
is changed from 270C to 470C. Find the activation energy for the reaction.
(R = 1.98 calories)
Solution : We know, the activation energy at two different temperature, can be calculated by
taking the help of the following equation.
k2 Ea T2 - T1
log =
k1 2.303 R T . T
2 1
Hence, log
4k1 Ea 320 - 300
=
k1 2.303 ´1.98 320 ´ 300
Ea 20
2.303 ´ 1.98 ´
or, 0.6021 =
320 ´ 300
\ Ea = 0.6021 ´ 2.303 ´ 1.98 4800
= 13180 calories
= 13.18 kcals.
1. Activation energy : The extra energy supplied to the reactant molecules to attain threshold
energy to undergo chemical reaction is called activation energy.
Activation energy, Ea = Eth - Er
2. Half-life period : It is the time during which the concentration of reactants falls down to
half of its initial value.
t1/2 = 0.693/k
3. Molecularity : Total number of molecules or atoms or ions taking part in the rate
determining step of chemical reaction.
4. Order of a reaction : Total number of molecules or atoms whose concentration actually

changes as a result of chemical reaction.
5. Rate of reaction : Rate of reaction at a particular instant is the instantaneous rate of

change of concentration of any one of the reactant or product at a particular instant.
6. (a) First order rate equation is k = 2 .303 log a

t (a -x)
(b) Zero order rate equation is k = x

t
7. The unit of rate constant for a given reaction is M1-n Ln-1 t-1 where n is the order of
reaction.
8. The rate of the reaction is equal to rate constants when the reactants are at their unit
concentration.
n
1
9. Amount of reactants left after 'n' number of half life periods a n = ( 2
a0 (a0 being the
initial concentration of reactants.

10. Hydrolysis of ester in presence of mineral acid is a first order and pseudo unimolecular
reaction whereas that in presence of alkali is a second order and bimolecular reaction.
11. The rate of a reaction is affected by nature of reactants, temperature, concentration of reactants
presence of catalyst, certain energy radiation and surface area of the reacting species.
12. Upon raising the temperature by 100C, it is found that the reactant becomes two or three
times the original value.
QUESTIONS
A. Very short type questions : (1 mark each)
1. What is the unit of the rate constant of a first order reaction ?
2. What is the unit of the rate constant of a second order reaction ?
3. Name any two factors which influence the rate of reaction.
4. The hydrolysis of ester in acid medium is a first or second order reaction ?
5. The rate of a reaction increases or decreases with the increase in temperature ?
6. Give an example of zero order reaction.
7. What is the half life period of a reaction having rate constant 6.93x10-4 sec-1?
8. What is the unit of second order rate constant?
9. What is the unit of first order rate constant?
10. What is the reaction order if the unit of rate constant is litre mol -1 sec-1?
11. Calculate the order of reaction having the rate expression
rate = k[A]1/2 [B]3/2.
B. Short answar type questions : (2 marks each)
1. What is half-life period ? How is it related to the rate constant for a first-order reaction ?
2. (a) The half-life period of a first order reaction is 30 seconds. Calculate its rate constant.
(b) What is the value of rate constant of a first order reaction having half life period 10
minutes ?
3. (a) The rate constant of a first order reaction is 0.60 sec -1. What is its half-life period?
(b) If the rate constant of a first order reaction is 6.93 ´ 10-4 per second, what is its
half-life period ?
4. Radioactive decay is a first order rate process. Two-third of a radioactive isotope
disintegrates in 30 minutes. What is the rate constant of the disintegration ?
5. The rate constant of a first order reaction is, k = 7.39 ´ 10-5 sec-1. Find the half-life of the
reaction.
6. What is the difference between order and molecularity of a reaction ?
7. Derive the half-life period from the 1st order rate equation.
8. Distinguish between order and molecularity of a reaction.
9. What is zero order reaction ? Give one example.
10. Name any two factors which influence the rate of a reaction.
11. Half-life period of a substance is 20 days. After 30 days what percentage of the substance
will be left.
12. Calculate the rate constant of a reaction (1st order) which is 90% complete in 10 minutes.
C. Short answer type questions : (3 marks)

1. State and explain how the molecularity and rate of reaction may be different. Give an
example of pseudo unimolecular reaction.
2. What do you mean by activation energy ? How the activation energy can be determined ?
3. Show that in a first order reaction, the time taken for the completion of some fraction of
change or any fraction of change is independent of the initial concentration of the reactant.
4. 75% of a reaction of the first order was completed in 32 minutes. When was it half
completed ? (Ans: 16 minutes)
5. Thermal decomposition of a compound is of first order. If 50% of a sample of the compound
is decomposed in 120 minutes how long would it take for 90% of the compound to
decompose ? (Ans : 400 minutes)
6. First order reaction, A ® B requires activation energy energy of 70 kJ mole-1. When a 20%
solution of A was kept at 250C for 30 miniutes, 25% decomposition took place. What will
be percentage decomposition in the same time in a 30% solution maintained at 40 0C ?
Assume that activation energy remains constant in this range of temperature.
(Ans : 67.21%)
7. A first order reaction is 20% complete in 10 minutes. Calculate the specific rate constant
of the reaction and the time taken for the reaction for 75% completing ?
8. At 3800C, the half-life period for the first order decomposition of H 2O2 is 360 min. The
energy of activation of the reaction is 200 kJ mole -1. Calculate the time required for 75%
decomposition at 4500C. (Ans : 20.36 min)
9. The decomposition of N2O5 according to the equation
2N2O5(g) ® 4NO2(g) + O2(g)
is a first order reaction. After 30 minutes from the start of the decomposition in a closed
vessel, the total pressure developed is found to be 284.5 mm of Hg and on complete
decomposition, the total pressure is 584.5 mm of Hg. Calculate the rate constant of the
reactions. (Ans : 3.70 x 10-4 sec-1)
10. The ionization constant of NH4+ in water is 5.6 ´ 10-10 at 250C. The rate constant for the
reaction of NH4+ and OH- to from NH3 and H2O at 250C is 3.4 ´ 10-10 lit mol-1 sec-1.
Calculate the rate constant for proton transfer from water to NH 3
(Ans : k = 6.07 ´ 10-5 sec-1)
D. Long questions : (7 marks each)

1. Derive an expression for rate constant of first order reaction. Give an example for first
order reaction.
2. Explain the terms molecularity and order of a reaction. Give one example from each of
first and second order reactions.
A 0.1 M HCN solution contained 0.2 moles of KCN per litre of the solution. What was the
hydronium ion concentration of the solution. (Ka for HCN = 7.2 ´10-10)
3. State the rate equation for a first order reaction. Derive the half-life period from the rate
equation.
A first order reaction takes 69.3 minutes for 50% completion. How much time will be
needed for 80% completion ?
a) Activation energy.
b) Half-life period.
c) Order and molecularity of a reaction.
5. Write notes on distinction between molecularity and order of reaction.
6. Derive the expression for first order rate constant. A first order reaction takes 69.3 minutes
for 50% completion. How long will it take for 80% completion?
7. What do you mean by molecularity and order of reaction? Give one example each of the
first and second order reaction.
E. Multi Choice Questions :

1. The unit of the rate constant for the second order reaction is :
(a) Mol-1 litre sec-1.
(b) Mol. litre-1 sec-1
(c) Sec-1
(d) Mol litre-1 sec.
2. In which of the following cases, does the reaction go farthest to completion ?
(a) k = 102
(b) k = 10-2
(c) k = 10
(d) k=1
3. The specific rate constant of a first order reaction depends upon the,
(a) concentration of the reactant.
(b) concentration of the product.
(c) time
(d) temperature.
4. Half-life period of any first order reaction is,
(a) Directly proportional to intial concentration of reactant.
(b) Half of the rate constant.
(c) Same for all reactions.
(d) Independent of initial concentration of reactant.
5. The rate law for the reaction.

RCI + NaOH(aq) ® ROH + NaCl is given by, Rate = k1 [RCl]. The rate of reaction will
be :
(a) Doubled on doubling the concentration of NaOH.
(b) Halved on reducing the concentration of alkyl halide to one half.
(c) Increasesed on increasing the temperature of the reaction.
(d) Unaffected by increasing the temperature of the reaction.
6. What will be amount of 53I128 (t1/2 = 25 minute) left after 50 minutes ?

(a) One half
(b) One fourth
(c) One third
(d) One eight.
7. 75% of a first order reaction was completed in 32 minutes. 50% of the reaction will be
completed in.
(a) 24 minutes.
(b) 16 minutes.
(c) 8 minutes.
(d) 22 minutes.
8. A large increase in the rate of reaction for a small rise in temperature is due to.
(a) Increase in number of collision.
(b) Increase in the number of activated molecules.
(c) Lowering of activation energy.
(d) Shortening of the mean free path.
9. For an endothermic reaction where DH represent the enthalpy of the reaction in kJ/mol,
the minimum value for energy of activation will be.
(a) Less than DH
(b) Zero.
(c) Equal to DH
(d) More than DH
10. The half-life of a radioactive element is 1580 years. How long will it take to reduce to 1/4th
of its original mass ?
(a) 3160 years
(b) 796 years
(c) 1580 years
(d) 6320 years
11. The isotope 19K42 has a half life of about 12 hours. What fraction of the initial concentration
of 19K42 remains after 48 hours.
(a) 1/4
(b) 1/8
(c) 1/12
(d) 1/16
12. The hydrolysis of ethyl acetate in acid medium is a reaction of the
(a) Zero order
(b) First order
(c) Second order
(d) Third order.
13. The rate constant k/a of one reaction is found to be double that of the rate constant k a// of
another reaction. Then the relation between the corresponding activation energies of the
two reactions Ea' and Ea" can be represented as,
(a) E'a > E''a (b) E'a < E''a
(c) E'a =E"a (d) E'a = 4E"a

14. When a graph is plotted between lnk and 1/T for a first order reaction, we get a straight
line. The slope of the line is equal to
(a) -Ea/2.303 (b) -2.303
Ea.k
(c) Ea/2.30k (d) -Ea/k

15. The temperature coefficient of most of the reactions lies between.
(a) 1 and 3 (b) 2 and 3
(c) 1 and 4 (d) 2 and 4
16. t1/2 for zero order reaction is
1/ 2
(a) µa (b) µa
(c) µ a2 (d) µ a3
17. The decomposition of N2O5 by
2N2O5 ® 4NO2 + O2 follows first order kinetics.

Hence,
(a) The reaction is bimolecular
(b) The reaction is unimolecular
(c) t1/2 µ a0 (d) None of the above
18. The hydrolysis of ester in alkaline medium is
(a) Bimolecular reaction
(b) Termolecular reaction.
(c) First order reaction.
(d) Second order reaction.
19. The reaction 2Na + Cl2 = 2NaCl is found to follow 3rd order kinetics, its molecularity is
(a) 1 (b) 2
(c) 3 (d) 4
20. If 'a' is the initial concentration of a substance which reacts according to zero order kinetic
and 'k' is rate constant the time for the reactant to go to completion is,
(a) a (c) k
k a
(b) 2 (d) 2k
ka a
21. Which one of the following does not influence the rate of reaction.
(a) Nature of reactant
(b) Concentration of reactant
(c) Temperature
(d) Molecularity,
22. When AgNO3 solution is added to aqueus NaCl, a white precipitate is obtained. This
reaction is :
(a) Slow
(b) With measurable speed
(c) Instantaneous
(d) None of the above.
23. The rate law for the single step reaction
2A + B ® 2C is given by
(a) Rate = k[A] [B]
(b) Rate = k[A]2 [B]
(c) Rate = k[A] [B]
(d) Rate = k[A]2 [B]0
24. The rate law of the reaction,
2A + B ® 2C is represented as,
Rate = k [A]2[B]. If A is taken in large excess, the order of the reaction will be,
(a) Three (b) Two
(c) One (d) Zero.
25. If the rate of reaction between A and B is given by, rate = [A][B] 2, then the reaction is,
(a) First order with respect to A
(b) Second order with respect to B
(c) Third order overall
(d) all are correct.
26. The rate at which a substance reacts is proportional to.
(a) equivalent weight
(b) Molecular weight
(c) number of moles
(d) number of moles per litre.
dx
27. Rate Expression of a chemical change is = k[A]2 [B] [C]0
dt
The order of the reaction is
(a) 2 (b) 3 (c) 1 (d) 0
28. A zero order reaction is one
(a) In which the difference of concentration of product and reactant is zero.
(b) In which concentration of the reactants do not change with time.
(c) In which one of the reactants is in large excess.
(d) In which reactants do not react.
29. The half-life period of a reaction is 100 minutes. In 400 minutes the initial concentration
of 2.0g will become.
(a) 0.25g (b) 0.75g
(c) 0.125g (d) 0.1g
30. Which of the following rate law applies to a second order reaction involving only one
reactant ?
(a) Rate is directly proportional to concentration.
(b) Rate is directly proportional to the square root of concentration.
(c) Rate is equal to square of concentration.
(d) Rate is proportional to the square of concentration.
31. In a second order reaction 2A ® products, the concentration is halved. The half life of
the reaction is,
(a) Halved (b) Doubled
(c) Becomes four fold (d) Unaltered
ANSWERS TO MULTIPLE CHOICE TYPE QUESTIONS
1. a 8.b 15.b 22.c 29.c

2. a 9. c 16. a 23. b 30. d
3. d 10. a 17. c 24. c 31. b
4. d 11. d 18. a,d 25. d
5. b,c 12. b 19. c 26. d
6. b 13. b 20. a 27. b
7. b 14. c 21. d 28. b
qqq
SURFACE CHEMISTRY 147
UNIT - V
CHAPTER - 5
SURFACE CHEMISTRY
5.1 ADSORPTION :
Introduction :
It is a known fact that there are unbalanced residual forces acting along the surface of a
liquid or a solid. This is because if we consider a molecule present within the bulk of a liquid or
solid we will find that the molecule is uniformly attracted from all sides by the molecules that are
present in the neighbourhood and the net force of attraction that this molecule experiences is nil.
On the otherhand if we consider a molecule present on the surface of the liquid or solid we will
find that this molecule is subjected to some sort of inward pull by the molecules that are present
in the bulk. The molecule has some unutilized valencies because there are no neighbouring
molecules above the surface to which it can be bonded. As a result of these unbalanced residual
forces the surface of the liquid or solid is always under strain and it has a tendency to attract and
retain molecules of other substances preferably gases with which they are brought into contact.
This ultimately results in higher concentration of the gas molecules on the surface of liquid or
solid than in the bulk.
This phenomenon of higher concentration of molecular species on the surface of
the solid or liquid than in the bulk is known as adsorption. The branch of chemistry dealing
with the processes or the reactions taking place on the surface of the substances is known as
Surface chemistry.
Adsorbent :
It is the substance upon whose surface the phenomenon of adsorption takes place. Colloids
due to their small dimensions possess large surface area & act as good adsorbents, Examples
include charcoal, silica gel, clay etc. (See Fig. 5.1)
Adsorbate :
The substance which is taken up on the surface is known as adsorbate.
Interface :
The common surface between the two phases where the adsorbed molecules concentrate
is known as the interface.
Desorption :
It is reverse of adsorption. The process of removal of adsorbed substance from the surface
of the adsorbent is known as desorption. The process is brought about either by heating or by
reducing the pressure.
Adsorbate
Adsorbed layer
Solid
Adsorbent
Fig. 5.1
Adsorption and Absorption :
Both adsorption and absorption are to be distinguished carefully. In adsorption the substance
is retained only on the surface, it does not pass on to the interior or bulk of the solid or liquid. It
is simply a surface phenomenon. But in case of absorption the substance in uniformly distributed
throughout the body of the solid or liquid. Thus,
(i) Water vapour is absorbed by anhydrous calcium chloride but adsorbed by silica gel.
(ii) Ammonia is absorbed by water but adsorbed by charcoal.
The difference between adsorption and absorption is illustrated in the following Fig. 5.2
and Table - 5.1
Adsorption Absorption
Fig. 5.2
Table - 5.1 Distinction between adsorption and absorption
Adsorption Absorption
1. It is a surface phenomenon and therefore 1. It occurs throughout the body
occurs only on the surface of the material.
2. It is rapid in the beginning but slows 2. It occurs at a uniform rate.
down later at equilibrium.
3. There is unequal distribution of the 3. There is uniform distribution of the
material at the surface and in the bulk. molecular species throughout the bulk.
Sorption :
It is a term used to describe a process in which both absorption and adsorption take place
simultaneously. This term has been introduced by Mc Bain. For example dyes get adsorbed as
well as absorbed by the cotton fibre. Hydrogen is adsorbed as well as absorbed by charcoal.
TYPES OF ADSORPTION
Positive and Negative Adsorption :
If the concentration of adsorbate is more at the surface than in the bulk the adsorption is
known as positive adsorption. On the otherhand if the concentration of adsorbate is less at the
surface than in the bulk the adsorption is negative adsorption. Negative adsorption is observed
only in case of solutions.
Basing on the nature of forces existing between adsorbate and adsorbent, the process of
adsorption may be classified into two types namely (i) Physical adsorption or vanderWaals'
adsorption (ii) Chemical adsorption or Langmuir adsoption.
(i) Physical adsorption :
The adsorbate is held on the surface of the adsorbent by weak intermolecular attractive
forces known as vanderWaals' forces. This type of adsorption is also known as vanderWaals'
adsorption or physisorption. Between solid and gas the equilibrium is established rapidly and it is
reversible. Adsorption is temporary because of weak forces of attraction between the adsorbate
and the adsorbent. This type of adsorption can be reversed by increasing the temperature or by
decreasing the pressure.
Example – Adsorption of gases on charcoal.
(ii) Chemical adsorption or Chemisorption :
The adsorbate is held on the surface of the adsorbent by forces of attraction of almost the
same strength as chemical bond. This type of adsorption is also known as Langmuir adsorption
or chemisorption. Compared to physical adsorption it is more permanent and can not be easily
reversed. Example– Adsorption of hydrogen by metals like Ni, Pd, Pt etc.
Heat of adsorption and Free Energy change :
As a result of adsorption the residual forces acting along the surface of the adsorbent go
on decreasing. There is decrease in surface energy which appears as heat. Therefore, adsorption
is necessarily exothermic and is accompanied by evolution of heat.
Molar heat of adsorption is the amount of heat evolved when 1 mole of gas or vapour is
adsorbed on the surface of solid
We know the thermodynamic equation
DG = DH – TDS where DG = change in Free Energy
DH = change in Enthalpy
DS = change in Entropy
Again DG should be negative for a feasible process. Since adsorption is an exothermic

process DH is –ve. Again since the adsorbate changes from more random gaseous state to less
random adsorbed state on the surface of the solid DS is –ve. Adsorption is thus accompanied with
decrease in enthalpy so also decrease in entropy of the system. Since DH and DS are both –ve, it
is clear that DH should have a high –ve value so as to make DG –ve. The heat of adsorption per
mole of the adsorbate goes on decreasing i.e. DH becomes less and less –ve as adsorption proceeds
further and further. At a particular stage DH becames equal to TDS and DG becomes zero. This
is the case of equilibrium.
Table - 5.2 Comparison between physical adsorption and chemical adsorption
Physical adsorption. Chemical adsorption.
1. Forces of attraction are weak 1. Forces of attraction are strong chemical

vanderWaals' forces. bond forces.
2. Occurs at low temperature. 2. Occurs at high temperature.
3. It is not specific. 3. It is highly specific.
4. Heat of adsorption is low, usually it is in 4. High heat of adsorption, in the range of
the range of 20–40 kJ mole–1. 40-400 kJ mole–1
5. It is multilayer adsorption. The adsorbed 5. It is single layer adsorption. The adsorbed
layer is several molecules thick. layer is only of unimolecular thickness.
6. It is a reversible process. 6. It is highly irreversible.
7. Rate of adsorption increases with 7. Rate of adsorption decreases with increase
increase of pressure of the adsorbate. of pressure of the adsorbate.
8. It does not require any activation energy. 8. It requires activation energy.
5.2 ADSORPTION OF GASES ON SOLIDS :

The adsorption of gas on the surface of solid is known as occlusion. The extent of
adsorption of a gas on solid adsorbent depends on the following factors.
1. Nature of the gas (Adsorbate) :
Physical adsorption is non specific. So a gas gets adsorbed on the surface of the solid to a
greater or lesser extent. It has been observed that readily soluble and easily liquefiable gases like
NH3, HCl, Cl2, SO2 etc are adsorbed more than the so called permanent gases like H 2, N2, O2 etc.
This is because the vanderWaals' forces involved in the adsorption are more predominant in the
former category than in the latter category.
On the otherhand chemical adsorption is highly specific. So adsorption of gas on the
surface of solid can take place only if it can form a chemical bond with it.
2. Nature of the solid (Adsorbent) :
Easily liquefiable gases can be adsorbed on the surface of most commonly used adsorbent
activated charcoal. Metals like Ni, Pt & Pd are also used as adsorbents for adsorption of permanent
gases like H2, O2, N2 etc. Activated charcoal is used in gas masks for adsorption of poisonous
gases.
3. Specific area of the solid (adsorbent) :
The extent of adsorption also depends upon the surface area of the adsorbent. The greater
the surface area per unit mass of the adsorbent (specific surface area), the greater is the extent of
adsorption. This is the reason why the porous or finely divided forms of the adsorbents adsorb
effectively.
4. Effect of temperature :
Adsorption is associated with evolution of heat. According to Lechateliers' principle the
extent of adsorption increases with fall in temperature. In adsorption an equilibrium is established
between the gas in contact with the solid and the gas on the surface.
Adsorption
Gas + Solid Gas adsorbed on the surface of the solid. DH is –ve.
Desorption
Adsorption isobar is the graph drawn between the extent of adsorption (x/m) and temperature 't'
at constant pressure. The adsorption isobars for both physical and chemical adsorption are shown
below in Fig-5.3.
- -
x x
m m
t® t®
(Physical adsorption) (Chemisorption)
x = mass of the adsorbate m = mass of adsorbent
Fig-5.3
x
In physical adsorption there is continuous fall in m with rise in temperature. But in
x
chemisorption there is rise in m value in the beginning and then a fall in value with rise in
temperature. Like chemical reactions, chemisorption requires energy of activation, hence there is
x
rise in m value in the beginning.
5. Effect of pressure of the gas.
We know that adsorption is a reversible
process and is accompanied with decrease of x
pressure. Thus increase of pressure tends to m
increase the magnitude of adsorption. The
variation of adsorption with pressure at constant Ps
P
temperature is generally represented gaphically as
in Fig-5.4. The plot is called the adsorption Fig-5.4 Adsorption isotherm
isotherm.
6. Activation of adsorbent :
Increasing the adsorbing power of the adsorbent is otherwisely known as activation of
adsorbent. The more the activation of adsorbent the more is the extent of adsorption. Activation
can be made by the following methods :
(a) by mechanical rubbing or making the surface of adsorbent rough and porous.
(b) by using adsorbent in finely divided form. This increases the surface area and also
the extent of adsorption.
(c) by the action of super heated steam on the adsorbent. Charcoal is activated by this
method.
5.3 FREUNDLICH'S ADSORPTION ISOTHERM :

x
At equilibrium pressure PS , m attains its maximum value and no more adsorption occurs
even if the pressure is increased further. This is called saturation state and P S is referred to as
saturation pressure. Such type of isotherm can be obtained if
(i) The adsorbed gas forms a unimolecular layer on the surface of the solid.
(ii) The adsorbed gas behaves ideally is the vapour phase.
x
Freundlich gave the following relationships between m and p
(a) At low pressure
x
The graph is almost linear and sloping, which indicates that m is directly proportional to
pressure (P) is
x
m
µP
x
or, m
= KP, where K is a constant.
(b) At high pressure (beyond saturation pressure PS)
x
The graph is a straight line parallel to the pressure axis. Hence m becomes independent of P..
x
m
µ Po
x
or, m
= KPo, where K is a constant.
x
(c) At intermediate pressure : Hence m depends upon pressure raised to the powers between
0 and 1. This is represented mathematically as
x
m
µ P 1n
1
x
or, = KP n where 'n' is constant that depends on the nature of
m
adsorbate and adsorbent. The value of 1n lies in
between 0 and 1.
The above relationship is known as Freundlich's adsorption isotherm.
Taking logarithms of both the sides of above equation,
x
log m = log K + 1n log P..
x
If log m is plotted against log P, a straight line will be obtained having a slope 1n and the
x
intercept on log ( m ) axis will correspond to logK. (see Fig-5.5)
x
log
m 1
slope = n
Intercept
= log K
log P
Fig. 5.5 Graph of log x vs log P
m
From the graph it is possible to find out the value of K and n.
5.4 LANGMUIR ADSORPTION ISOTHERM :

The theory of adsorption of gas on the surface of a solid was proposed by Langmuir. The
surface of the solid is considered to be made up of a number of elementary sites. Each site
adsorbs one gas molecule. All the adsorption sites are assumed to be equivalent. It is also as-
sumed that a dynamic equilibrium exists between the adsorbed molecules and the free mol-
ecules. If A is the gas molecule and X is the surface of the solid.
Ka
A(g) + X (surface) AX
Kd
Where, Ka Rate constant for forward reaction i.e absorption.
Kd Rate constant for backward reaction i.e desorption.
If N Total number of sites on the surface
q Fraction of the surface sites occupied by gas molecules
(N – Nq) i.e N (1 – q) Number of vacant sites on the surface
PA Pressure of A
Then, the rate of adsorption = KaPA N (1 – q ) .........(1)
and the rate of desorption = Kd Nq ..............(2)
At equilibrium the rate of adsorption is equal to the rate of desorption
So, from equ. (1) & (2)
Ka PAN (1 – q) = Kd Nq...............(3)
or KPA ( 1 – q) = q ..................(4)
K
a
where K = K
d
Equation (4) can be written as
1- q 1
=
q KPA .................... (5)
1 1
or, q - 1 = KP ..................... (6)
A
1 1 1 + KP
or, q - = KP + 1 = KP
A
......................(7)
A A
KPA
q= ......................(8)
1 + KPA
Equ. (8) is called the Langmuir Adsorption isotherm.

Assumptions involved in the derivation of Langmuir Adsorption isotherm
(i) The gas adsorbed forms a monolayer on the surface of the adsorbent.
(ii) The adsorbed gas behaves ideally in the vapour phase
(iii) Each binding site on the surface of the adsorbent has same affinity for the gas mol-
ecules, The surafce of the solid in thus homogeneous.
(iv) The molecules adsorbed on different sites do not interact with each other.
(v) Adsorption is localised and takes place on collision of the gas molecules with the
vacant sites on the surface of the solid.
(vi) For all sites the heat of adsorption is the same. It is independent of pressure and
fraction of the surface of the adsorbent covered by gas molecules.
Study of adsorption isotherm
KP
Consider equation (8) . q = 1 + KP
A
(a) At low pressure KPA << 1, so that

q = KPA ....................(9)
Thus, the fraction of the surface covered is directly proportional to the partial pressure of
the gas molecules. This corresponds to 1st order reaction. When q is plotted against pressure the
nature of the curve is as depicted below. (Fig. 5.6)
q q ~ 1 (zero order)
KPA
q=
1+KPA
q = KPA (1st order)
Pressure
(Fig. 5.6)
(b) At high pressure, KPP >>1, so that
KPA .......... (10)

q= =1
KPA
Thus at high pressure q tends to become unity. The surface sites are completely covered
with gas molecules. The reaction rate becomes independent of pressure and therefore the reac-
tion becomes zero - order.
(c) At intermediate pressure
From equation (9) & (10)
At high pressure q = 1
At low pressure q = KPA
Hence, at intermediate pressure q = KPA1/n
1
where is a value lying between zero and one.
n
Since there is adsorption of single layer of molecules on the surface, the fraction q is
proportional to the amount of gas adsorbed per unit mass of adsorbent.
Representing this quantity by ‘a’,
we have, a a q or, a = K1 q where K1 is another constant.
x 1
a= = K 1 q = K 1 KPA n = kPA n ............................. (11)
1
So , 1)
m
where, x = amount of gas adsorbed and
m = gram of adsorbent
Equation (11) is the same as Freundlich adsorption isotherm.
Limitations
(i) Langmuir’s theory of adsorption holds good only at high temperature and low pressure
(ii) As the pressure increases or temperature decreases some additional layers are formed.
The adsorption becomes multimolecular, it no longer remains monomolecular.
5.5 APPLICATIONS OF ADSORPTION :

The phenomenon of adsorption has a wide range of applications. A few applications are
given below.
1. Removal of poisonous gases : Activated charcoal is used in gas masks in which all poisonous
gases and vapours like CH4, CO etc are adsorbed by charcoal leaving the pure air through
its pores.
2. Removal of colouring matter : Animal charcoal is used as a decolouriser in the manufacture
of cane-sugar.
3. Control of humidity : Silica and alumina gels are used as adsorbents for removing moisture
and controlling humidity.
4. Creation of high vacuum : If a bulb of charcoal cooled in liquid air is connected to a
vessel which has already been evacuated by a vacuum pump, the remaining traces of air are
adsorbed by charcoal and a high vacuum is created.
5. Chromotographic analysis : Chromatographic purification of compounds is based upon
adsorption.
6. Supply of nutrients to the plants : Colloidal particles of clay present in the soil adsorb
certain amount of moisture in which the nutrients such as compounds of nitrogen, phosphorus
and potassium dissolve and pass onto the plants through roots.
7. Catalysis : The phenomenon of adsorption plays an important role in heterogenous catalysis.
The use of finely divided iron in the manufacture of ammonia and finely divided Nickel in
hydrogenation of oils are the examples.
8. Removal of hardness of water : The use of ion exchange resins for removal of hardness
of water is based on adsorption.
9. Medicines : Various drugs can be adsorbed by body tissues. The effectiveness of medicines
is controlled by their selective adsorption.
10. Analytical chemistry : In volumetric analysis adsorption indicators are used. Also there
are selective adsorption of certain ions on some precipitate. For example Ba(NO 3)2 can not
be used for the precipitation of BaSO4 because of the adsorption of NO3– ion on BaSO4
precipitate.
5.6 CATALYSIS :
A substance that alters the rate of a chemical reaction without itself undergoing a change
is known as a catalyst. At the end of the chemical reaction the catalyst can be recovered unchanged.
A catalyst may accelerate or retard the rate of a chemical reaction. When it accelerates the
rate it is known as a positive catalyst whereas in case of retardation it is known as a –ve catalyst.
eg. In the Haber's process for synthesis of Ammonia Iron acts as a positive catalyst where
as in the process of decomposition of H2O2, acetanilide acts as a negative catalyst.
5.6.1 Characteristics of a Catalyst

1. The catalyst remains unaffected in amount, so also in chemical compostion at the end of
a chemical reaction.
eg. Consider the manufacture of H2SO4 in lead chamber process. In this case nitric
oxide acts as a catalyst.
1
NO(g) + O NO2(g)
2 2(g)
NO2(g) reacts with oxygen to form sulphur trioxide. At the end of the process Nitric oxide
is regenerated.
NO2(g) + SO2(g) SO3(g) + NO(g)
2. The catalyst in a very small quantity is required for the reaction.

e.g. Colloidal platinum at a concentration of 10 –8 mol dm–3 catalyses the decomposition
of H2O2.
However in certain cases the rate of the reaction depends upon the concentration of catalyst.
e.g. (i) Rate of inversion of cane sugar depends upon the concentration of H + used as
catalyst.
(ii) In some heterogeneous reaction the rate of the reaction increases with increase
in surface area of the catalyst. This is the reason why the efficiency of a solid
catalyst increases when it is present in finely divided state.
3. In a reversible reaction, a catalyst can not alter the state of equlibrium.
A catalyst catalyses both forward and backward reaction to the same extent in a reversible
reaction and therefore does not have any effect on equilibrium constant.
4. A catalyst gets termporarily involved in the reaction providing an alternative reaction
path of comparatively lower activation energy than that for uncatalysed reaction.
5. Tha catalyst can not initiate the reaction. The reaction can occur, though slowly, even in
the absence of catalyst.
6. The catalyst is gnerally specific in action.
e.g. MnO2 catalyses the decomposition of KClO3 but not KClO4 or KNO3.
Enzymes have also specific catalytic action.
7. The catalyst can not alter the nature of the products of the reaction.
e.g. KClO3 on decomposition gives oxygen. This thing happens in the presence or in
the absence of catalyst MnO2. Similarly the combination of H2 and N2 always results
in the formation of NH3 whether a catalyst is added or not.
However, there are certain exceptions.
(i) Chlorination of toluene in the absence of catalyst and in the presence of sunlight
results in the formation of benzyl chloride where as in the presence of halogen
carrier like Fe or I2 and in the absence of sunlight forms o – & p – chlorotoluene.
CH3 CH2Cl
+ Cl2 ¾Sunlight
¾ ¾ ¾¾® + HCl
Toluene Benzyl chloride
CH3 CH3 CH3

I
+ 2 Cl2 ¾¾®
¾ 2 + + 2 HCl
2
dark Cl Cl
o- chlorotoluene p- chlorotoluene
8. A catalyst is poisoned by certain substances.

e.g. (i) The rate of formation SO3 in the contact process can be slowed down considerably
in the presence of some arsenic compounds, even in traces.
(ii) In the hydrogenation of ethene the catalytic activity of Cu can be reduced by the
presence of Hg even in traces.
(iii) But in certain cases it is necessary to poison the catalyst so as to get the required
product.
Acid chlorides can be reduced to aldehydes by catalyst Pd suspended on BaSO 4.
O O
|| ||
R – C – Cl + H2 ¾¾Pd
¾¾® R – C – H + HCl
BaSO4
acid chloride Aldehyde
The function of BaSO4 is to poison the catalyst Pd thereby not allowing the reaction
to proceed further to alcohols.
9. A catalyst has an optimum temperature at which its efficiency becomes maximum.
10. The catalytic activity can be enhanced by the presence of certain substances known as
promoters.
e.g. In the synthesis of NH3 by Haber's process molybdenum acts as promoter to the
catalyst iron.
5.6.2 Types of catalysis

There are two types of catalysis
(a) Homogeneous catalysis
(b) Heterogeneous catalysis
Besides the above two there is a third category known as Enzyme catalysis which is due
to its own characteristics.
(a) Homogeneous Catalysis

In this case the reactants and the catalyst form a single phase. Examples are summerized
in the following table - 5.3.
Table - 5.3
Homogeneous Catalysis
Process Products Typical Catalyst
1. Lead chamber process for SO3(g) NO

manufacturer of H2SO4
NO(g)
2SO2(g) + O2(g) ¾¾¾¾® 2SO3(g)
2. Oxidation of CO(g) by O2(g) CO2(g) NO
3. Inversion of Cane sugar Glucose and Fructose H+
4. Hydrolysis of an ester Carboxylic Acid and H+
Alcohol
5. Decomposition of CH3CHO CH4 I2 Vapour
(b) Heterogeneous Catalysis

In this case the catalyst is in a different phase than that of the reactants. The catalyst is
usually a metal or an oxide
It is present in finely divided state to provide large surface area. The reactants are usually
liquids or gases. Most commonly used catalysts are metals like Pt, Ni, Fe, Cu & metal oxides like
ferric oxide, zinc oxide and molybdenum oxide. Examples are summarised in the following
Table - 5.4.
Table - 5.4
Heterogeneous catalysis
Process Products Typical Catalyst
1. Polymerization of Propylene Polypropylene Ti (IV) chloride

2. Contract process for SO3 Pt.
manufacture of H2SO4
3. Bosch process for manufacture of H2 CO2 and H2 Fe
4. Ammonia Synthesis NH3(g) Fe with Al2O3,
MgO, CaO, K2O etc.
5. Alkylation of Benzene C6H5 – CH3 H3PO4 on SiO2
6. Hydrogenation of oils Vegetable (fat) ghee Ni
5.7 ENZYME CATALYSIS :

Enzymes are complex nitrogeneous substances (proteins) with high relative molar mass
of the order of 10,000 or even more and are derived from living organisms. Certain reactions may
be catalysed either by the organisms in the bulk like yeast or by the chemical synthesised by and
extracted from them like yeast extract. Most of the biochemical processes such as digestion and
biosynthesis are catalysed by enzymes.
Characteristics of enzyme catalysis
1. Reactions catalysed by enzymes are highly specific. Each reaction is catalysed by a specific
enzyme. For example the enzyme urease catalyses the hydrolysis of urea and no other
reaction.
NH2CONH2 + H2O ¾Urease ¾ ¾¾® 2NH3 + CO2

2. In case of enzyme catalysis the rate of the reaction is more dependant on the amount of
the catalyst (enzyme) than it is in case of other type of catalysis.
3. There exists an optimum temperature for all reactions catalysed by the enzymes. At this
temperature the efficiency of the catalyst is maximum. The enzyme loses its catalytic
activity above this temperature and below this temperature the rate of the reaction becomes
slow due to temperature effects. The optimum temperature for maximum enzyme activity
varies between 15°C to 25°C.
4. The catalytic activity of the enzymes is due to their capacity to lower the activation energy
needed for a particular reaction.
5. The enzyme lose their catalytic activity in the presence of electrolytes and on exposure to
ultraviolet radiations. The addition of electrolyte results ultimately in coagulation of
enzymes.
6. For each enzyme there is one specific co-enzyme. Co-enzymes are the activators or
promoters for enzyme reactions. The activity of enzymes gets paralysed in case the co-
enzyme is separated from the enzyme.
7. Enzyme reactions are far more sensitive to catalysitc poisons than any other type of catalytic
reactions. Some typical poisons are HCN, H2S, CS2 etc.
8. The rate of a chemical reaction catalysed by an enzyme in maximum at a particular value
of pH called optimum pH value which is between 5-7. The following table summarizes
the examples of reactions catalysed by particular enzymes.
Table - 5.5
Enzyme Catalysis
Reaction Catalyst
1. C12H22O11 + H2O ® C6H12O6+C5H12O6 Invertase
sucrose glucose fructose
2. (C6H10O5) + nH2O ® C12H22O11 Diastase
starch maltose
3. C6H12O6 ® 2C2H5OH + CO2 Zymase
glucose
4. NH2CONH2 + H2O ® 2NH3 + CO2 Urease
urea
5.8 EFFECT OF THE CATALYST ON ACTIVATION ENERGY :

The effect of catalyst can be explained by intermediate complex theory. Consider the
following reaction.
2KClO3 ¾MnO
¾ ¾¾2
® 2KCl + 3O2
In this case MnO2 catalyses the reaction so as to increase the rate considerbly. According
to this theory the catalyst forms temporary bonds with reactants forming an intermediate complex.
The complex formed has transitory existence and it decomposes to yield the products and the
catalyst. The catalyst provides an alternative pathway involving lower activation energy. The potential
energy barrier is thus lowered in presence of the catalyst as is evident from the following figure 5.7.
Reaction path
without catalyst
Potential E2 E1
Energy Reaction path
Reactants with catalyst
Products
Reaction Co-ordinate
E1 ® Energy of activation without catalyst.
E2 ® Energy of activation with catalyst.
Fig. 5.7 Effect of catalyst on activation energy
The lower the value of activation energy of a reaction the faster will be its rate. This is
also evident from Arrhenius equation k = A.e–Ea/RT
5.9 ADSORPTION THEORY OF HETEROGENEOUS CATALYSIS :

According to this theory when the reactant molecules in gaseous state or in solution are
adsorbed on the surface of solid catalyst, the rate of the reaction is increased due to greater
accumulation of reactant molecules on the surface of the catalyst. Since adsorption is an exothermic
process, the heat of adsorption is used in increasing the rate of the reaction. The catalytic activity
is localised on the surface of the catalyst and this can be explained by a suitable machanism. The
mechanism involves a number of steps.
1. Reactant molecules are diffused to the surface of the catalyst.
2. Reactant molecules get adsorbed on the surface of the catalyst.
3. Formation of an intermediate.
4. Desorption of reaction products from the surface of the catalyst.
5. Diffusion of reaction products away from the catalyst's surface.
The above five steps can be pictorially summarised by the following figure 5.8.
A
+ A+B
Reacting B
molecules
Surface of catalyst
having free valencies Adsorption of
reactant molecules
+ A–B A
Desorption
of product B
Catalyst Intermediate
Fig. 5.8 Adsorption of reacting molecules,

formation of intermediate and desorption of product
5.10 IMPORTANT FEATURES OF SOLID CATALYSTS :

1. Activity : We know that the reactant molecules are to be adsorbed on the surface of the
catalyst. The activity of a catalyst depends upon the strength of chemisorption to a greater
extent. The reactant molecules must get adsorbed reasonably strongly on the surface of
the catalyst to become active. But the adsorption must not be that strong enough to make
the reactant molecules immobile.
e.g. In case of hydrogenation reaction the catalytic activity increases from Gp5 to Gp11
metals with maximum activity shown by Group 7-9 elements.
Pt
2H2(g) + O2(g) ¾¾® 2H2O(l)
Activity is thus the ability of the catalyst to increase the rate of a chemical reaction, the
degree of increase can be as high as 1010 times in certain cases.
2. Selectivity : The selectivity of a catalyst is its ability to direct a reaction to yield a particular
product. The same reactants may lead to form different products in presence of different
catalysts.
Cu/ZnO - Cr O
e.g. (a) CO(g) + 2H2(g) ¾¾ ¾ ¾ ¾ ¾2¾¾
3
® CH3OH(g)
Ni
(b) CO(g) + 3H2(g) ¾¾®
¾ CH4(g) + H2O(g)
(c) CO(g) + H2(g) ¾Cu

¾¾® HCHO(g)
Thus the action of a catalyst is highly selective in nature. A substance which acts as a
catalyst in one reaction may fail to catalyse another reaction.
5.11 COLLOIDAL STATE :

Introduction :
Thomas Graham while working on diffusion observed that solutions of some substances
diffused easily through a parchment membrane whereas others did not. He divided the soluble
substances into two categories namely crystalloids and colloids. This observations led to the
development of a new branch of knowledge known as colloid science.
Crystalloids :
There are substances the solutions of which can diffuse rapidly through vegetable or
animal membrane. Such substances are called crystalloids. Examples of crystalloids include salt,
sugar, urea, acids and bases.
Colloids :
There are substances the solutions of which show little or no tendency to diffuse through
vegetable or animal membranes. Such substances are called colloids. Examples include gelatin,
glue, albumen, silicic acid etc.
After careful observation Thomas Graham and other investigators came to a conclusion
that between crystalloid and colloid there was no rigid distinction since the same substance could
behave both as crystalloid and colloid when dispersed in different medium. For example, soap
forms a colloidal solution in water but behaves as a crystalloid in alcohol. NaCl is a crystalloid
when dissolved in water but acts as a colloid in benzene. The term "colloidal substance" has
therefore lost its importance and "colloidal state" is most commonly used for all purposes since
almost all substances can be brought into colloidal state by suitable means.
5.12 TYPES OF COLLOIDAL SYSTEM :

(i) A colloidal system consists of finely divided particles of any substance with diameters
lying within the range 1 to 100 nm (i.e 10 to 2000 A0) dispersed in any medium.
(ii) A colloidal system is a two phase system comprising of dispersed phase and dispersion
medium.
(iii) The continuous phase is known as dispersion medium in which extremely minute particles
of discontinuous phase or dispersed phase lying within the colloidal range are suspended.
(iv) The dispersed phase and dispersion medium may be solid, liquid or gas. Thus different
colloidal systems are possible depending upon the nature of dispersed phase and dispersion
medium. (as shown in table- 5.6)
Table - 5.6 (Different Colloidal systems)
Dispersed Dispersion
Colloidal system. Examples
phase medium.
Solid Solid Solid Sol Mineral, gem stones
Solid Liquid Sol Paints, Proteins, gold sol, Ink.
Solid Gas Aerosol of solid Smoke, dust storm
Liquid Solid Gels Butter, Jellies, Boot polish
Liquid Liquid Emulsion Milk, medicines.
Cod-liver oil.
Liquid Gas Aersol of liquid Fogs, clouds, mists
Fine insecticide sprays.
Gas Solid Solid foam Rubber, Pumice stone.
Gas Liquid Foam or Froth Soap suds, lemonad froth
True solutions, Colloidal solutions and Suspensions

Depending upon the size of particles constituting the dispersed phase and dispersion
medium the solutions are divided into three categories.
(i) True solutions : Water soluble substances like sugar or sodium chloride when added to
water dissolve giving a homogeneous solution. The particles of the solute are of molecular
size, invisible and do not settle down on standing. True solutions are therefore called
molecular solutions.
(ii) Suspensions : Insoluble substances like barium sulphate or clay when added to water
settle down on standing for sometime. The particles are large enough to be visible in
naked eye. Suspensions are known as coarse dispersions.
(iii) Colloidal solutions : In between the two extremes lie particles which are bigger than
molecules but are too small to be visible even under a most powerful microscope. They
have a little or no tendency to settle down when suspended in a liquid. Colloidal solutions
are known as colloidal dispersions.
The properties of true solution, suspension and colloidal solution are summarised in
Table-5.7.
Table - 5.7 Properties of True solution, colloidal solution and suspension

Properties True solution Colloidal solution Suspension.
1. Size Less than 1 nm Between 1 nm & 100nm. > 100 nm.
2. Diffusion. Diffuse readily Diffuse No diffusion
through parchment slowly through
membrane. parchment membrane.
3. Visibility Invisible even Visible under Visible even
under ultramicroscope ultramicroscope in naked eye.
4. Scattering No scattering Scattering takes Do not show
of light place (Tyndall effect) Tyndall effect.
5. Filtration Possible through Possible through Neither possible through
filter paper & filter paper but filter paper nor
parchment membrane not through through parchment
parchment paper. paper.
5.13 CLASSIFICATION OF COLLOIDS :
On the basis of affinity of dispersed phase for dispersion medium the colloidal solutions
may be classified as follows.
(a) Lyophilic Colloids
(i) These are solvent loving.
(ii) These are stable colloids.
(iii) They have strong attraction for the dispersion medium.
(iv) On evaporation of the dispersion medium from colloidal sol, the residue can pass
into colloidal state on mere addition of the liquid. Hence these are also known as
reversible colloids.
(v) Examples are proteins, starch and rubber.
(b) Lyophobic Colloids
(i) These are solvent hating.
(ii) These are less stable.
(iii) They have very little attraction for the dispersion medium.
(iv) The residue left on evaporation can not readily be reconverted to a sol. Hence
these are also known as Irreversible colloids.
(v) Examples are Ferric hydroxide, Arsenic sulphide, Gold and other metals.
Colloidal solutions in water are called hydrosols and those in alcohol are called alcosols.
Hydrosols may be hydrophilic or hydrophobic depending upon their affinity for water. Gelatin,
gum etc. are hydrophilic colloids where as metal sulphides and metal hydroxides are hydrophobic
colloids.
Difference between lyophilic and lyophobic colloids are summarised in Table-5.8.
Table – 5.8 Distinction between lyophilic and lyophobic sols
Property Lyophilic sols Lyophobic sols.
1. Surface Tension Lower than that of dispersion Same as that of the dispersion
medium. medium.
2. Visibility Particles can not be detected even Particles can be readily detected
under ultramicroscope. under ultra-microscope.
3. Viscosity Much higher than that of the Same as that of the medium.
medium.
4. Reversibility Reversible Irreversible.
5. Stability More stable Less stable.
6. Action of Addition of small quantity of Addition of small quantity is
electrolytes electrolytes has very little effect sufficient to cause coagulation.
and larger amount is needed to
cause coagulation.
7. Migration in an Particles may migrate in either Particles migrate either towards
electric field. direction or not at all in an electric anode or towards cathode in an
field. electric field.
8. Hydration Particles are extensively hydrated. No hydration.
5.14 CLASSIFICATION OF COLLOIDS ON THE BASIS OF MOLECULAR SIZE :

On the basis of molecular size colloids have been classified into three types.
(i) Multimolecular colloids
The dispersed phase consists of aggregate of a large number of a small molecules having
molecular size less than 1 nm i.e 10–9 m. The aggregate has dimensions of colloidal size. The
particles are held together by weak forces of attraction like vander Waals forces. They are usually
lyophobic in nature. Examples include platinum sol, gold sol, sulphur sol etc.
(ii) Macromolecular colloids
The dispersed phase consists of macromolecules or polymers having very high molecular
mass. The molecular size is of colloidal dimensions. They are usually lyophobic in nature. Ex-
amples include starch, cellulose, plastic, protein etc.
(iii) Micelles or Associated colloids
The dispersed phase consists of aggregates of large number of particles of colloidal size
in concentrated solutions. The aggregated particles are called micelles at higher concentration.
The molecules contain both lyophilic and lyophobic groups. Examples include soaps and syn-
thetic detergents.
5.15 PREPARATION OF COLLOIDAL SOLUTION :

Colloidal state (10 Ao to 103 Ao) is an intermediate state between suspension (> 10 3 Ao)
and a true solution (1 – 10 Ao). Two types of methods are generally employed for preparation of
colloidal solution.
1. Dispersion methods : These methods involve the DRIVING
breaking of coarse particles into colloidal BELT
dimensions. The dispersion methods may be of HOLLOW SHAFT

METAL DISC
following types.
(a) Mechanical dispersion : DISCHARGE DISCHARGE
(i) The substance is finely ground and then

METAL DISC
shaken with the dispersion medium to form DRIVING
a coarse suspension. BELT
(ii) The Coarse suspension is broken down to

Fig -5.9
particles of colloidal dimensions in a colloid
mill.
(iii) In the colloid mill there are two metal discs nearly touching each other and rotating
in opposite direction with very high speed.
(iv) The suspension is allowed to pass through the rotating disc and broken down to
particles of colloidal size
(b) Electro-dispersion. (Bredig's arc method)
(i) This method is suitable for preparing
colloidal solutions of metals like silver,
gold, platinum etc.
(ii) An electric arc is struck between the
metal electrodes that are immersed in
the dispersion medium. The dispersion
medium is placed in the freezing
mixture.
(iii) The electrodes should be made up of Fig-5.10
the same metal whose colloidal solution
is to be prepared.
(iv) The enormous heat of the arc turns the metal into vapour which get condensed by
the ice cold water to give particles of colloidal dimensions. (Fig-5.10)
(v) A little KOH is added to the dispersion medium to stabilise the sol.
(c) Peptisation :
(i) The process of conversion of a precipitate into colloidal dispersion by chemical
means is known as peptisation.
(ii) An electrolyte having an ion in common with the material to be dispersed is necessary
for the formation of sol. The electrolyte added is known as the peptising agent.
(iii) The peptising action is due to the preferential adsorption of one of the ions of the
electrolyte on the surface of particles of the material.
(iv) When a small amount of FeCl3 is added to freshly prepared Fe(OH)3, a dark reddish
brown colloidal solution results. Here FeCl3 is the peptising agent. Fe3+ ions from
FeCl3 get adsorbed on the surface of Fe(OH)3 . Since like charges repel each other,
colloidal particles of the type [Fe(OH) 3]Fe3+ get separated. Similarly Al(OH)3 sol
is obtained when dilute HCl is added to freshly prepared Al(OH) 3.
2. Condensation or Aggregation Methods.
In these methods particles of atomic and molecular dimensions are allowed to aggregate
to form bigger particles of colloidal dimensions. The method includes the following.
(a) Double decomposition : Arsenous sulphide sol is prepared by passing H2S gas through
a dilute solution of As2O3 and removing excess H2S by boiling.
As2O3 + 3H2S ® As2S3 + H2O
yellow.
(b) Oxidation :
When H2S gas is passed through an aqueous solution of SO2, colloidal sulphur is formed.
It is a light yellow coloured aquosol.
SO2 + 2H2S ® 2H2O + 3S.
(colloidal)
(c) Reduction :
When gold chloride solution is treated with SnCl 2, a violet gold sol is obtained.
2AuCl3 + 3SnCl2 ® 3SnCl4 + 2Au
Reducing (colloidal gold sol)
agent
(d) Hydrolysis :
A colloidal solution of Fe(OH)3 is obtained by boiling a dilute solution of FeCl 3.
FeCl3 + 3H2O ® Fe(OH)3 + 3HCl
Similarly, by hydrolysis of AlCl3 and sodium silicates, colloidal solutions of Al(OH) 3 and
silicic acid are also obtained.
(e) Exchange of solvents :
Sulphur and phosphorus are soluble in alcohol. When an alcoholic solution of sulphur is
poured in excess of water hydrosol is formed. The substance present in molecular state in
alcohol precipitate out in water in the form of particles of colloidal size.
Purification of colloidal solutions

The colloidal solutions are rendered unstable by the presence of impurities. These
impurities are therefore removed by suitable methods which are discussed below.
(1) Dialysis :
The process of separating a crystalloid from a colloid by diffusion through a parchment
membrane is known as dialysis and the apparatus used to this effect is known as dialyser. There
are two types of dialysers.
(a) Graham's dialyser :
An impure colloidal solution is taken in the dialyser made up of parchment or cellophane
paper. It is suspended in a beaker containing running distilled water. The rate of flow of water is
adjusted so as to keep the level of water constant. The impurities in the form of crystalloid pass
through the parchment membrane leaving behind the colloidal solution in the pure form inside
the dialyser (parchment bag) (Fig - 5.11).
For example, Sodium silicate is allowed to react WATER
with dilute HCl and the mixture is taken in the
parchment bag immersed in water to get a colloidal
IMPURE
solution of silicic acid (H2SiO3) COLLOIDAL
SOLUTION
Na2SiO3 + 2HCl ® H2SiO3 + 2NaCl
In this case NaCl and unused HCl pass through MEMBRANE
the membrane leaving behind pure colloidal solution

of silicic acid.
Fig-5.11
(b) Electrodialyser :
The process of dialysis is ordinarily quite slow
but it can be hastened by the application of electric field.
The impure colloidal solution is taken in a parchment
bag suspended in a vessel through which fresh water in IMPURE
COLLOIDAL
continuously passing. The ions of the electrolyte in the SOLUTION
bag migrate faster under the influence of electric field

towards the oppositely charged electrodes leaving
MEMBRANE
behind the colloidal solution in the bag. The process is
WATER
known as electrodialysis. (Fig-5.12)
(2) Ultrafiltration : Fig-5.12
The separation of colloids from crystalloids can also be made by ultrafiltration. Ordinary
filter paper have pores larger than 1 m i.e 10–6m through which colloidal solution along with the
impurities (crystalloids) can easily pass. The pores of the filter paper can be made smaller by
soaking it in a solution of gelatin or collodion and then hardening them by soaking in formaldehyde.
The pores thus become very small so as not to allow the colloidal particles to pass through them.
Only the crystalloids can pass through such filter paper leaving behind the colloidal solution. The
filter paper is known as ultrafilter and the process is known as ultrafiltration.
This process is very helpful in removing soluble impurities from colloidal solution.
Cellophane membranes are the best ultrafilters.
5.16 PROPERTIES OF COLLOIDAL SOLUTION :
(i) Heterogeneous nature : A colloidal solution is heterogeneous in nature. It consists of
two phases : the dispersed phase and dispersion medium.
(ii) Diffusibility : The colloidal particles constituting the dispersed phase do not diffuse
through the parchment paper. This property forms the basis of colloid chemistry.
(iii) Filtrability : The colloidal particles can readily pass through ordinary filter paper. However
the particles can be filtered through ultrafilters.
(iv) Colour : The colour of the colloidal particles is not always the same as colour of the
substance taken in bulk. For example colloidal sulphur is colourless whereas sulphur is
yellow. Colloidal gold is red whereas gold is yellow.
(v) Visibility : Even by the help of most powerful microscope the colloidal particles can not
be seen. However in recent times u.v rays or cathode rays are used for seeing these particles.
The electron microscope may also be used for the purpose.
(vi) Colligative properties : Colligative properties are those which depend upon the number
of solute particles that are present in the given mass of solvent. These properties include
lowering of vapour pressure, depression in freezing point, elevation in boiling point etc.
Colloidal particles are not simple molecules, these are physical aggregation of molecules.
So the number of particles present in the sol is always less than the number of particles
present in true solution. Hence all the colloidal dispersions show a low value of colligative
properties.
(vii) Surface area : Since colloidal particles are very small in size they provide a large surface
area.
(viii) Optical properties
Tyndall effect : Tyndall observed that a MICROSCOPE
beam of light passing through a true BRIGHT
TYNDALL CONE
solution could be seen only if the eye is
placed directly on its path. But the same INTENSE
CONVERGING
beam of light when passed through a LIGHT BEAM
FROM DARKNESS
colloidal solution became visible as a ARC LAMP
bright streak. This phenomenon is know

COLLOIDAL SOLUTION
as Tyndall effect and the illuminated path
is known as Tyndall cone (Fig-5.13) Fig-5.13
Tyndall effect is due to scattering of light from the surface of colloidal particles. The
effect is shown if the following conditions are satisfied.
(i) The wavelength of light used must be greater than the diameter of the particles
constituting the dispersed phase.
(ii) The difference in value of refractive indices of the dispersed phase and dispersion
medium must be appreciable.
In true solution the beam is invisible because there are no particles of sufficiently large
diameter to scatter light.
Tyndall effect is well defined in case of lyophobic sol since the difference between the
values of refractive indices of the dispersed phase and dispersion medium is appreciable. On the
other hand in case of lyophilic sols the particles are largely solvated and as a result the difference
in refractive indices of the two phases is lowered and the effect becomes much weaker.
Example of Tyndall effect
A beam of light entering a dark room lights up the dust particles present in the air. The
dust particles are large enough to scatter light rendering the path of light visible.
Uses : (i) The effect distinguishes between the lyophilic and lyophobic colloids.
(ii) Colloidal particles which are invisible can be made visible by using dark background
illumination.
(iii) The effect has been used by Zsigmondy and Sicdentopf in devising ultramicroscope.
(ix) Mechanical property

Brownian movement :
An English botanist Robert Brown molecules
of dispersion
observed that pollen grains in aqueous colloidal colloidal medium
suspension were in a state of constant rapid particle particle
zigzag motion. When viewed under BROWNIAN MOVEMENT

ultramicroscope it was found that the particles
of hydrophobic sols executed similar type of Fig -5.14
ceaseless random motion. (Fig-5.14)
This kinetic activity of particles suspended in a liquid is called Brownian movement.
Cause : The movement is due to unequal bombardment of the molecules of dispersion
medium with the colloidal particles. Brownian motion is inversely proportional to the size of the
colloidal particles. The movement slows down with the increase in particle size. The reason for
slow movement in case of bigger particle is decrease in chance of unequal bombardment on it. As
a result of the movement the colloidal particles acquire almost the same amount of energy as
possessed by the molecules of dispersion medium.
Applications :
(1) Diffusion of particles from solution of higher concentration to solution of lower
concentration can be explained on the basis of the Brownian movement of colloidal
particles.
(2) The motion offers an explanation for the random kinetic motion of molecules of a liquid.
Origin of charge on Colloidal particles.
The sols are associated with little amount of electrolytes and without the presence of
electrolytes the sols become highly unstable. The charge on the colloidal particles is due to
preferential adsorption of a particular type of ion on their surface. If the particles prefer to adsorb
positive ions they acquire positive charge and if they have a preference to adsorb negative ions
they become negatively charged.
For example–
(i) Ferric hydroxide sol is positively charged. Since it is formed by the hydrolysis of Ferric
chloride, the +ve charge on the sol is due to preferential adsorption of Fe 3+ ion on the
surface of the particles of Fe(OH)3. The Fe3+ ions are generated due to ionisation of FeCl3
which is present in traces.
(ii) In Arsenic sulphide sol traces of H2S are present. There is preferential adsorption of
sulphide ion on the surface of particles of Arsenic sulphide. Hence the sol is –vely charged.
The sulphide ions are furnished by the dissociation of H 2S.
(iii) Stannic oxide sol carries a +ve charge if peptised by a small amount of HCl. But if it is
peptised by small amount of NaOH it carries a –ve charge. This is because in the former
case a small amount of SnCl4 is formed and Sn4+ ions are adsorbed on the surface of
stannic oxide particle and the sol carries +ve charge. In the latter case small amount of
Na2SnO3 is formed and the SnO 2- 3
ions are adsorbed giving the sol –ve charge.
(iv) Another interesting example is furnished by silver iodide sol which may be +vely or –
vely charged. If a dilute solution of AgNO3 is added to slight excess of dilute solution of
sodium iodide, the AgI sol formed is –vely charged. This is due to adsorption of I – ions.
Again if a dilute solution of sodium iodide is added to slight excess of AgNO 3, the AgI
sol formed is +vely charged. This is due
to adsorption of Ag+ ion (Fig-5.15),
However, if silver nitrate and sodium
iodide are mixed in equivalent amounts,
AgI is precipitated, but no sol is formed.
Conclusion :
(a) The ion which is more nearly related
chemically to the colloidal particle is Fig - 5.15
adsorbed preferentially. ( Ref. example
(i) & (ii) )
(b) The ions adsorbed by the colloidal particles are those which are common to them.
(Ref.. example (iv))
(c) On the surface of colloidal particle there is an electrical double layer of opposite charges.
(Ref. example iv)
(x) Electrokinetic Properties :

ZETA POTENTIAL
A colloidal particle is a charged particle and is surrounded by ions of opposite charge.
Hence an electrical double layer is formed at the surface of separation between two phases.
Consider solid-liquid interface. The double layer formed at the interface is made up of a layer of
ions in aqueous solution which are firmly held to the solid (fixed layer) and a more diffused
mobile layer extending into the solution. The fixed layer may consist of +ve or –ve ions but the
mobile or diffused layer consists of ions of both the signs. The resultant charge of the diffused
layer is equal in magnitude but of opposite sign to that of the fixed layer. (Fig-5.16)
+ I – + – – I + – +
+ I – – + – I + + +
+ I – – – – I + – –
+ I + – – – I – + –
Solid + I – + + Solid – I + + +
+ I – – + – I + – +
+ I – + – – I + + –
+ I + – + – I + + +
+ I – – – – I – + –
Fixed Fixed
Diffused layer Diffused layer
layer Fig - 5.16 layer
Since separation of charge is a seat of potential, there develops a difference in potential

between the fixed and the mobile layer.
This difference in potential between the fixed layer and the diffused layer having opposite
charge is known as electrokinetic potential or Zeta potential.
4 phm
Zeta potential (Z) is given by the relationship. Z =
D
where h = Coefficient of viscosity of dispersion medium.
m = Electrophoretic mobility of particles
D = Dielectric constant of the medium.
The value of Z is about 50 millivolts. when Z approaches zero, coagulation of sol particles
takes place.
Since solid particles and the liquid medium carry opposite charges, on application of an
electric field, the solid particles and the liquid medium will move in opposite directions.
(a) If experiments are so arranged that only the particles move and not the medium, the
phenomenon is known as Electrophoresis or Cataphoresis.
(b) On the otherhand if the experiments are designed such that only the medium moves and
not the particles, the phenomenon is known as Electro-osmosis.
Electrophoresis :
The migration of electrically charged sol particles under the influence
of an applied electric field is known as Electrophoresis or Cataphoresis.
This phenomenon can be demonstrated in a U-tube. (Fig 5.17) WATER
(i) The U-tube is provided with a stop cock through which it is connected
to a reservoir of funnel shape.
(ii) Small amount of water is taken in the U-tube and sol of Arsensic
sulphide is taken in the reservoir.
(iii) Stop cock is opened slightly and the sol is allowed to enter the U-
tube by gradually raising the reservoir. Water is displaced upwards
and a sharp boundary is produced in each arm.
(iv) Two platinum electrodes are dipped in water layer and a voltage of Fig-5.17
50 to 200 volts is then applied.
(v) The position of boundary in both the arms is marked by means of a lens or cathetometer.
In the present case the boundary on the negative electrode side is seen to move down and
that on the +ve electrode side is seen to move up indicating that the particles migrate
towards the positive electrode.
(vi) The direction of motion of the particles determines the charge carried by the particles.
Since Arsenic sulphide sol is –vely charged, in this case the flow is towards the +ve
electrode.
Electrophoretic mobility of colloidal particles :

The rate at which the colloidal particles move under the influence of electric field can be
expressed in terms of their electrophoretic mobilities. The electrophoretic mobility of colloidal
particles is defined as the distance travelled by them in one second under a potential gradient of
1 volt per centimetre.
Advantages
(i) It is possible to separate the colloidal materials from their mixtures since different colloidal
materials are associated with different mobilities. For fractionation of proteins,
polysaccharides, nucleic acids etc this method is very helpful.
(ii) It is used in precipitation of smoke from chimney gases.
(iii) It is used to determine the charge on colloidal particles.
(iv) It is used in removal of dirt from sewage.
COAGULATION OF COLLOIDAL SOL (Flocculation)

The stability of colloidal particles is due to the charge present on them. In lyophobic
colloids the stability is due to their electric charge where as in case of lyophilic colloids the
stability is due to their charge and extensive solvation. Tendency of sol particles to settle render
them unstable.
In lyophobic sols the particles carry same type of charge and repel each other and resist
the tendency to combine or settle. In lyophilic sol same type of electrostatic repulsion operates
along with another added factor of solvation. There is attraction between the solvent molecules
and the suspended particles which results in solvation of particles and prevent the particles from
coming closer.
If by some means the charge on the colloidal particles can be destroyed then such particles
settle down in the form of a precipitate. The precipitation of particles of the dispersed phase is
known as Coagulation or Flocculation. When the charges on the colloidal particles are destroyed
the zeta potential around the particles drops below 0.02V and this results in reduction of repulsion
between the colloidal particles leading to coagulation or flocculation.
Coagulation of lyophobic sol : The removal of charges can be done in different ways.
(1) By addition of other electrolytes :
Although traces of electrolytes are required for the stability of the sols, the presence of
large amount of electrolytes cause their coagulation. The reason is that the colloidal particles take
up the ions carrying charge opposite to that present on them and as a result the charge on them get
neutralised and the sol gets coagulated or precipitated. For example,
(i) Arsenous sulphide sol gets precipitated upon addition of sodium chloride to it. Na + ion is
the flocculating ion, it neutralises the –ve charge carried by the sol particles. As 2S3 sol
can also be coagulated by addition of positive ions like Mg 2+, Ca2+, Ba2+ etc.
(ii) Fe(OH)3 sol which is +vely charged can be coagulated by negative ions such as Cl - ,
- -
NO3 , SO24 etc.
(2) By mutual precipitation : When two sols having opposite charges are mixed together in
suitable proportions, mutual precipitation takes place. For example, when +vely charged
sol Fe(OH)3 and –vely charged sol As2S3 are mixed in suitable proportions their charges
are neutralised with each other and both are partially or completely coagulated or
precipitated.
(3) By persistent dialysis : On prolonged dialysis the traces of electrolytes present in the sol
are removed and the sol becomes unstable.
(4) On boiling the sol : On boiling the sol, the amount of electrolyte present in the sol is
reduced and in some cases the sol may precipitate.
(5) On freezing the sol : If freezing of sol is carried out for enough time there is removal of
medium and the sol becomes unstable.
(6) By mechanical means : Stirring the sol for a long time may coagulate it. Also the vibratory
action caused by ultrasound may result in coagulation.
Hardy-Schulze Rule :
According to this rule coagulation is brought about by the ions having opposite charge to
that carried by the sol particles. Hence –ve ions cause coagulation of +ve sol and +ve ions cause
the coagulation of –ve sol.
The quantity of the electrolyte necessary to coagulate a definite amount of the sol depends
upon the valency of the ion carrying a charge opposite to that of colloidal particles. This is known
as Hardy-Schulze rule. For the coagulation of As2S3 sol flocculating power of the cations decreases
in the order Al3+ > Ba2+ > Na+. Also for the coagulation of Fe(OH)3 the flocculating power of
anions is in the order
-
[Fe(CN)6]4– > PO 34 > SO2-
4
> Cl - .
Flocculation value : The minimum concentration of an electrolyte required to cause coagulation
or flocculation of a sol is called its flocculation value. This is expressed in millimoles per litre
of the electrolyte. The following table represents the flocculation values of different elctrolytes
for As2S3 and Fe(OH)3 sols.
Coagulation of Lyophilic sols :
(1) By adding electrolytes (Salting out)
The coagulation of lyophilic sol by the addition of electrolyte is not due to neutralisation
of charge on the particle as in case with the lyophobic sol. The electrolyte added binds part of the
water and get hydrated. As a result the polymer molecules in lyophilic sol get dehydrated and
there is reduction in values of their zeta potential. The dehydration results in coagulation. The
effect is called salting out. The salting out effect depends upon the nature of the ions and salts of
a given metal. Various ions are arranged in order of their effectiveness in a series known as
Lyotropic series or Hofmeister series.
The order of cations is
Mg2+ > Ca2+ > Sr2+ > Ba2+ > Na+ > K+
The order of anion is
2- - -
Citrate3– > Tartrate2– > SO4 > CH3COO– > Cl– > NO 3 > ClO 3 > I– > CNS–
(2) By addition of a suitable solvent :
Solvents like alcohol and acetone have large affinity for water. When these solvents are
added to lyophilic sols, the dispersed phase undergoes dehydration and therefore the stability of
such particles is due to their charge only. If in this condition small amount of electrolyte is added
that results in coagulation of the sol.
Protection of Colloid :
It is a fact that the lyophobic sols are easily coagulated as compared to lyophilic ones by
the addition of small quantity of electrolyte. But the lyophobic sol becomes less sensitive to
coagulation when a large amount of lyophilic sol is added to it. The presence of lyophilic colloid
thus inhibits the flocculating action of an electrolyte on a lyophobic colloid. For example, the
coagulation of gold or silver sol can be prevented by the addition of lyophilic sol like gelation or
albumin. The lyophilic sol is known as the protective colloid and its effect on lyophilic one is
known as protective action. Hence the process by which the sol particles are prevented from
coagulation by the addition of electrolyte is known as protection of colloid. The reason for
protection is due to the fact that the sol particles adsorb the protective colloid particles forming
a protective layer around them. This layer prevents the flocculating ion from reaching the sol
thereby not allowing the sol to precipitate.
Gold Number
Zsigmondy introduced the principle of gold number in order to measure the relative
protective power of lyophilic colloids. It is defined as the number of milligrams of protective
colloid which prevents the coagulation of 10 ml of a given gold sol when 1 ml of a 10% solution
of NaCl is added to it.
The protective action of a lyophilic sol depends upon factors like dispersity and the molar
mass of the sol and also the pH of the solution at which the experiment is carried out. The smaller
the gold number the greater is the protective action of the protective colloid. For example, gelatin
is having a small gold number (Table - 5.9), hence acts as a very good protective colloid.
Table -5.9 Protective action of lyophilic colloids on some hydrophobic sols.
Protective colloids Gold number
Gelatin 0.1
Dextrin 20
Saponin 115
Potato starch 20
Haemoglobin 0.03-0.07
Egg albumin 2.5
Gum arabic 0.5
5.17 APPLICATIONS OF COLLOIDS :

Colloids play a vital role in our day to day life as well as in agriculture, medicine, industry
etc. Some of the applications in various fields are discussed below.
1. Medicines : Most of the medicical preparations are emulsions that are colloidal in nature.
Medicines in the form of emulsions are easily assimilated and therefore more effective.
2. Foods : Most of our foods are colloidal in nature. Milk is an emulsion which is stabilised
by casein, a lyophilic colloid. The smoothness of icecream can be preserved by the addition
of gelatin, a protective colloid. Similarly jelly, jam, whipped creams etc are of colloidal
nature.
3. Rubber plating : Rubber plating can be carried out by the process of electrophoresis for
the porpose of insulating various tools. The article to be rubber plated is made anode.
Upon application of an electric field the rubber particles being –vely charged, migrate
towards anode and get deposited on the article.
4. Sewage disposal : For sewage disposal the electrophoretic property of colloidal particles
is of great use. Particles of dirt, mud etc of colloidal size are contained in sewage water.
These particles carry electric charge and therefore do not settle down easily. On application
of an electric field in the sewage tank these particles migrate towards oppositely charged
electrode, get neutralized and settle down in the form of a precipitate at the bottom.
5. Artificial rain : Electrified sand is thrown from aeroplanes on the clouds which consist of
charged particles of water dispersed in air. The colloidal water particles of the clouds get
neutralised and coagulate to bigger water drops which ultimately results in artificial rain.
6. Purification of water : The presence of –vely charged fine particles of clay causes slight
turbidity in water. The addition of potash alum ie Al 3+ ions neutralises the –ve charge
carried by the collodal clay particles and cause their coagulation. The clay particles settle
down leaving water in clear state.
7. Smoke precipitation : In industrial areas the
smoke coming out of the chimneys contains
electrically charged colloidal particles of
carbon dispersed in air. Principle of
electrophoresis is employed for the removal
of these particles. In cottrell precipitator (Fig-
5.18), the smoke is allowed to pass through
chambers fitted with highly electrically
charged plates. The colloidal carbon particles
present in smoke are discharged and
deposited on the oppositely charged electrode
Fig-5.18
leaving the gas to escape through the chimney.
8. Detergent action of soap : Soap solutions are used to remove the dirt and dust particles
sticking to the fabric. But most of the dirt or dust sticks on the oily or greasy materials
which ultimately gather on cloth. It is difficult to wash the cloth simply by water since
grease is not readily wetted by water. The interfacial tension existing between water and
grease can be lowered upon addition of soap and this causes the emulsification of grease
in water. Mechanical action such as rubbing helps in removal of dirt.
9. Formation of delta : River water contains negatively charged colloidal particles of sand
and clay. Sea water contains a large number of dissolved salts and therefore serves as
electrolyte containing Na+, Ca2+, Mg2+ etc. When river water touches sea water coagulation
of clay particles takes place at the point of contact because of charge neutralisation. As a
result the clay particles coagulate and settle down raising the river bed. The river water
adopts a separate coarse and this results in formation of delta.
10. Smoke screens : Smoke screens consist of fine particles of titanium oxide dispersed in
air. These are used in warfare for the purpose of concealment and camouflage. When
ejected from aeroplanes smoke screen containing heavy particles of titanium oxide drops
down rapidly forming a curtain of dazzling whiteness.
11. Blue colour of the sky : It is due to scattering of blue light by the colloidal dust and
water particles present in the sky.
5.18 EMULSION :
The colloidal systems in which both dispersed phase and dispersion medium are liquids
are otherwise known as emulsions. Any two immiscible liquids can thus form an emulsion.
Emulsions are usually unstable and upon standing form two separate layers. Examples are milk,
cod-liver oil etc.
Types of Emulsions
There are two types of emulsions
(a) Oil in water type (o/w)
Here oil is the dispersed phase and water is the dispersion medium. Water is the continu-
ous medium in which oil droplets are dispersed.
Example-Milk is an emulsion of this type since fat globules are dispersed in water.
(b) Water in oil type (w/o)
Here water is the dispersed phase and oil is the dispersion medium. Oil is the continuous
medium in which water droplets are dispersed.
Example- Butter is an emulsion of this type
Water Oil
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
~~~~~~~~~~~~~~ ~ ~~~~~~~~~~~~~~
~
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
~~~~~~~~~~~~~ ~~~~~~~~~~~~~
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
~~oil
~~~~~~~~oil~~~~ ~~~~~~~~~~~~~~
~~~~~~~ ~~~ ~~~~~ ~~~~~~~
~~~ ~~~~~
~~~~~~~ ~~~~~~~ ~~~~~~~~~~~~~~
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
~~~oil
~~~~~~~oil
~~~~ ~~~~~~~~~~~~~~
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~
Fig. 5.19 Oil in water (o/w) type Fig.5.20 Water in oil (w/o) type
Identification of emulsions
(i) Dye test - Add a small amount of oil soluble dye to the emulsion under examination. If it
is of w/o type i.e if oil is the continuous medium then it acquires the colour of the dye
immediately. On the otherhand if the emulsion is of o/w type the dye will not mix and the
emulsion remains colourless.
(ii) Electrical conductivity - If water is in excess, more will be the electrical conductvity. In
o/w type emulsion or aqueous emulsion the electrical conductivity is more than w/o type
emulsion or oily emulsion.
(iii) Dilution test - If on adding water the emulsion character is retained then the emulsion is
identified as o/w type. On the otherhand by adding oil if the emulsion character is re-
tained then the emulsion is identified as w/o type.
Emulsifiers
(i) Emulsifiers are the agents required for stabilising the emulsions.
(ii) They lower the interfacial tensions between the constituents of emulsion.
(iii) They form thin films around the droplets of dispersed phase thereby not allowing them to
come closer preventing their coagulation.
(iv) Examples of emulsifiers or emulsifying agents include soaps, detergents and lyophilic
colloids.
Role of Emulsifier
Consider two immiscible liquids such as a hydrocarbon oil and water . If we shake the
two solutions vigorously, a milky solution results. This is an emulsion of o/w type. The emulsion
is highly unstable. It is necessary to add a small amount of another substance i.e an emulsifier or
emulsifying agent to stabilise the emulsion.
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~
~~ ~ ~~ ~ ~ ~
~~~~~~~ ~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
~~~~~~~~~~~~~~
The emulsifier consists of both ionic as well as non -ionogenic surfactants. The ionic
surfactants which act as emulsifiers include soaps, long chain sulphonic acids and alkyl sulphates.
These ionic surfactants are long chain organic compounds with polar groups. These surfactants
get adsorbed at the interface between the dispersed phase and the dispersion medium forming a
monomolecular layer thereby lowering the interfacial tension between oil and water facilitating
the mixing of two liquids. The soap molecules contain polar groups ( –COONa) and non polar
end hydrocarbon chain. The concentration of soap at the interface is made in such a way that the
polar end interacts with water and nonpolar end with oil. The emulsion thus gets stabilised.
The non –ionogenic surfactants include lyophilic colloids such as proteins, gums, gelatin
etc. In milk, a protein is there known as casein. Casein forms a multimolecular protective layer
around the droplets of fat dispersed in water. Milk is therefore a stable emulsion.
Properties of Emulsions
(i) Emulsions are colloidal systems.
(ii) They exhibit all the electrical and optical properties of colloids like Brownian move-
ment, Tyndall effect, Electrophoresis, Coagulation etc.
(iii) Size of particles range from 1000 A0 to 10,000 A0.
Use of Emulsions
(i) They find use in concentration of ore particularly in Froth floatation process.
(ii) Digestion of fats in the intestine involves emulsification.
(iii) Various medicines like lotions, creams and ointments are available in the form of emul-
sions.
(iv) The cleansing action of soaps and detergents is based on formation of w/o type emulsion.
(v) Milk which acts as an important part of our diet is an emulsion of o/w type.
1. Crystalloids : Substances the solutions of which can readily diffuse through animal or
vegetable membrane. Example– salt, sugar, urea, acids, bases.
2. Colloids : Substances the solutions of which show little or no tendency to diffuse through
animal or vegetable membrane. Example– gelatin, albumin, glue etc.
3. Size of colloidal particles lie within the range 1 to 100 nm i.e. 10 to 2000 A o.
4. A colloidal system consists of dispersed phase and dispersion medium.
5. Lyophilic colloids are solvent loving and stable colloids. Example- Proteins, starch,
rubber etc.
6. Lyophobic colloids are solvent hating and less stable colloids. Example– Ferric hydroxide,
Arsenic sulphide sols.
7. Dialysis : The process of separating a crystalloid from a colloid by diffusion through a
parchment membrance is known as dialysis.
8. Tyndall effect is due to scattering of light from the surface of colloidal particles.
9. The difference in potential between the fixed layer and the diffused layer having opposite
charge is known as electro kinetic potential or zeta potential. (Z)
4 phm
Z=
D
10. Electrophoresis : The migration of electrically charged sol particles under the influence of
an applied electric field is known as Electrophoresis.
11. Coagulation : The precipitation of particles of dispersed phase is known as Coagulation or
Flocculation.
12. Hardy-Schulze Rule
Coagulation is brought about by the ions having opposite charge to that carried by the sol
particles.
13. Flocculation value : The minimum concentration of an electrolyte required to cause
coagulation or floculation of a sol is called its flocculation value.
14. Gold number : The number of milligrams of protective colloid which prevents the
coagulation of 10 mL of a given gold sol when 1 mL of a 10% solution of NaCl is added
to it.
15. Adsorption : The phenomenon of higher concentration of molecular species on the surface
of the solid or liquid than in the bulk is known as adsorption.
16. Adsorbate : The substance which is taken up on the surface of the adsorbent.
17. Adsorbent : The substance upon whose surface the phenomenon of adsorption takes place.
18. Desorption : It is reverse of adsorption. The process of removal of adsorbed substance
from the surface of the adsorbent is known as desorption.
19. Absorption : The substance is uniformly distributed throughout the body of the solid or
liquid.
20. Sorption : Both adsorption and absorption take place simultaneously.
21. Positive and negative adsorption : When the concentration of adsorbate is more at the
surface than in the bulk the adsorption is positive adsorption. But if the concentration of
adsorbate is less at the surface than in the bulk it is a case of negative adsorption.
22. Physical adsorption : The adsorbate is held on the surface of adsorbent by weak
vanderWaals' forces. It is reversible.
23. Chemical adsorption : The adsorbate is held on the surface of adsorbent by forces of
attraction of almost the same strength as chemical bond. It is irreversible.
24. Molar Heat of adsorption : It is the amount of heat evolved when 1 mole of gas or vapour
is adsorbed on the surface of the solid.
25. Extent of adsorption increases with fall in temperature and increase of pressure.
QUESTIONS
Very short answer type questions. (1 mark each)

1. Distinguish between crystalloid and colloid.
2. What is the binding force in physisorption ?
3. What is gold number ?
4. By what method a colloid can be separated from crystalloid.
5. What is the name of the process of removing an adsorbed substance from the surface on
which it is adsorbed.
6. Liquid-liquid colloidal systems are termed ———
(sols, hydrosols, emulsoids, suspensoids)
7. Why animal charcoal is used for purification of sugar ?
8. A colloidal solution has two phases namely ——— phase and ——— phase.
9. Why colloids can not be filtered by ordinary filter paper ?
10. A colloidal solution is called a ———
11. What is the size of a colloidal particle ?
12. Why does a colloidal solution coagulate on addition of an electrolyte ?

13. What is the cause of Tyndall effect ?
14. Why are the colloidal particles charged ?
15. Why colloidal solution is heterogeneous.
16. What is desorption ?
17. Define molar heat of adsorption.
18. Give an example of emulsion
Short answer type questions. (2 marks each)
1. Explain Gold number.
2. Give a method of preparing colloidal solution of arsenous sulphide. Give equation.
3. What is Tyndall effect ? What is it due to ?
4. What is adsorption ?
5. What is electrophoresis ?
6. What is colloidal solution ?
7. Why alum is used for clearing muddy water.
8. Name the factors (any four)that govern the adsorption of a gas on a solid.
9. What is detergent ? How it works ?
10. What is a colloidal solution ? How does it differ from a true solution ?
11. Give two examples of lyophilic sols and how are they formed ?
12. Why animal charcoal is used for purification of sugar ?
13. What is the difference between adsorption and absorption ?
14. A powerful beam of light is passed through two beakers, one containing a solution and the
other a colloidal solution. How each of the solution acts towards the beam of light ?
15. Why some colloidal particles migrate to electrodes in an electric field ?
16. Why are colligative properties almost negligible in case of colloidal solutions ?
17. Why is adsorption exotheromic ?
18. Explain why the gases like NH3, HCl, CO2 etc can be liquefied easily than the permanent
gases like H2, N2, O2 etc.
19. Among [Fe(CN)6]4–, PO 34- , SO 24- which is more effective in coagulating Fe(OH) 3 sol ?
20. Distinguish between adsorbent and adsorbate.
21. Distinguish between lyophilic and lyophobic colloids.
22. When a river meets the occan, it generally form delta. Give reasons.
23. Why cannot colloidal sol be filtered by ordinary filter paper ?
24. Name any two/four applications of adsorption (four)
25. When rivers meet the ocean, they generally form delta, give reasons.
26. Distinguish between homogeneous and heterogeneous catalysis.
27. What is meant by selectivity of a catalyst ?
Long answer type questions. (10 mark each)

1. Write notes on
(a) Tyndall effect
(b) Soap and Detergent
(c) Gold number
(d) Brownian movement
2. Explain different types of adsorption. Write any four applications of colloids.
3. Give one method of preparation of colloidal solution. Give an account of electrical and
optical properties of colloidal solution.
4. Give a brief account of soap and detergent.
5. Explain the terms adsorption and absorption with examples. Name the factors on which
the extent of adsorption of a gas on solid depends.
6. How are colloids classified ? Discuss any two properties of colloidal solution.
7. State and discuss Hardy-Schulze rule.
8. Explain the following
(a) Brownian movement (b) Gold number (c) Dialysis.
9. What is adsorption ? Distinguish between physical adsorption and chemisorption.
10. Explain various applications of colloidal solution
11. Discuss the factors that affect the phenomenon of adsorption.
12. What do you understand by the term "Electrophoresis" ? How would you demonstrate this
phenomenon.
13. What is a colloid ? How does colloid differ from crystalloid ? "Colloid is a state of matter,
not a class of matter" – discuss the statement.
14. Explain three of the following.
(a) Peptisation (b) Dialysis (c) Emulsions (d) Lyophobic sols.
15. Give a note of the following.
(a) Origin of charge on colloidal particles.
(b) Zeta potential.
16. Write a note on Cataphoresis. (5 marks)
17. Discuss important features of solid catalysts with reference to activity and selectivity.
18. Explain adsorption theory of heterogeneous catalysis.
19. Discuss effect of catalyst on activation energy with examples.
20. What is enzyme catalysis ? Discuss its characteristics with suitable examples.
21. What is a catalyst ? Discuss the characteristics of a catalyst with examples.
MULTIPLE CHOICE QUESTIONS WITH ANSWERS

1. A mixture of colloid and crystalloid can be separated by
(a) diffusion (b) cataphoresis (c) dialysis (d) filtration
2. Tyndall effect in colloidal solution is due to
(a) Scattering of light (b) Reflection of light (c) Absorption of light
(d) Presence of electrically charged particles
3. The capacity of an ion to coagulate a colloidal solution depends on
(a) its shape (b) the amount of its charge (c) the sign of the charge
(d) both of the amount and the sign of charge.
4. The Brownian motion is due to
(a) Temperature fluctuation within the liquid phase
(b) Attraction and repulsion between the charges on the colloidal particles.
(c) Impact of the molecules of the dispersion medium on the colloidal particles.
(d) Convection current.
5. Lyophilic sols are more stable than lyophobic sols because
(a) The colloidal particles have +ve charge
(b) The colloidal particles have –ve charge.
(c) The colloidal particles are solvated
(d) There are strong electrostatic repulsion between the negatively charged colloidal particles.
6. An Arsenous sulphide sol carries a –ve charge. The maximum precipitating power for this
sol is possessed by
(a) K2SO4 (b) CaCl2 (c) Na3PO4 (d) AlCl3
7. Which of the following substances gives a positively charged sol ?
(a) Gold (b) A metal sulphide (c) Ferric hydroxide (d) An acidic dye
8. On adding a few drops of dil HCl to freshly precipitated Fe(OH) 3, a red colour colloidal
solution is obtained. The phenomenon is known as
(a) Peptisation (b) Dialysis (c) Protective action (d) Dissolution
9. Which of the following will have high coagulating power for As 2S3 colloid ?
(a) PO 34- (b) SO 24- (c) Al3+ (d) Na+
10. The sky looks blue due to
(a) Dispersion of light (b) Reflection (c) Transmission (d) Scattering
11. Which of the following is not a colloid
(a) Chlorophyll (b) Smoke (c) Transmission (d) Milk
12. Fog is an example of colloidal system of
(a) liquid dispersed in gas (b) gas dispersed in gas
(c) solid dispressed in gas (d) solid dispersed in liquid
13. ——— is an example of emulsion.
(a) milk (b) jelly (c) boot polish (d) froth
14. Gold number gives

(a) The amount of gold present in the colloid
(b) The amount of gold required to break the colloid
(c) The amount of gold required to protect the colloid
(d) None of the above.
15. Which of the following can adsorb large volume of hydrogen gas.
(a) Finely divided platinum (b) Colloidal solution of palladium.
(c) Finely divided nickel (d) colloidal Ferric hydroxide
16. Which of the following can act as a protective colloid.
(a) gelatin (b) silica gel (c) oil in water emulsion (d) all correct.
17. The blue tinge of smoke is due to
(a) Scattering (b) Coagulation (c) Brownian motion (d) Electro osmosis.
18. Tyndall effect is not observed in
(a) true solution (b) suspension (c) emulsion (d) colloidal solution.
19. The migration of +vely charged colloidal particles under the influence of an electric field
towards the cathode is called
(a) Electro-osmosis (b) Electrophoresis (c) Dialysis (d) Coagulation
20. When the dispersion medium is water, the colloidal system is called
(a) Sol (b) Aerosol (c) Organosol (d) Aquasol
21. Which of the following is a hydrophobic sol ?
(a) Starch solution (b) Gum solution
(c) Protein solution. (d) Arsenic sulphide sol
22. A colloidal solution in which a solid is dispersed in a liquid is called
(a) Gel (b) Emulsion (c) Sol (d) Precipitate
23. Which of the following is a homogeneous system
(a) Muddy water (b) Bread (c) Concrete (d) A solution of sugar in water
24. Which of the following is not represented by sols ?
(a) Adsorption (b) Tyndall effect (c) flocculation (d) Paramagnetism
25. Maximum coagulation power is in
(a) Na+ (b) Ba2+ (c) Al3+ (d) Sn4+
ANSWERS TO MULTIPLE CHOICE QUESTIONS
1.c 2.a 3.d 4.c 5.c 6.d 7.c

8.a 9.c 10.d 11.a 12.a 13.a 14.d
15.a 16.a 17.a 18.a 19.b 20.d 21.d
22.c 23.d 24.d 25.d
qqq
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 187
UNIT - VI
CHAPTER - 6
GENERAL PRINCIPLES AND

PROCESSES OF ISOLATION OF
ELEMENTS
6.1 INTRODUCTION :
All the known elements have been divided into four classes and each category occupies
a definite place in the long form of the Periodic Table.
1. Inert gases
2. Metals
3. Non-metals
4. Metalloids.
1. Inert Gases: Six elements namely Helium, Neon, Argon, Krypton, Xenon and Radon are
known as inert gases. They occupy Zero group of the periodic table. Except Helium they
have eight electrons in their valence shells, so atoms of these elements neither gain nor
lose electrons. As they are unable to share electrons with other elements, they are not
given any electro negativity value. They are colourless and monoatomic.
2. Metals: Atoms of the metals have the tendency to donate electrons in chemical reactions.
They possess low electronegativity (1.7 down)
Properties:
(a) Soluble metallic oxides (Na2O, K2O etc,) yield OH- ions when treated with water.
(b) Both soluble and insoluble metallic oxides are known as basic oxides as they are
good proton acceptors and they form OH - (proton acceptor ion) in water.
(c) Metals are malleable (can be spread into thin sheets) and ductile, (can be drawn
into wires) have high electrical conductivity, high thermal conductivity and metallic
lusture when freshly cut.
3. Non-Metals: Atoms of non-metals have the tendency to accept electrons from metals in
chemical reactions. Covalent bonds are formed when they combine with one another.
Their electronegativity ranges from 2.4 to 4.0.
Properties:
+
(a) Non-metallic oxides yield H3O (hydronium ion) when treated with water. Hence
they are called acidic oxides.
(b) They are non-malleable, non-ductile and have no metallic lustre.
(c) Non-metals which are gases at ordinary conditions exist as diatomic molecules.
4. Metalloids: Metalloids are borderline elements. They exhibit both metallic and non-
metallic properties to some extent. They usually act as electron donors with non-metals
and electron acceptors with metals. Example : Boron, Silicon, Germanium, Arsenic,
Antimony and Tellurium.
Properties:
(a) Metalloids form acidic oxides
(b) They are solids at room temperature.
(c) They are poor conductors of heat and electricity and brittle in character.
(d) The compounds of metalloids are mostly covalent in nature.
Electrochemical Series:
Elements arranged in the decreasing order of their chemical reactivity in a table is termed
as Electrochemical series.
Example: Li, K, Ba, Sr, Ca, Na, Mg, Al, Mn, Zn, Cr, Cd, Fe, Co, Ni, Sn, Pb, H, Sb ,
Bi, As, Cu, Hg, Ag, Pt, Au… (arranged in the decreasing order)
Significance:
Decreasing order of chemical reactivity signifies the following:
a) Li is the most reactive one while Au is the least reactive.
b) Metals from Li to Na, produce H2 from cold water, steam and acids.
c) Metals from Mg to Fe produce H2 from steam and acids.
d) Metals from Co to Pb produce H2 from acids.
e) Ag, Pt and Au do not produce H2 from water and acids but form oxides by indirect
method.
f) Metal oxides from Cu to Au can be easily reduced by hydrogen.
6.2 OCCURRENCE OF METALS IN NATURE :

Metals are available in nature either in
1) Free state or native state.
2) Mineral state, or
3) Form of an ore.
1. Free State – A metal is said to occur ‘free’ or ‘native’ when it is found in nature in the
metallic state.
Example: Cu,Ag, Au
Significance: Such metals are less electropositive than Hydrogen.
2. Mineral: Metals which exist in the form of compounds with impurities like sand are
called minerals.
Example Zincite (ZnO), Horn Silver(AgCl), Cuprite(Cu2O)etc).
3. Ores: An ore is a naturally occurring substance from which the metal may be extracted
economically and profitably.
Example: Galena(PbS), Copper glance(Cu 2S), Zinc oxide(ZnO), Calcium

phosphate [Ca3(PO4)2]etc.
All ores are minerals, but all minerals are not ores.
Occurrence of Metals in nature
In the free state In the state of combination with

Example: Gold, Plati- other elements
num Example: Sodium, Calcium,
Silver, Mercury Potassium,
Aluminium, Lead etc.
Table - 6.1
Metals and their important Minerals
Metal Mineral Chemical Formulae
Sodium Rock Salt NaCl

Chile Saltpetre NaNO3
Borax Na2B4O7
Potassium Carnallite KCl, MgCl2.6H2O
Nitre KNO3
Kainite K2SO4, MgSO4, MgCl2.6H2O
Magnesium Magnesite MgCO3
Dolomite MgCO3.CaCO3
Epsom salt MgSO4.7H2O

Kieserite MgSO4.H2O
Carnallite MgCl2KCl, 6H2O
Calcium Limestone CaCO3
Dolomite MgCO3, CaCO3
Gypsum CaSO4, 2H2O
Copper Copper pyrites CuFeS2
Copper glance Cu2S
Malachite Cu(OH)2, CuCO3
Azurite Cu(OH)2, 2CuCO3
Cuprite Cu2O
Silver Horn Silver AgCl
Silver glance Ag2S
Zinc Zincite ZnO
Zinc Blende ZnS
Calamine ZnCO3
Mercury Cinnabar HgS
Aluminium Bauxite Al2O3.2H2O
Cryolite Na3AlF6
Alunite K2SO4, Al2(SO4)3, 4Al(OH)3
Spinel MgO, Al2O3
Tin Tin Stone SnO2
Lead Galena PbS
Manganese Pyrolusite MnO2
Chromium Chromite FeO, Cr2O3
Iron Magnetite Fe3O4
Haematite Fe2O3
Limonite Fe2O3, 3H2O
Iron pyrites FeS2
6.3 EXTRACTION OF METALS OR METALLURGY :
Metallurgy:
It is the process or processes by which metals are extracted from their respective ores.
Gangue or Matrix:
The rocky or earthy materials almost always found to be associated with the ores as
impurities and looked upon as waste materials are called gangue or Matrix. (Latin word Matte =
Mother i.e. earthy or stony substance in which minerals are found embedded)
6.3.1. Concentration of the ore:
In any metallurgical operation, concentration means to remove impurities (gangue) form
the ore. It is effected by many processes like:
(i) Breaking and Crushing: Big masses of rocks containing the ore must be reduced to
small lumps so that they may be completely exposed to the action of the subsequent
operations. It is usually done by machines like crushers etc.
(ii) Grinding and Pulverizing: Some times the concentration and further treatment of some
ores demand their reduction into very fine state. This is also effected by machines like
grinding and pulverizing mills.
(iii) Washing: This process includes all methods of concentration in which water in motion
is used. Washing machines are generally used for such purpose.
(iv) Floatation: Here concentration of the powdered ore is effected by taking advantage of
difference in the behaviour towards oil or water. Sulphides, for example, do not get wet,
as do silica and most oxides when treated with water. They will, therefore, float on the
surface when silica etc. will sink.
(v) Froth Floatation Process : This method is used for the concentration of sulphide ores,
as sulphide ores get preferentially wetted compared to the gangue materials.
The powdered sulphide ore is added to a tank containing water and eucalyptus oil or
turpentine oil. Then the suspension is violently agitated with a rotating paddle. This paddle
draws air in it and froth is formed. The sulphide ore particles stick to the froth and rise to
the surface with froth. The gangue particles left behind in the tank. The froth is dried for
recovery of the ore particles.
Pine oils, fatty acids, xanthates etc. known as “collectors” enhance non-wettability of the
mineral particles and “froth stabilises” e.g. cresols, aniline etc. stabilise the froth.
“Depressants” are used to separate two sulphide ores. For example, in case of an ore
containing ZnS and PbS, NaCN is used as a depressant. It selectively prevents ZnS from
coming to the froth but allows PbS to come with the froth.
(vi) Magnetic Separation: This method is applicable for concentrating ores, which differ
from their impurities in magnetic character.
Example: The main impurity of Tinstone (SnO2) is ferrous tungstate (FeWO4). It is also
known as Wolfram. To remove the impurity from tinstone, it is to be powdered first
and then the powdered ore is to be dropped over a belt revolving round the two rollers,
out of which one roller is a magnet.
ORE
MAGNETIC
PULLEY
HOPPER
BELT
WOLFRAM SnO2
Fig. 6.1 Magnetic separation
The magnetic part of the ore is attracted by the magnetic roller and separates out, whereas
the non-magnetic part of the ore is separated out a little away from the magnetic impurities.
(vii) Leaching : “The process of treating the powdered ore with a suitable reagent which can
selectively dissolve the ore but not the impurities” is known as leaching.
(a) Leaching of alumina from bauxite : The bauxite ore contains aluminium in
the form of Al2O3 along with SiO2, iron oxides and titanium oxide as impurities. The
powdered ore is heated with a concentrated solution of NaOH at 473 – 523K and 35–36
bar pressure. Alumina is leached out as sodium aluminate and SiO 2 as sodium silicate
leaving behind the impurities.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) ® 2Na [Al(OH)4] (aq)
SiO2(s) + 2NaOH(aq) ® Na2SiO3(aq) + H2O(l)
The resulting solution is filtered to remove the undissolved impurities. Then it is cooled
and its pH is adjusted either by dilution of by neutralization with CO 2 when aluminium
hydroxide gets precipitated. In this stage, the solution is seeded with freshly prepared
samples of hydrated alumina to get it precipitated leaving behind sodium silicate in the
solution.
2Na [Al(OH)4] (aq) + CO2(g) ® Al2O3 . x H2O(s) + 2NaHCO3(aq)
The hydrated alumina is filtered, dried and heated to give back pure Al 2O3.
Al2O3 . x H2O(s) ¾1470K

¾ ¾¾® Al2O3(s) + x H2O (g)
(b) Leaching of silver and gold: Some metals like gold and silver are extracted
from their concentrated ores by leaching. They are dissolved in suitable reagents like
acids or bases leaving behind insoluble impurities. The metal is recovered from the solution
by precipitation or crystallization. For example, silver ore is leached with dilute solution
of sodium cyanide. Silver dissolves forming a complex, sodium dicyanoargentate(I). The
solution is further treated with scrap zinc to get the precipitate of silver.
Ag2S + 4 NaCN 2 Na [Ag (CN)2 ] + Na2S
Sodium dicyanoargentate(I)
2 Na [Ag (CN)2 ] + Zn Na2 [Zn (CN)4 ] + 2Ag¯
Sodium tetracyanozincate (II) ppt.
Similarly, native gold is leached with potassium cyanide solution and it is recovered from
the solution by addition of scrap zinc.
4 Au + 8KCN + O2+ 2H2O ® 4 K[Au (CN)2] + 4 KOH
2 K [Ag (CN)2 ] + Zn ® K2 [Zn (CN)4] + 2 Au¯
ppt
Flux:
It is the substance added to the ores, before heating, with the object that it will react
chemically with the impurities (gangue) present in the ores and form a fusible slag.
The nature of flux depends upon the impurity to be removed. Accordingly three kinds of
fluxes are generally used.
(a) Acidic Flux:
Sand is an example under this category. It is used to remove basic impurities such as
metallic oxides.
Example: FeO + SiO2 FeSiO3
(Impurity) (Fusible slag)
(b) Basic Flux:
Calcium oxide(CaO) is an example under this category. It is used to remove acidic impu-
rities such as sand(SiO2)
SiO2 + CaO CaSiO3
(Impurity) (Flux) (Fusible slag)
P2O5 + 3CaO Ca3(PO4)2
(Impurity) (Flux) (Fusible slag)
(c) Neutral Flux: Fluorspar(CaF2)
Slag :
The fusible compounds formed by the union of flux and the impurities especially when it
is the waste product of an operation is termed as slag.
Slag = Flux + Impurities(gangue)
6.3.2. Extraction of crude metal from the concentrated ore :

Calcination and Roasting:
These two terms are related to the process of extraction of metals from their concentrated
ores. Before the concentrated ores are subjected to the final metallurgical operations to get the
metals in the free state preliminary chemical treatment is necessary. The objective of this treat-
ment is to (i) get rid of impurities, which would cause difficulties in the later stages and (ii) convert
the ore into its oxide
Calcination:
It is a process of heating the concentrated ore in absence of air but at a temperature
insufficient to melt it with a view to driving off the volatile matters.
Example:
1. When calamine (ZnCO3), an ore of Zn is calcined, carbon dioxide is expelled and zinc
oxide (ZnO) is formed.
calcination
ZnCO3 ZnO + CO2
2. Bauxite (Al2O3, 2H2O), an ore of Aluminium, when subjected to calcination, anhydrous
aluminium oxide (Al2O3) is formed
calcination
Al2O3, 2H2O Al2O3(s) + 2H2O
3. Fe2O3,3H2O Fe2O3 + 3H2O
4. PbCO3 PbO + CO2
5. CaCO3, MgCO3 CaO + MgO + 2CO2
6. CuCO3 CuO + CO2
7. 4FeO + O2 2Fe2O3
8. 2Al(OH)3 Al2O3 + 3H2O
Roasting :
It is the process of heating the concentrated ore in excess of air but at a temperature
insufficient to melt it(i.e. below the point of fusion) with a view to oxidising it.
Example:
1. Zinc sulphide when roasted, gives zinc oxide
2ZnS + 3O2 2ZnO + 2SO2-
2. Cuprous sulphide when roasted gives cuprous oxide
2Cu2S+ 3O2 2Cu2O + 2SO2-
3. 2PbS + 3O2 2PbO + 2SO2-
Calcination or roasting process is generally carried out in a specially designed furnace
called reverberatory furnace (Fig.6.2)
FUEL GASES
FEED HOLE
Fig. 6.2 Reverberatory Furnace

Distinction between Calcination and Roasting:
Calcination Roasting
1 It is the process of heating 1 It is process of heating an ore
an ore in absence of air. in presence of air.
2 It is usually employed for carbonate 2 It is usually employed for sulphide ores.
and hydrated oxide ores.
3 It renders the ore dehydrated and spongy. 3 It renders the ore into its oxide form.
Also decomposes carbonate ores. 2ZnS + 3O2 ® 2ZnO + 2SO2
Heat
CaCO3 CaO + CO2
Smelting :
It is an operation in metallurgy in which a metal is extracted in the state of fusion.
During roasting, the ore is converted to the oxide of the metal. But it is still mixed with
some gangue which is not removed in the processing. To remove the last of the gangue, the
roasted ore is now smelted. Therefore, smelting is regarded as the process of reduction of the ores
in a fused state. Coke or charcoal is therefore used which acts as the reducing agent. Further an
additional substance called flux is also used to get the fusible product called slag after heating to
a high temperature above its melting point.
Impurities + Flux = Fusible slag
(in the ore)
The selection of flux depends upon the nature of impurities. If the impurities are basic
(like CaO, FeO, MnO3 etc.) then the flux employed is acidic (i.e. Silica)
CaO + SiO2 = CaSiO3
Basic impurity Flux Slag
(acidic)
On the other hand if the impurities are acidic (like SiO 2, P2O5 etc) then the flux used is
basic (i.e. CaO)
P2O5 + 3CaO = Ca3(PO4)2
Acidic impurity Flux Slag
(acidic)
The smelting of ores is carried out in different types of furnaces depending upon the raw
materials used.
Reduction of the metal oxide to the free metal :

The roasted or calcined ore is then reduced to the metal by using a suitable reducing
agent. Some metal oxides get reduced easily while others are very difficult to be reduced. For
both the cases heating is required. To understand the pyrometallurgy (variation in temperature
requirement for thermal reductions) and to predict which element will suit as the reducing agent
for a given metal oxide (MxOy), Gibb’s energy interpretations are made.
6.4 THERMODYNAMIC PRINCIPLES OF METALLURGY :

The theory of metallurgical transformations can be understood from the thermodynamic
concepts of Gibb’s free energy change.
According to thermodynamics : DG = DH – TDS (i)
Where, DG = Gibb’s free energy change.
DH = Change in enthalpy
and ‘T’ is the specified temperature in Kelvin scale.
For a reaction of equillibrium : DG° = – RT lnK (ii)
where ‘K’ is the equilibrium constant for the reversible reaction at specified temperature
‘T’. A study of above two equations leads to following conclusions.
(1) Feasibility of a reaction :
A reaction is feasible only when ‘DG’ is –ve. As is evident from equation (i), if ‘DS’ is
+ve for a process (for all spontaneous processes DS is +ve), on increasing the temperature ‘T’,
the value of TDS will increase and when TDS becomes greater than DH, DG will be negative and
the reaction will proceed in the forward direction.
(2) Coupling of reactions :
A reaction with ‘DG’ value ‘+ve’ can be made to occur by coupling it with another reaction
having large negative DG, so that net DG of the two reaction will be –ve.
Explanation : Let for a reaction A®B DG1 = +ve.
and C®D DG2 = –ve
After coupling both the reactions : A + C ® B + D and
DG = DG1 + DG2 = – ve, when DG2 > DG1
So the coupling of two reactions enables the system to produce the products. Such coupling
reactions can be easily understood in terms of Ellingham diagram which plots standard free
energy of formation of oxides (i.e. DfG°) per mole of O2, as a function of absolute temperature.
6.4.1 Ellingham Diagram :
Ellingham diagram (Fig. 6.3) is a plot of DfG° vs T for formation of oxides of elements.
Similar diagrams can also be constructed for sulphides and halides of elements. This diagram
helps in predicting the feasibility of thermal reduction of an ore (DG = –ve). We can study the
Ellingham Diagram in two steps.
Fig. 6.3 : Gibbs energy (DG°) vs T plots (schematic) for formation

of some oxides (Ellingham diagram)
Step-1 : Formation of metal oxide :
Let us consider a reaction of the type
2xM(s) + O2(g) ® 2MxO(g)
for formation of a metal oxide.
Here dioxygen in gaseous state is used in giving MxO, a solid as the product.
For gas ® solid phase change DS is –ve. With increase in value of T, TDS becomes more
and more –ve, hence leading to DG value less –ve, i.e. with rise in temperature, DG value increases.
So Df G° vs T graph gives a +ve slope for most of the reactions involving the formation
metal oxides, MxO(s) (Fig. 6.3)
Step-2 : Phase Change :
When there is a phase change (i) solid to liquid or (ii) liquid to gas, there is an increase in
the slope on the +ve side as DS becomes +ve.
For example : In the Zn – ZnO plot, at the boiling point of Zn (1180K), there is an abrupt
increase in the +ve slope of the curve. Similarly, in Mg – MgO curve the +ve slope increases
abruptly at boiling point of Mg i.e. at 1380K. The small circles on the left indicate the M.Pts and
on the right indicate the B.Pts.
Limitations :
(1) This diagram only suggests whether the reduction of a metal oxide with a particular
reducing agent is possible or not. But it does not tell anything about the rate of the reaction.
(2) The interpretation of DG° is based upon equillibrium constant ‘K’ (i.e. DG° = RT lnK),
thus presuming that there is an equillibrium between reactant and product.
MxO + A (reducing agent) xM + AO (oxidising agent). But this is not always true
because reactants and/or products may be in solid state.
6.4.2 Theory of Pyrometallurgy :
The thermodynamic principles as well as the Ellingham diagram together can explain the
feasibility of reduction of a metal oxide with reducing agents like carbon or any other metal.
(a) Reduction by carbon :
The process of extraction of a metal by reduction of its oxide with carbon is called smelting.
This process takes place in following steps :
1
(i) Reduction : MxO(s) ® xM (s or l) + O (g) ............. (i)
2 2
1
(ii) Oxidation : C(s) + O (g) ® CO(g) ............................ (ii)
2 2
Equation (i) is actually reverse of equation (iii) representing the oxidation of the metal.
1
x M (s or l) + O (g) ® MxO(s); DG° (M, M O) ............. (iii)
2 2 x
If complete oxidation of C to CO2 occurs,
1 1 1
C(s) + O2(g) ® CO2(g); DG° (C, CO ) .................... (iv)
2 2 2 2
Similarly, if CO is used as reducing agent.
1
CO(g) + O (g) ® CO2(g); DG° (CO, CO ) ............................... (v)
2 2 2
On subtracting (iii) from each of the three equations (ii), (iv) and (v), we have,
MxO(s) + C(s) ® x M (s or l) + CO (g) .............................. (vi)
1 1
MxO(s) + C(s) ® x M (s or l) + CO2 (g) .................... (vii)
2 2
MxO(s) + CO(g) ® x M (s or l) + CO2(g) ........................... (viii)
These three equations (vi), (vii) and (viii) describe the actual reduction of the metal oxide,
MxO to the free metal M.
The DfG° values for these reactions, in general, can be obtained by subtraction of the
corresponding DfG° value from the Ellingham diagram (Fig 6.3). The –ve value of DfG° predicts
feasibility of the reduction process.
So, it can be understood that, at any given temperature, any metal will reduce the oxide of
other metals which lie above it in the Ellingham diagram, because the free energy change (DfG°)
for the combined redox reaction will be negative.
Magnesium can reduce Al2O3, ZnO, FeO and Cu2O more readily than Aluminium can
reduce ZnO, FeO, Cu2O. This is because the DfG° values in the former cases are more –ve. Thus
the relative tendency of these metals to act as reducing agents is : Mg > Al > Zn >Fe > Cu. For
Ag2O and HgO, as it is seen from the diagram, DfG° becomes +ve at higher temperature. This
suggests that these oxides are unstable at high temperature and hence decompose to liberate the
corresponding metal.
2 Ag O (s) ¾Heat
2 ¾¾® 4Ag(s) + O (g). 2
630K
2 HgO (s) ¾¾¾
¾® 2Hg(l) + O2(g).
6.4.3 Effect of temperature on the Free Energy Change (DfG°) of a Reduction process :
As we know that DG = DH – T D S,. If a reaction does not occur at low temperature, it can
occur at high temperature, if DfG° for the redox reaction becomes –ve at that temperature. In the
Ellingham diagram (Fig. 6.3), this temperature is indicated by the intersection of the two curves :
(a) Curve for formation of MxO
and (b) The curve for oxidation of the reducing agent.
At the point of intersection of the two curves, DG° = O. Below this temperature, the DG°
is –ve and the oxide is stable. But above this temperature DG° is +ve and the oxide being unstable
breaks to give metal and oxygen. Al can reduce MgO to Mg above 1623K.
6.5 EXTRACTION OF IRON FROM ITS OXIDE ORES :

6.5.1 Occurrence
The different ores of iron are oxide ores, carbonate ores and sulphide ores.
1. Oxide ores
(a) Haematite, Fe 2O3 (Red in colour)
(b) Magnetite, Fe3O4 (Richest ore of iron, black in colour)
(c) Limonite, Fe2O3.3H2O, (hydrated ferric oxide) (yellow, brown or red in
colour)
2. Carbonate ore
Siderite or spathic iron, FeCO 3
3. Sulphide Ores
(a) Iron pyrites, FeS2
(b) Chalcopyrites, CuFeS2
Iron pyrite is usually used for the preparation of SO 2, chalcopyrite is used for the
extraction of copper.
6.5.2 Extraction
The actual process employed in the extraction of iron from its ores depends on the
type of iron desired. Different types of iron arise out of varying carbon content. The three
important types are
1. Pig or Cast iron (About 2 to 4% carbon)
2. Wrought iron (0.1 to 0.25% carbon)
3. Steel (0.15 to 1.5% carbon)
The metal is extracted (as cast or pig iron) usually from haematite ore. Haematite ore
contains siliceous impurities with a little P,S, Al 2O3 etc. The process of extraction involves
the following three steps.
1. Concentration of the ore.
2. Conversion of the ore to pig iron.
3. Refining (Conversion of pig iron to steel).
1. Concentration of the ore : In order to increase the efficiency of the extraction process,
the ore obtained directly from mines is subjected to concentration.Concentration
increases the percentage of iron oxide in the raw ore.
The ore is crushed into small pieces and washed with stream of water to remove
earthy and siliceous impurities. The ore may be subjected to froth floatation process
to carry the real haematite ore into the froth. Since the iron ores are magnetic in
nature,the powdered ore can be allowed further to travel on a running belt in a magnetic
field so the the magnetic haematite is deposited close to the magnetic field leaving
the gangue (impurities) farther away.
2. Conversion of ore to pig iron (Manufacture of pig iron) : The process involves
two steps.
1. Calcination and Roasting
2. Smelting
Calcination and Roasting : The concentrated ore is heated in excess or air
with a little coke (C) in shallow kilns. The ore undergoes following changes.
(a) Moisture is removed : 2Fe 2O3.3H2O 2Fe2O3 + 3H2O-
If ferrous carbonate is in the ore : FeCO 3 FeO + CO2-
(b) Impurities such as P,S, As, Sb etc. are removed as their volatile oxides.
S8 + 8O2 8SO2 - P4 + 5O2 2P2O5 - 4As + 5O2 2As2O5 -
(c) Ferrous oxide is oxidised to ferric oxide.
4FeO + O2 2Fe2O3
(d) During the process the entire mass becomes porous so that the ore can be
easily reduced during smelting.
Smelting : The extraction of a metal from its ore by a process involving melting
is known as smelting. It is also referred to as chemical reduction.
For extracting iron, smelting is Charge

carried out in a blast furnace (Fig. 6.4)
A blast furnace is a huge cylinder made
of steel. Its height may vary from 120
to even 200ft and width is about 30 ft.
in diameter. The inside of the furnace Water Fe2O3 ore fire-brick
is lined with very high melting refractory gases
coke lining
bricks. the calcined and roasted ore along
with limestone (CaCO3) and coke (C) (ore
480K limestone
8 parts, lime stone 1 part and coke 4 parts)
reducing zone
are lifted to the top of the furnace and CO
released at the mouth of the furnace
provided with a cup and cone
arrangement. Near the bottom of the drops of irorn
furnace blast of hot air is forced into the
drops of slag
furnace through water cooled nozzles
called tuyers. 1785K
hot air
The following reactions take place hot air
slag outlet
in different zones of the blast furnace molten slag
molten iron
within the temperature range 480 - 1575K.
Near the bottom, hot air in contact with Fig. 6.4 The Blast Furnace
falling coke reacts to give
C + O2 CO2 + heat
The reaction is exothermic. The upward carbon dioxide comes in contact with layers of
coke and gets reduced to carbon monoxide.
CO2 + C 2CO - heat
Now carbon monoxide acts as a reducing agent and reduces iron oxides to iron.
Fe2O3 + 3CO 2Fe + 3CO2- (675 - 975K)
(Molten)
3Fe2O3 + CO 2Fe3O4 + CO2 -
Fe3O4 + CO 3FeO + CO2 -
Fe2O3 + CO 2FeO + CO2 -
FeO + CO Fe + CO2 -
(Molten)
2FeO + C 2Fe + CO2 -
(Molten)
Molten iron, thus formed is collected at the bottom of the furnace.
Lime stone acts as flux and removes siliceous impurities in the form of slag.
D
CaCO3 ¾¾® CaO + CO2 CaO + SiO2 CaSiO3 (slag)
Calcium silicate
(1075 - 1275K)
CaO + Al2O3 Ca (AlO2)2 (slag)
Calcium aluminate
The molten slag is lighter than the molten iron and floats on the top which can be
removed through the outlet-holes provided. Carbon monoxide, coming out of the furnace is
used to heat the air-blast initially given to the furnace.
The silicates, phosphates, manganates and aluminates present as impurities in the ore
are converted to the corresponding oxides of Si, P and Mn. These oxides are finally reduced
to their corresponding elements. These elements are partly absorbed by molten iron and
partly by molten slag.
SiO2 + 2C Si+ 2CO 2P2O5 + 10C 4P + 10CO
MnO2 + 2CO Mn + 2CO
Some of the phosphate impurities react with sand and carbon.
2Ca3(PO4)2 + 3SiO2 + 10C 3(2CaO.SiO2) + 4P + 10CO
Molten metal may combine with phosphorus and carbon as follows.
3Fe + P Fe3P 3Fe + C Fe3C
(Cementite)
Molten iron is tapped off from the furnace and solidified into blocks known as pigs.
Molten iron on sudden cooling is converted to white cast iron and on slow cooling to grey
cast iron. Cast iron is either converted to wrought iron or steel.
It is possible to manufacture 1000-3000 tons of pig iron per day using blast furnace
of suitable dimension. A blast furnace may work non-stop for about five years. Thereafter
operation is stopped and the furnace is overhauled.
3. Refining : Conversion of Pig iron to Steel (Manufacture of Steel) :
Steel is more useful than iron. Various steels are prepared by regulating the carbon
content. Steel is softer and more malleable than pig or cast iron. Conversion of pig iron to
steel is a purification process.
There are three methods for the manufacture of steel.
1. Bessemer process
2. Open Hearth process
3. Electric Furnace process.
(a) Bessemer process
Molten pig or cast iron is poured into the Bessemer converter ( Fig 6.5) The converter
is a pear-shaped furnace about 20ft. high and 10ft. in diameter and lined with refractory
silica (SiO2) bricks. If the pig iron contains appreciable amount of phosphorus, the converter
is lined with lime (CaO) and Magnesia (MgO) instead of silica. Some lime is added to the
molten pig iron. Air or air mixed up with oxygen is forced through the bottom of the converter
into the molten pig iron. The temperature inside the converter is about 1880K.
Blue flames of CO
Acidic or
basic lining
Molten cast iron
Hot air Tuyers
Fig. 6.5 Bessemer’s converter used for the manufacture of steel from cast iron.
The following reactions take place.

Si + O2 SiO2 2Mn + O2 2MnO 2Fe + O2 2FeO
MnO + SiO2 MnSiO3 (slag) FeO + SiO2 FeSiO3 (slag)
manganese silicate ferrous silicate
If phosphorus is present as an impurity it is oxidised to phosphorus pentoxide and
then to calcium phosphate.
4P + 5O2 2P2O5 P2O5 + 3CaO Ca3(PO4)2 (slag)
The slag calcium phosphate, called Thomas slag is used as an important fertiliser.
Carbon mostly present in the form of Fe 3C further reacts with FeO and O 2.
FeO + Fe3C 4Fe + CO 2Fe3C+ O2 6Fe + 2CO
Free carbon also burns with oxygen to carbon monoxide
2C + O2 2CO
The evolved CO reacts with air (oxygen) to form CO 2 and a blue flame is seen at the
mouth of the converter. As soon as the blue flame dies down, it is evident that all the carbon
is oxidised.
At this stage no further air is supplied into the converter. Then requisite amount of
carbon (charcoal) along with manganese (in the form of spiegeleisen: 15-- 20% Mn and rest
iron) is added to molten iron. The steel thus prepared in the Bessemer converter has the
approximate composition: Fe 98.4%, C 0.4%, Mn 0.9%, P 0.1%, Si 0.1%).
This steel in its molten state is called O2

Bessemer steel which is poured directly into moulds Lance
and high quality pipes, tubes, etc. are made out of it. Slag
Hot
The L.D. process spot
In the Bessemer process nitrogen present in
the air blast badly affects the mechanical properties
of steel. Therefore in the L.D. (Lintz and Donawitz)
process (Fig. 6.6) blast of pure oxygen in place of air
is blown into the molten pig iron from the top. Lining of
Magnesite
In this process impurities like sulphur and
phosphorus are quickly oxidised and the oxidation
Fig. 6.6. Converter for L.D. process
of carbon is regulated. This process manufactures
better quality of steel than the Bessemer process.
(b) Open Hearth process or Siemens - Martin process
This is the modern process in which a steel of exact composition is obtained. The
furnace used consists of an open hearth (Fig.6.7) lined with silica or calcined dolomite
(CaO.MgO) depending upon the nature of impurities present in the pig or cast iron. If the
impurities are of Mn, Si, etc., silica lining is used. Calcined dolomite lining is used if P is
present in appreciable amount.
STEEL SLAG
Fig. 6.7. Open Hearth Furnace

In this process, a mixture of pig or cast iron, scrap iron, iron ore (Haematite) and
lime is melted in an open hearth furnace. The furnace attains a temperature of about 1870K
by burning fuel gas and air.
Impurities like Si and Mn are oxidised to their respective oxides by haematite (Fe 2O3).
Both Mn and Si are removed as manganous silicate (slag).
3Si + 2Fe2O3 4Fe + 3SiO2 3Mn + Fe2O3 2Fe + 3MnO
MnO + SiO2 MnSiO3 (slag) CaO + SiO2 CaSiO3 (slag)

Phosphorus present reacts with lime and is removed as calcium phosphate slag.
12P + 10Fe2O3 6P2O5 + 20Fe 2P2O5 + 6CaO 2Ca3(PO4)2 (slag)

Carbon and sulphur are oxidised to volatile gases.
3S + 2Fe2O3 4Fe + 3SO2
3C + Fe2O3 2Fe + 3CO
Iron containing Fe 3C reacts with Fe2O3 to form steel.
3Fe3C + Fe2O3 11Fe + CO
Samples of steel prepared are drawn from time to time and tested for carbon content.
Finally spiegeleisen is added to the molten mass to get the desired steel. The slag formed
over the surface protects the steel from oxidation. The process is much slower than Bessemer’s
process, but a better quality of steel is formed. This process has added advantage for the
following reasons.
(i) Scrap is re-used.
(ii) Economy of fuel is achieved by using regenarative system.
(iii) The temperature can be controlled as the heating is done externally.
(c) Electric Furnace process :
The electric furnance method differs from the open hearth process primarily in the
method of heating. This process of making steel is costly and is carried out in those countries
where electricity is cheap. The furnance (Fig.6.8) is made of steel with inside refractory
bricks and has a good lining of dolomite or magnesite. The Bessemer steel alongwith some
lime and ferric oxide are charged into the furnace.
An arc is then struck between the graphite electrodes and the surface of the charge.
The enormous heat produced in the furnace melts the charge. The impurities such as P, S, Si
and Mn react with the basic lining to form slag. Carbon is oxidised to CO.
ADJUSTABLE
GRAPHITE ELECTRODE
BASIC LINING
Fig. 6.8. Electric steel furnace
This process is used to manufacture high melting alloy-steels, since high temperature
is maintained in the furnace.
Manufacture of Wrought iron
Wrought iron is manufactured from pig or cast iron by puddling process. The cast
iron is melted on the hearth of a special type of reverberatory furnance (Fig.6.9) by hot gases
and stirred with long iron rods. The furnance is lined with haematite (Fe 2O3) which oxidises
the impurities and subsequently they are removed as slag.
Fig. 6.9. Preparation of wrought iron in a reverberatory furnace.

3C + Fe2O3 2Fe + 3CO 3Si + 2Fe2O3 Fe + SiO2
3Mn + Fe2O3 3MnO + 2Fe MnO + SiO2 MnSiO3

(slag)
6P + 5Fe2O3 10Fe + 3P2O5 P2O5 + Fe2O3 2FePO4 (slag)
When impurities are removed, the melting point of iron metal rises and it becomes a
semi-solid mass. The semi-solid mass is taken out in the form of balls and beaten under
steam hammers to squeeze out as much of slag as possible.
Wrought iron, thus manufactured is almost pure iron.
6.5.3 Types of iron :

There are three commercial varieties of iron depending upon the percentage of carbon
content.
Pig or Cast iron: It is the most impure form of iron containing highest percentage of
carbon (about 4%). 2% of other combined impurities such as S, P, Si and Mn are also present.
Molten pig iron from the blast furnace when cast into moulds by cooling and remelting, cast
iron is prepared.
Properties :
1. Cast iron is hard and brittle.
2. It cannot be forged or welded by hammering.
3. When molten cast iron solidifies, it expands slightly.
4. Cast iron is succeptible to rusting.
Uses :
1. Cast iron finds extensive applications in casting articles of various shape.
2. Cast iron is used to manufacture toys, stoves, cooking-range, stools, radiators,
pipes and agricultural implements.
3. It is also used to make wrought iron and steel.
Wrought iron:
It is the pure form of iron and contains 0.1 to 0.25% of carbon.
Properties:
1. Wrought iron is soft, ductile and malleable.
2. It is tough and resistant towards rusting and corrosion due to presence of a
very small percentage of slag in it.
3. Since it softens at about 1280 K it can be forged and welded.
4. It has fibrous structure and thus can withstand high stresses.
Uses:
1. Wrought iron is used to make magnets in dynamos and electric cranes.
2. Since it can withstand sudden stress, it is used to manufacture chains, nails,
bolts, hooks, wires, bars and railways carriage couplings.
Steel:
Steel is the most commercial variety of iron containing 0.15 to 1.5% carbon. In steel
this percentage of carbon remains in between that of cast iron and wrought iron.
Properties :
1. Steel is extremely hard due to presence of 10% manganese.
2. It melts at about 1650K and can be welded.
3. Heat treatment on steel : The hardness of steel depends on its carbon content
and heat treatment.
(a) Quenching : Hard steel can be further hardened by heating it to bright redness
(1125K) and suddenly cooling it by plunging into cold water or oil. The steel
becomes hard and brittle.
(b) Tempering : If the quenched steel is reheated to a temperature much below
redness, 505K to 575K and is then cooled slowly, it retains its hardness but
the brittleness considerably decreases. This process is known as tempering.
(c) Annealing : If steel is heated to red heat and then cooled slowly the process
is called annealing. By annealing steel becomes soft.
(d) Nitriding: Nitriding is the process when steel is heated in an atmosphere of
ammonia. Steel becomes hard with a coating of iron nitride on its surface.
Uses of steel :
1. Steel is used to make domestic articles, utensils, cutlery, swords, armour
plates etc.
2. Extensively used for structural purposes, machineries and rail roads.
3. In making bar magnets, magnetic needles, watch springs, razors etc.
Types of steel:
(a) Mild steel : It has low percentage of carbon between 0.1 to 0.4 It shows the
properties of wrought iron along with elasticity and hardness.
(b) Hard steel : Hard steel has percentage of carbon content varying in between
0.5 to 1.5. It is hard and brittle.
(c) Special steels or alloy steels : Steel mixed with small amounts of chromium,
manganese, cobalt, nickel, molybdenum and tungsten acquires special
properties. Such products are called special steels or alloy steel.
Table - 6.2 : Comparison in properties of cast iron, steel and wrought iron
Properties Pig or Cast iron Steel Wrought iron
1. Carbon content ~4% 0.15 to 1.5% 0.1 to 0.25%
2. Structure Crystalline Crystalline Fibrous
3. Hardness Hard Hard and soft Soft
4. Malleability Brittle Malleable and brittle Malleable
5. Melting point ~ 1500K ~ 1620K ~1770K
6. Welding Cannot be welded Can be welded Can be welded
Table - 6.3 : Compositions, properties and uses of some alloy steels
Name of the alloy Metals added to Properties Uses

steel steel
1. Stainless steel Cr 11.5%, Ni 8% Resists corrosion Common articles,
ornamental pieces,
automobile parts,
cutlery
2. Chrome steel Cr 1 to 2% High tensile strength Cutting machinery
cutlery
3. Chrome Cr 1%, High tensile strength Springs, shafts, axles
Vanadium steel V 0.15%
4. Manganese steel Mn 13% Very had and tough, Rock crushing
resistant to wear machinery, rock
drills, safes, helmets
5. Nickel steel Ni 2 to 4% Resistant to corrosion, Cable wires, cutting
Hard and elastic tools, automobile
gears and drive shafts,
aeroplane parts,
armour plates.
6. Invar Ni 36% Small coefficent of Measuring scales and
expansion tapes, pendulum,
clock pendulums,
balance parts
7. Permalloy Ni 78% Strongly magnetised by Ocean cables,
electric current, loses electromagnets.
magnetism when
current is cut off.
8. Molybdenum steel Mo 0.5 to 3% Hard Cutting tools and axles
9. Tungsten steel W 5 to 20% Very hard High speed cutting
Cr 3 to 8% tools use in lathe
works.
6.6 COPPER, Cu
6.6.1 Occurrence
Copper is a fairly abundant metal. It occurs as native (in free state) copper in large
quantities in Michigan (U.S.A.). Native copper is 99.9% pure.
Most copper is extracted from its ores :
1. Chalcopyrite, CuFeS2 (Metallic lustre with colour of copper metal)
2. Chalocite or Copper glance, Cu2S (Dark grey colour)
3. Cuprite, Cu2O (Ruby red colour)
4. Malachite, CuCO3.Cu(OH)2, Basic copper carbonate (Green colour)
5. Azurite, 2CuCO3.Cu(OH)2 (Blue colour)
6.6.2 Extraction of copper from cuprous oxide :

In the Ellingham diagram shown in Fig 6.3 the (Cu, Cu 2O) curve is almost at the top
while (C, Cu) and (CO, CO2) lines lie much below it, particularly in the temperature range
500 – 600K. So it is very easy to prepare metallic copper by heating cuprous oxide with
coke. Therefore the sulphide ores are first change to oxide. The detailed procedure of
extraction is carried out in following five steps.
1. Concentration 2. Roasting 3. Smelting 4. Bessemerisation 5. Refining
1. Concentration : The sulphide ores are concentrated by the froth floatation
process. The ore is finely crushed in ball-mills, suspended in water containing
a small quantity of pine oil and vigorously agitated by blast of air. The particles
of sulphide ore remain in oil-froth and float on the surface. The gangue
(impurity) particles wetted by water sink to the bottom and separated.
2. Roasting : The enriched ore is roasted in a current of air in the reverberatory
furnace to remove As, Sb and much of sulphur.
2CuFeS 2 + O 2 ® Cu 2 S + 2 FeS + SO 2
2Cu 2 S + 3O 2 ® 2Cu 2 O + 2SO 2
2 FeS + 3O 2 ® 2 FeO + 2SO 2
3. Smelting : The roasted ore together with a little coke(C), and silica (SiO 2) is
charged into a blast furnace and melted. As a result of smelting iron sulphide
is oxidised to iron oxide and then converted into fusible ferrous silicate which
is removed as a slag.
2 FeS + 3O 2 ® 2 FeO + 2SO 2 - FeO + SiO2 ® Fe SiO3 (slag)
Part of ferrous sulphide melts along with cuprous sulphide at the high
temperature giving rise to matte that contains about 50% copper.
4. Bessemerisation : The molten copper matte obtained from the blast furnace
is transferred to a Bessemer converter and a blast of air is blown through the
molten matte. On forcing the air blast through the melt, sulphur, arsenic, etc.
are oxidised and escape as gases while ferrous oxide reacts with silica to form
a slag.
Cuprous sulphide is oxidised mostly into cuprous oxide and partly into cupric
oxide and cupric sulphate. Cupric oxide and cupric sulphate react with cuprous
sulphide to produce metallic copper as follows.
2 Cu 2 S + 3O 2 ® 2 Cu 2 O + 2SO 2 - 2 Cu2S + 5O2 ® 2CuSO4 + 2CuO
2 Cu 2 O + Cu 2 S ® 6Cu + SO 2 - CuSO4 + Cu2S ® 3Cu + 2SO2 -
Cu 2 S + 2CuO ® 4Cu + SO 2 -
After completion of the reaction the molten copper is poured into sand moulds.
On cooling, the solid copper obtained assumes a blister surface. This due to
the impression of evolved sulphur dioxide bubbles on the surface of molten
copper during solidification. This copper metal is called blister copper.
5. Refining :
(a) By electrolytic method
The blister copper is cast into blocks and refined by electrolysis. Blister
copper contains about 98% copper and very small amount of impurities
like zinc, iron, nickel, silver, gold etc.
Large heavy plates of blister copper are suspended at intervals in a
lead lining tank containing copper sulphate solution as electrolyte.
Impure copper (blister) plates serve as anodes. The cathodes are pure
and thin copper plates, coated with graphite to scrap off the deposited
copper metal on it (Fig 6.10).
When electrolysis is carried out copper from the anode along with traces of
Zn, Fe or Nickel dissolve into the electrolytic solution while less reactive metals i.e.
silver and gold are left undissolved and settle at the bottom near the anode as anode
mud or anode slime or anode sludge. Copper alone is deposited at cathode, leaving
more active metals Zn, Fe, or Ni in solution. This is because copper ions are more
easily reduced.
At the anode: Cu Cu2+ + 2e (Cu2+ ion passes into the solution)
At the cathode: Cu2+ + 2e Cu (Cu metal is deposited at cathode)
Copper obtained by electrolytic refining method is 99.9% pure. In the
electrolytic refining process, gold and silver are also recovered.
Battery
Cu2+
SO42-- Pure Cu-plate
Impure
Cu-plate Cu2+F (cathode)
(anode) SO42--
Anode mud
(15% CuSO 4 + 5% H 2 SO 4 )solution
Fig. 6.10 : Electrolytic refining of blister copper.
(b) By poling
The crude blister copper is melted in the reverberatory furnace that has a silica
lining. Sulphur and arsenic impurities are oxidised to their oxides. Reactive metals
Fe, Zn etc. form oxides in the form of scum and are skimmed off. Some Cu 2O formed
is reduced by stirring the molten metal with green wood poles. Copper refined in this
process is about 99.5% pure.
Extraction of copper by Hydrometallurgical process
This process is employed to extract copper metal usually from low grade sulphide
ores. A large amount of crushed ore in heaps is exposed to air and water. Copper sulphide is
oxidised to copper sulphate by moist air and the process is completed in about a year.
2 Cu 2S + 5O 2 ® 2CuSO 4 + 2CuO CuS + 2O 2 ® CuSO 4
2 FeS 2 + 7O 2 + 2 H 2 O ® 2 FeSO 4 + 2 H 2 SO 4
2 Fe 2 S 3 + 11O 2 + 2 H 2 O ® 4 FeSO 4 + 2 H 2 SO 4
CuO + H 2 SO 4 ® CuSO 4 + H 2 O
The copper sulphate liquor is collected from the bottom of heaps and run into concrete
pans and iron scraps are added to precipitate copper metal.
CuSO 4 + Fe ® FeSO 4 + Cu
The precipitated copper is dried and then refined.
Extraction of copper from non-sulphide ores

The non-sulphide ores such as malachite and azurite are usually leached with dilute
sulphuric acid. In the leaching process copper is converted to copper sulphate solution and
recovered by electrolysis.
Alternatively, these oxide and carbonate ores are mixed with a flux and powdered
coke and reduced in a reverberatory furnace.
CuCO 3 ® CuO + CO 2 - A; Cu( OH ) 2 ® CuO + H 2 O
CuO + C ® Cu + CO ; Cu 2 O + C ® 2 Cu + CO
6.7 ZINC, Zn
6.7.1 Occurrence :
Zinc found in different ore forms, including
Zinc spar, ZnCO3 Calamine, ZnCO3
Zinc Blende, ZnS Zincite, ZnO
Willemite, 2ZnO, SiO 2 Franklinite, (ZnFe) O.Fe2O3 and Zinc Spinel, ZnO.Al2O3
6.7.2 Extraction :
Zinc is extracted using two processes
(a) Roasting of sulphide ore to obtain Zinc oxide
2ZnS + 3O2 ¾1173K

¾ ¾¾® 2ZnO + 2SO2
(b) Reduction with charcoal which involves release of zinc from the oxide.
Carbonate ore, calamine is calcined to get oxide and CO 2 is driven off.
Calcination
ZnCO3 ZnO + CO 2
D
(Calamine)
Extraction of Zinc from Zinc oxide :
As seen in the Ellingham diagram in Fig. 6.3, the intersection of (Zn, ZnO) and (C,
CO) curves lies at a higher temperature. So the reduction of ZnO with coke is carried out at
a higher temperature.
It can also be seen that, the three curves representing the oxidation of carbon [i.e. (C,
CO); (C, CO2) and (CO, CO2)] lie above the oxidation curve of Zn till the boiling point the
Zinc (i.e. 1180K) is reached.
Above 1180K the DfG° for the formation CO decreases and that for formation of ZnO
increases and intersects the (C, CO 2) curve at 1270K.
So it can be concluded that above 1270K reduction of ZnO by carbon is negative and
hence ZnO is easily reduced by coke.
ZnO is made into brickettes with coke and clay and heated at the temperature around
1673K and the reduction process goes to completion.
Since this temperature is above the boiling point of Zinc, the metal is distilled off
and collected by rapid chilling.
6.8 ELECTROCHEMICAL PRINCIPLES OF METALLURGY :

Some molten metals are reduced by the process of electrolysis. for the process of
electrolysis:
DG° = – nFE° ..................... (i)
where n = number of electrons involved in the process of reduction.
F = Faraday of charge.
and E° = The standard electrode potential of the redox couple (M/M n+) present in the
system. When two metal electrodes are coupled with each other and the difference of two E°
values of them corresponds to a positive E°, then the less reactive metal will come out of the
solution and the more reactive metal will go to the solution.
Ex : Cu2+ (aq) + Fe(s) ® Cu(s) + Fe2+ (aq)
Depending upon the reactivity of the metal produced, the materials of the electrodes
are selected. Sometimes, a flux is added for making molten mass more conducting.
Electrolytic method is used for the extraction of active metals like Na, Mg, Ca, Al etc.
Metals like Na, K, Mg, Ca and Al are very reactive metals. Their oxides, chlorides and
hydroxides are very stable. They cannot be reduced to free metals either by carbon or Aluminium.
In such cases the metals are obtained by reduction of suitable molten salts like chlorides and
hydroxides by the passage of electricity. The process is known as Electrolytic reduction or
Electrometallurgy.
The metal is liberated at the cathode. The aqueous solution of salt of the metal is not
taken for electrolytic reduction, since the metal liberated at the cathode reacts with water forming
metal hydroxide and H2. Hence molten salt of the metal is taken for electrolysis.
6.8.1 Occurrence and extraction of Aluminium :

Aluminium ores include Bauxite (Al 2O3×2H2O), Diaspore (Al2O3×H2O), Corundum
(Al2O3) & Cryolite (Na 3AlF6). The process of extraction of metals by electrolysis of their
fused salts is called electrometallurgy. Aluminium is extracted from pure bauxite ore following
the principle of electrometallurgy. The ore is concentrated by the process of leaching
(discussed before). Then cryolite (Na 3AlF6) and fluorspar (CaF 2) are added to alumina to
(i) reduce its m.pt. to around 1140K
and (ii) make it a good conductor of electricity.
Graphite
Anode Copper
lamp
Na3AlF6
+ Steel vessel with
Al2O3 carbon lining
Outlet
Molten Aluminium
Fig. 6.11 : Electrolytic cell for extraction of aluminium
Then the electrolysis of this mixture is carried out by Hall and Heroult process. The
electrolysis of the molten mass is carried out in an iron tank which is lined with carbon (acts as
cathode) and graphite rods suspended above which serve as anode. The molten alumina is covered
with a layer of powdered coke to prevent oxidation and loss of heat due to radiation. The process
is carried out at about 1173K.
Cathode : Al3+ (melt) + 3e– ® Al (l)
Anode : C(s) + O2– (melt) ® CO + 2e–
C + 2O2– (melt) ® CO2(g) + 4e–
About 0.5 kg of carbon burns during the formation of 1 kg of Aluminium. The graphite
anodes are therefore changed from time to time.
At 1173K temperature the Aluminium metal liberated at cathode melts and this molten
metal sinks to the bottom. This metal is collected through a tapping hole. The metal obtained by
this method is 99.95% pure.
6.9 EXTRACTION OF NON-METALS BY OXIDATION :

Non-metals are generally extracted from their compound by the process of oxidation.
Isolation of chlorine :
Chlorine is extracted from brine solution by the process of oxidation.
2 Cl– (aq) + 2H2O (l) ® 2OH– (aq) + H2(g) + Cl2(g)
This extraction is done by the process of electrolysis.
DG° for this reaction is +422 kJ
- DG°
So, E° = = –2.18V = –2.2V..
nF
The electrolysis requires an excess potential to overcome some other hindering reactions.
Thus, Cl2 is obtained by electrolysis giving out H2 and aqueous NaOH as by-products. Electrolysis
of molten NaCl gives sodium metal along with Cl2 gas.
For the oxides not reducible with carbon:

It must be borne in mind that in the cases of the oxides of those metals which cannot be
reduced with carbon. In such cases, the halide process (Method No. 7) is adopted. For example,
the oxides of calcium etc are not reducible with carbon. To get calcium from its ores we prepare
the chloride first by treating the ore, the carbonate, with HCl and then either – (i) fuse the chlo-
ride with sodium or (ii) electrolyse the fused chloride.
CaCO3 (treated with HCl) CaCl2 (fused & electrolysed) (Ca at the cathode)
(Cl2 at the anode)
6.10 REFINING OF METALS :

The metals obtained during extraction from ores even after reduction are not always pure.
They are often contaminated with slag, dissolved gases and other metals like arsenic, phosphorus,
silicon, carbon etc. whose compounds happen to occur in the same ore. Hence the last step in the
metallurgical process is finally carried out to get the pure metal which is known as refining or
purification.
This is generally done in many ways depending upon the nature of the metal concerned.
The common refining methods are listed below.
1. Liquation 2. Distillation
3. Oxidation 4. Chemical treatment
5. Electrolytic refining. 6. Vapour phase refining
7. Chromatographic methods.
1. Liquation: Metals with low melting points e.g. – mercury, bismuth, tin etc can be sepa-
rated from most impurities – simply by melting the metal and pouring it off. The impure
metal is placed on a sloping hearth of a furnace and heated gently. The metal melts and
flows down leaving behind the solid impurities on the hearth.
CHARGE
IMPURITIES
SL
OP
IN
GH
EA MOLTEN
RT
H ORE
Fig. 6.12 : A Sloping hearth

2. Distillation: Metals with low boiling points such as zinc, cadmium, mercury and bis-
muth can be separated from most impurities by distilling the impure metal in a retort. The
vapours of the metal so produced are condensed in a suitable receiver. The impurities are
left behind in the retort.
3. Oxidation: This type of refining is usually employed for lead, silver, copper and such
other metals. The molten metal is subjected to oxidation through application of air by (i)
tossing- when the molten metal is tossed with the help of ladles (ii) puddling – i.e. stir-
ring the molten metal with long wooden bars, (iii) bessemerisation- when compressed air
is blown through the molten metal in specially designed furnaces, and (iv) Cupellation-
when the molten metal is taken in small dishes made of bone ash and air passed over the
melt. The impurities are oxidized and the volatile oxides thus produced escape. The pure
metal remains behind.
4. Chemical treatment : An important example of chemical treatment of impure metals is
the action of nitric acid on gold. When impure gold is treated with nitric acid. The impu-
rities in it dissolve in the acid and the metal itself remains unattacked.
5. Electrorefining: Probably the most widely used refining process is the electrolytic pro-
cess. A large piece of impure metal is made the anode in the electrolytic cell; a thin piece
of very pure metal is made the cathode. The electrolyte is the solution of a water soluble
compound of the metal concerned. On electrolysis, less active metals which may be present
as impurities fall to the bottom of the electrolytic tank and are collected as ‘mud’ near
anode called anode mud. Metals more active than the one being purified electrolytically
remain in solution as ions. Thus, in the electrorefining of copper, a large piece of impure
copper is made anode in the electrolytic cell; a thin piece of very pure copper is made the
cathode. As the anode material dissolves slowly in the electrolyte, the less active metals
such as zinc and lead go into solution and stay there as ions. The noble metals like gold
and platinum, which remain unaffected, sink to the bottom and settle as anode mud while
copper itself is deposited on the cathode.
ANODE
CATHODE
BAR OF IMPURE
PURE COPPER
COPPER
COPPER
SULPHATE
SOLUTION
MUD CONTAINING GOLD AND SILVER
Fig. 6.13 : Electrorefining of metals

6. Zone Refining : It is also known as fractional crystallization method. In order to obtain

metals of high purity for specific applications, this method is generally employed. Sili-
con and germanium used as semiconductors are obtained by this process. It is based on
the principle that the impurity has greater solubility with the liquid than in solid state of
the metal.
7. Vapour Phase Refining : In this method refining of the metal is done in vapour phase.
The process is carried out only when the following two requirements are fulfilled.
(a) The metal should form a volatile compound with an available reagent.
(b) The volatile compound should be easily decomposable to the original metal.
Examples :
(i) Mond process for refining Nickel : In this process, nickel is heated in a stream
of carbon monoxide forming nickel tetracarbonyl. Nickel tetracarbonyl being
volatile in nature decomposes at higher temperature giving the pure nickel.
Ni + 4CO ¾330
¾¾ -350K
¾¾ ¾® Ni(CO)4
Ni (CO)4 ¾450
¾¾ -4¾
70¾
K ® Ni + 4CO
¾
(ii) van Arkel method for Refining Zirconium or Titanium : Oxygen and nitrogen
are present in the form of impurity in certain metals like Zirconium and Titanium.
The crude metal is heated in an evacuated vessel with iodine. The metal iodide
being more covalent, sublimes.
Zr + 2I2 ® ZrI4
The metal iodide is decomposed on a tungsten filament, electrically heated to
about 1800K. The pure metal get deposited on the filament.
Zr I4 ® Zr + 2I2
8. Chromatographic methods : As discussed in Volume I of this book, chromatographic
methods are of several types depending on the station any phase used like
(a) Paper chromatography
(b) Column chromatography
(c) Gas chromatography etc.
The common principle followed is that, different components of a mixture are differently
adsorbed on the adsorbent. The mixture is put in a liquid or gaseous medium which is
moved through the adsorbent. Different components are adsorbed at different levels on
the column. Later the adsorbed components are eluted (removed) using suitable eluants.
Mixture of
compounds
Stationary
phase Coloured band
Fig. 6.14 : Schematic diagram showing column chromatography
6.11 USES OF METALS :

(A) Aluminium :
(1) Aluminium is a good conductor. So it is used for making transmission cables and
for winding the moving coils of dynamos or motors.
(2) The fine dust of aluminium is used in paints and laequers.
(3) Aluminium being a reactive metal is used for extraction of metals like chromium
and manganese from their oxides.
(4) Aluminium foils are used as wrappers for chocolates, medicines, photographic
films etc.
Table 6.4 : Alloys Aluminium and their uses
Alloy Composition Uses

Aluminium Bronze Al 95% Cu 5% Coins, Utensils, Jewellery
Magnalium Al 95% Mg 5% Balance beams, Pressure cooker
Duralumin Cu 4% Mn 0.5% Aeroplanes, Automobile parts,
Al 95%, Mg 0.5% Pressure cooker etc.
(B) Copper :
Uses of Copper :
1. Since copper has high electrical conductivity, it is extensively used in the
electrical industries for making cables, wires, battery plates, generators,
transformers, etc.
2. It is used in the making of cooking utensils, heating apparatus, steam pipes,

boiler parts, calorimeters, etc.
3. It is used for making coins, in electroplating and electrotyping.
4. Copper salts have numerous uses in agriculture and industries.
5. Copper forms a large number of important alloys which find numerous
applications.
Table - 6.5 : Alloys of Copper and their uses
Alloy Percentage composition Uses
1. Brass Cu 60 to 80%, Zn 40 to 20% Kitchen utensils, condenser tubes,

musical instruments, catridges,
castings, wires, parts of machinery
2. Bronze Cu 75 to 90%, Sn 25-10% Coins, utensils, statues, bells, propeller
blades, medals.
3. German Silver Cu 60%, Zn 25%, Ni 15% Utensils, ornament plating, resistance
coils.
4. Monel metal Cu 30%, Ni 67%, Fe+Mn 3% Acid container, alkali industry, acid
pumps.
5. Gun metal Cu 87%, Sn 10%, Zn 3% Gun barrels, gears, castings.
6. Bell metal Cu 80%, Sn 20% Bells, Gongs, utensils.
7. Aluminium bronze Cu 90%, Al 9.5%, Sn 0.5% Coins, bolts, gears, statues, picture
frames, cheap ornaments, paints.
8. Manganin Cu 86%, Mn 12%, Ni 2% Electrical apparatus.
(C) Uses of Zinc :

(1) Zinc is used for galvanising iron.
(2) Zinc-dust is used as reducing agent in the manufacture of dye-stuffs, paints
etc.
(3) Zinc plates and rods are used in batteries and dry cells.
(4) Zinc forms alloys with copper which are listed above.
Alloys and Amalgams :
An alloy is a homogeneous solid obtained by melting together (i) two or more metals or
(ii) metals and non-metals (usually carbon, phosphorus, silicon etc.)
Metal + Metal = Alloy
Amalgam : When one of the constituent metal of an alloy is mercury, it is known as
amalgam.
Metal + Mercury = Amalgam.
Examples of some Alloys :
Name of the alloy Percentage composition Method of preparation

of metals in the alloy
Brass Cu - 90% By fusion
+Zn - 10% or by electro deposition
Bronze Cu - 90% By fusion

+Sn - 10% or by electro deposition
Solder Pb - 67% By compression

+Sn - 33%
Pewter Sn - 85%
+Cu - 7% By compression
+Bi - 6%
+Sb - 2%
Ferro Chrome Fe - 33% By chemical process

+Cr - 67%
Aluminium Bronze Cu - 90% By chemical process

+Al - 10%
22Carats gold Au - 92% By fusion

+Cu - 8%
Steel alloy Fe – 98-99.9% By fusion & by

+C – 0.1 to 2% other special methods.
Type metal Pb - 82% By special method

+Sb - 15%
+Sn - 3%
Wood’s Metal Bi - 50% By special method

+Pb - 25%
+Sn - 12.5%
+Cd - 12.5%
Stainless steel Fe - 70%

+Cr - 19%
+Ni - 9%
+Cu - 1%
+Mo - 0.8%
+C - 0.2%
Examples of some Amalgams :
Name of the amalgam Presence of other metal Use

with mercury
Sodium amalgam Na + Hg Used as a good reducing agent
Copper amalgam Cu + Hg Used for filling dental cavities
Tin amalgam Sn + Hg Used for the preparation of cheap

mirrors.
1. Alloy : It is a homogeneous mixture of two or more metals.
2. Amalgam : An alloy containing mercury as one of the constituents is called amalgam.
3. Ferro-alloy: An alloy containing iron as one of the constituents is called Fero-alloys
4. Non-Ferrous alloy: An alloy without iron content is called non-ferrous alloy.
5. Aluminothermy: It is a process, which involves the reduction of some metal oxides with
aluminium.
6. Calcination: It a process of heating the concentrated ore in absence of air but at a

temperature insufficient to melt it with a view to driving off the volatile matters.
7. Concentration: It is a process of removing impurities (gangue) from the ore.
8. Flux: It is the substance added to the ores before heating, with the object that it will react
chemically with the impurity (gangue) present in the ore and form a fusible slag.
9. Gangue (Matrix): These are rocky or earthy materials associated with the ores as
impurities.
10. Ore: It is a naturally occurring substance from which the metal may be extracted
economically.
11. Roasting: It is the process of heating the concentrated ore in excess of air but at a
temperature insufficient to melt it (i.e. below the point of fusion) with a view to oxidising it.
12. Slag: It is the fusible compound formed by the union of flux and gangue (impurities).
13. Smelting: It is the process in which the metal is extracted by reducing the oxide ore of
the metal with carbon in presence of flux which combines with the impurities to form a
fusible slag.
14. Leaching : It is the process of extracting metals like sliver, gold etc by dissolving their,
concentrated ore in suitable reagent like acids or bases and then through reprecipitation
or crystallisation.
15. Ellingham diagram is a plot of DfG° vs T for formation of oxides of elemens. The dia-
gram helps us in predicting feasibility of thermal reduction of an ore.
****
QUESTIONS
Very Short Answer: Type (1 mark each)
1. What is calcination ?
2. What is Roasting?
3. What is the difference between flux and slag?
4. Which ore is suitable for carbon reduction?
5. What is slag?
6. Name an important ore of copper.
7. What method in employed to concentrate a sulphide ore?
8. Name one substance, which acts as a flux.
9. For a transition metal oxide, name one effective reducing agent.
10. Name a metal which can be extracted by electrolytic reduction. (Na, Cu, Ag, Zn)
11. What is formed when a flux reacts with a gangue material?
12. Can a mineral be termed as an ore?
13. The oxides of the metals are________
14. What is slag? Give an example of it.
15. Distinguish between mineral and ore.
16. What happens to the ore during roasting?
17. Distinguish between ‘Calcination’ and ‘Roasting’.
18. What do you understand by ‘carbon-reduction, in metallurgy? Give an example.
19. What type of metals are extracted electrolytically?
20. What is the compound formed from the reaction of calcium oxide and silicon dioxide?
21. Metals are ductile. The statement means that metals can be
(a) hammered (c) drawn into wire
(b) made to withstand high pressure (d) Magnetised
22. Which of the following is a constituent of slag?
(a) BaSO4 (b) CaF2
(c) CaSiO3 (d) NaAlO2
23. The impurity in a mineral is called___________.
24. Name two elements that occur in the nature in the native state.
25. What is the method of concentrating iron pyrite ore?
26. Froth floatation process is generally used for the metallurgy of _______.
(oxide ore, chloride ore, sulphide ore, carbonate ore)
27. What is the function of limestone in the extraction of iron in the Blast furnace method?
28. What is formed when a flux reacts with gangue materials?
29. What are the reducing agents inside a Blast furnace?
30. Name two metals purified by electrolytic refining process.
31. What is the name of the main constituent of slag in the blast furnace during the extraction
of iron?
32. In which type of ores, froth floatation process is generally used for metallurgy ?
33. Balance the following equation
Al + Fe3O4 ® Al2O3 + Fe
34. Name the process by which sulphide ore is concentrated.
35. Give an example of acidic flux.
Short Answer Type (2 marks each) :

1. What is the difference between a flux and slag?
2. What is the role of lime stone in the extraction of iron from red Haematite?
3. How does roasting differ from calcination?
4. Explain with a suitable example the term cathodic reduction.
5. Name a flux which is used for removing acidic impurities.
6. Name three types of refining process.
7. Liquation is a refining process. Explain with an example.
8. Name a metal which is commonly used as a reducing agent in metallurgical operations.
(Hint- Al)
9. Name two characteristic features of transition elements.
10. Name various methods commonly employed for the concentration of an ore.
11. What is self-reduction in metallurgy? Give example.
12. What is meant by smelting in metallurgy ?
13. Which ore is suitable for carbon reduction? Explain with one example.
14. What do you understand by carbon reduction in metallurgy? Give an example.
15. What happens to the ore during roasting?
16. What is flux? Give an example.
17. What the function of limestone in the extraction of iron ? Give equation to explain its
action.
Short Answer type (3 marks each)

1. What is the significance of Leaching in the extraction of Aluminium?
2. When a metal is formed in the liquid state, then the process of reduction is easier. Com-
ment on this statement.
3. Which one out of Zn and Cu, can be extracted by hydrometallurgy. Explain.
° °
[Ans : Cu, Because E Cu 2+ / Cu = + 0.34V, E 2H + / H 2 = 0.00 V and E °Zn 2+ / Zn = - 0.76 V]
4. What is the role of (a) depressant (b) froth stabilisers in ‘froth floatation process’?
5. What is the role of silica in the metallurgy of copper?
6. What is Mond’s process? Describe in detail.
7. What is ‘Leaching’?
8. How noble metals like Au and Ag are extracted from their ore?
(a) Zone Refining
(b) Column chromatography
10. State the role of silica in the metallurgy of copper.
11. What is meant by the term chromatography.
Long Answer type (7 marks each)

1. What do you understand by the terms ‘alloys and amalgams’
2. Give a brief account of the following terms as used in the extraction of metals.
(i) Calcination (ii) Roasting
(iii) Smelting (iv) Refining and
(v) Magnetic separation
3. Differentiate between:
(i) Mineral and ore (ii) Alloy and amalgam
(iii) Calcination and roasting.
4. What do you understand by electrochemical series? Discuss the importance of
electrochemical series.
5. What is the difference between
(a) An ore and a mineral.
(b) An alloy and amalgam.
(c) Slag and flux (1.1.T. 1978)
(d) Smelting and roasting (1.1.T. 1978)
6. What do you understand by concentration of ores?
7. What is meant by carbon reduction and electrolytic reduction with examples? What is the
role of flux in the metallurgical operation? Name one mineral that can be used as a flux
and describe its working.
8. Fill in the blanks and rewrite the whole statement.
(i) A metal, which can be, obtained as powder________.
(ii) A non-metal which shines like a metal and good conductor of electricity is _____.
(iii) Two metals used in alloy formation___________.
(iv) Two non-metals used in alloy formation__________.
(v) Two metals which occur in native state_________.
(vi) A metal which gives acidic oxide__________.
9. Discuss the various processes which are generally employed for concentration of the ore.
10. (a) What do you understand by the following tems?
(i) Metallurgy (ii) Ore (iii) Mineral (iv) Gangue
(b) How do metals occur in nature?
11. Write notes on -
(i) Aluminothermic process
(ii) Electrolytic reduction
12. What are the different methods of extracting a metal from its ore? Explain each method
with one example.
13. Give the meaning of the following with example
(a) Ore (b) Minerals
(c) Refining (d) Smelting
14. Write notes on :
(i) Aluminothermic process
(ii) Carbon reduction process
15. Write down the reactions taking place at different zones of blast furnace during the
extraction of Iron.
16. Write the chemical reactions taking place in the extraction of Zinc from Zinc blende.
Write three uses of It.
17. What is Ellingham diagram ?
With reference to this diagram explain the following:
(a) Mg is more reducing than Zn.
(b) Al acts as a better reducing agent than Fe.
(c) Extraction of metals like Ag and Hg from their oxides take place high temperature.
FILL IN THE BLANKS WITH ANSWERS
1. Sulphide ores, generally, concentrated by _______ process.
2. The process of heating ore in the absence or limited supply of air, is called____.
3. Roasting is heating of ore in presence of __________of air
4. Minerals, from which metal can be extracted economically, are called _________.
5. The art of extracting metals from their ores is called_______.
6. The process of removal of gangue or matrix from the ore is known as __________.
7. Coke used during smelting of iron acts as fuel as well as __________agent.
8. Substance used during smelting to remove gangue in the form of slag, is called_____.
9. The flux combines with the gangue to form fusible mass, called______.
10. The process of purification of metals to get extra-pure metals is known as _____.
11. A mineral used in the extraction of metal is called___________.
12. Highly electropositive metals such as alkaline earths are extracted by _________.
13. In electrolytic refining, the crude metal is made_____________.
14. Reduction of metal oxides by aluminium metal is called__________.
15. During carbon reduction process, an additional substance added to get rid of the
impurities is called ____________.
16. _____________is the product obtained when flux combines with the impurities.
17. Calcination helps to remove ________and ________.
18. Na/Hg is prepared in order to decrease the ________. It is also used as a ________.
ANSWERS
1. Froth floatation 2. Calcination 3. Excess
4. Ores. 5. Metallurgy 6. Concentration
7. Reducing 8. Flux 9. Slag
10. Refining 11. Ore 12 Electrometallurgy
13 Anode 14 Aluminothermy 15 Flux
16 Slag 17 Moisture, volatile 18 Activity of sodium,
impurities reducing agent
Multiple Choice questions with answers

1. The impurities associated with the ore after mining are collectively called:
(a) Flux
(b) Slag
(c) Minerals
(d) Gangue
2. An ore after levigation is found to have acidic impurities. Which of the following can be
used as flux during smelting operation?
(a) H2SO4
(b) CaCO3
(c) Both CaCO3 and SiO2
(d) SiO2
3. The process in which metal oxide is reduced to metal is called:
(a) Smelting
(b) Aluminothermy
(c) Hydrothermy
(d) No specific name
4. Extraction of silver from Ag2S by the use of sodium cyanide is an example of:
(a) Roasting
(b) Hydrometallurgy
(c) Electrometallurgy
(d) Smelting
5. Which of the following metals can be extracted by smelting?
(a) Aluminium
(b) Magnesium
(c) Iron
(d) None of these
6. The most abundant element in earth’s crust is :

(a) Nitrogen
(b) Oxygen
(c) Iron
(d) Magnesium
7. Which of the following barium salts is soluble in water?

(a) barium sulphate
(b) barium cabonate
(c) barium nitrate
(d) barium phosphate
8. The most abundant metal in the earth’s crust is:
(a) Fe
(b) Cu
(c) Al
(d) Ag
9. Coper is extracted from
(a) Cuprite (b) Copper glance
(c) Malachite (d) Copper pyrite
10. The salt which least likely to be found in minerals is
(a) Sulphides (b) Chlorides
(c) Nitrates (d) Sulphates
ANSWERS
1. (d) 2. (b) 3. (b) 4. (b) 5. (c) 6. (b) 7. (c) 8. (c) 9. (d) 10. (c)
qqq
GROUP 15 ELEMENTS : NITROGEN FAMILY 231
UNIT - VII
p - BLOCK ELEMENTS
CHAPTER - 7
GROUP 15 ELEMENTS : NITROGEN FAMILY
The elements nitrogen, phosphorus, arsenic, antimony and bismuth occupy the group
15 of the periodic table. These elements are also known as the nitrogen family of elements
as the first element is nitrogen. Nitrogen is present in the atmosphere in about 78% by volume.
The family shows a change from nonmetallic and electronegative behaviour (N and P) to
metallic and weakly electropositive behaviour (bismuth) through metalloids like arsenic and
antimony.
7.1 OCCURRENCE :
Molecular nitrogen comprises about 78% by volume of our atmosphere. The chief ores
of nitrogen found in earth's crust are sodium nitrate, NaNO 3 (chile salt petre) and potassium
nitrate, KNO3 (Indian salt petre). It is an important constituent of proteins in plants and
animals.
Phosphorous is very reactive in nature. Therefore it does not occur in free state. It is
found in minerals of the "apatite family", Ca 9 (PO4)6 × CaX2 [X = F, Cl or OH].
e.g : (i) Fluorapatite, Ca9 (PO4)6 × CaF2
(ii) Chlorapatite, Ca9 (PO4)6 × CaCl2
(iii) Hydroxyapatite, Ca9 (PO4)6 × Ca(OH)2
These minerals are the major components of phosphate rocks.
Phosphoproteins are present in milk and eggs. It also occurs in ADP (Adenosine Di-
Phosphate) and ATP (Adenosine Tri Phosphate) which have vital importance for production of
energy in cells.
Arsenic, Antimony and Bismuth mainly occur as sulphide minerals.
e.g : (i) Stibnite, Sb2S3
(ii) Bismuth glance, Bi2S3.
7.2 TRENDS IN PHYSICAL PROPERTIES :
7.2.1 Electronic configuration :

The general outermost electronic configuration is given by ns 2np3. In all these elements
the completely filled s-orbital and half-filled p-orbitals make their electronic configuration
extra stable.
Table 7.1 : Properties of elements of nitrogen family
Property N P As Sb Bi
Atomic number 7 15 33 51 83
Atomic mass/g.mol–1 14.01 30.97 74.92 121.75 208.98
Electronic [He]2s22p3 [Ne]3s23p3 [Ar]3d10 [Kr]4d10 [Xe]4f14
configuration 4s24p3 5s25p3 5d106s256p3
First Ionisation 1403 1060 946 833 703
Enthalpy (kJmol–1)
Electronegativity 3.0 2.1 2.0 1.9 1.9
Atomic radius (A°) 0.75 1.06 1.19 1.38 1.46
Melting point/K 63a 317b 1089c 904 544
Boiling point/K 77.2a 554b 888d 1860 1837
(aMolecular N2, bWhite phosphorus, cGrey µ – form at 38.6 atm, dSublimation temperature)
7.2.2 Atomic Radii :

There is a considerable increase in atomic radii (covalent radii) from Nitrogen to
Phosphorus. But from Arsenic to Bismuth only a small increase in covalent radius is observed
(Table 7.1). This is becuase of the presence of completely filled 'd' and/or 'f' orbitals in those
heavier elements.
7.2.3 Ionisation Enthalpy :
The ionisation enthalpy of Group 15 elements is much greater than that of the
corresponding elements (present in the same period) of Group 14. This is because of the
presence of extra-stable half-filled p-orbitals. On moving top to bottom along the group the
Ionisation Enthalpy decreases (Table 7.1).
7.2.4 Electronegativity :
Nitrogen is the most electronegative element of the group. Though electronegativity of
the elements decreases down the group, but the difference is not much pronounced for heavier
elements.
7.2.5 Physical State :

Dinitrogen, the first member of this group exists in the gaseous state. But all other
members are solids at room temperature and also exist in different allotropic forms.
7.3 TRENDS IN CHEMICAL PROPERTIES :

7.3.1 Oxidation States :
The outer ns2np3 electronic configuration of the elements of this group suggests the
common oxidation states from –3 to +5. Nitrogen being the smallest and most electronegative
element of the group shows –3 oxidation state. Ex.: Mg 3N2, Ca3N2 etc.
Other elements of this group also form compounds with –3 oxidation state. Ex.: Ca 3P2,
Mg3Bi2, Zn3Sb2 etc.
As we move down the group this tendency to show –3 oxidation state decreases due
to increase in size and metallic character.
Nitrogen also exhibits +1, +2, +4 oxidation states when it reacts with oxygen. Table
7.2 summarises the oxidation states shown by nitrogen in different compounds. It's oxidation
states from +1 to +4 tend to disproportionate in an acid solution.
Table 7.2 : Oxidation states of nitrogen

Oxidation state Compound
5 N2O5
4 N2O4
3 N2O3
2 NO
1 N2O
0 N2
–1 NH2OH
–2 N2H4
–3 NH3
+3 +5 +2
For ex : 3H N O 2 ® H N O 3 + H 2 O + 2 N O
In case of phosphorus nearly all intermediate oxidation states disproportionate into '+5'
and '–3' both in alkali and acid.
+3
D +5 -3
Ex : 4H 3 P O3 ¾¾® 3H 3 P O 4 + P H 3
The '+3' oxidation state of Arsenic, Antimony and Bismuth become increasingly stable
with respect to disproportionation, because of inert pair effect.
Presence of four orbitals (one 's' and three 'p') of nitrogen in its valence shell restricts
the covalency upto 4. So it can not form compounds like NF5, NCl5 etc. But the vacant d-
orbitals present in the heavier elements of this group enable them to extend their covalency
beyond 4. Ex : PCl5, [PF6]–, AsF5, [SbF6]– etc.
7.3.2 Reaction with Hydrogen :
All the elements of this group form hydrides, MH 3. They are all covalent and pyramidal
in shape. The basic character of the hydrides decreases in the order NH 3 > PH3 >AsH3 > SbH3
³ BiH3
NH3 + HCl ® NH4Cl
PH3 + HI ® PH4I
Stability of the hydrides decreases and reducing character increases on moving down
the group, BiH3 being the strongest.
7.3.3 Reaction with Halogens :
All the elements of this family form trihalides. Trihalides of nitrogen except NF 3 are
very unstable. They are readily hydrolysed by water.
NCl3 + 3H2O ® NH3 + 3HOCl
PCl3 + 3H2O ® H3PO3 + 3HCl
SbCl3 + H2O SbOCl + 2HCl
BiCl3 + H2O BiOCl + 2HCl
These halides are predominantly covalent. Ionic character increases on moving down
the group. BiCl3 is quite ionic.
Pentahalides are formed by phosphorus and other elements and are more covalent than
trihalides. This is because, higher the possitive oxidation state of the central atom more will
be its polarising power and more is the covalency. Nitrogen does not form pentahalides due
to non-availability of d-orbitals. Bismuth does not form pentahalides because of inert pair
effect of 6s-electrons.
7.3.4 Reaction with Oxygen :
All the elements of nitrogen family form oxides of type M 2O3 and M2O5. N2O3, P2O3
and As2O3 are acidic with acidity decreasing down the group. Sb 2O3 is amphoteric while Bi2O3
is basic. Nitrogen also forms N2O, NO, NO2, and N2O4. N2O5 is the strongest acidic oxide and
Bi2O3 is the weakest.
7.3.5 Reaction with Sulphur :
Except nitrogen all other elements of the group react with sulphur to form sulphides.
The stability of sulphides increases down the group due to increase in electo positive character.
7.3.6 Formation of Oxyacids :

Nitrous acid, HNO2 and nitric acid, HNO3 are the two common oxyacids of nitrogen.
Phosphorus forms a large number of oxyacids like phosphorus acid, H 3PO3, orthophosphoric
acid, H3PO4, pyrophosphoric acid, H4P2O7 and metaphosphoric acid, HPO3. Arsenic forms
oxyacids, arsenious acid (H3AsO3) and arsenic acid (H3AsO4).
Antimony forms unstable H3SbO3 and bismuth, stable HBiO3 (metabismuthic acid).
7.4 ANOMALOUS BEHAVIOUR OF NITROGEN :

Nitrogen differs from other members of the group in its behaviour because of
(i) Its very small size and high electronegativity
(ii) Nonavailability of vacant d-orbital.
(i) Effect of small size : Because of small size nitrogen can form pp – pp multiple bonds
with itself and with other elements having small size and high electronegativity; ex:
CN, NO etc. The small size of the atom leads to effective overlapping between atomic
orbitals which is not possible in case of other members of the group. For the same
reason nitrogen itself exists as diatomic molecule with triple bond. However, the
repulsion of the non-bonding electrons make single N–N bond weaker which decreases
its catenation tendency.
(ii) Effect of non-availability of vacant d-orbitals : Absence of vacant d-orbitals in
nitrogen restricts (a) its covalency beyond 4 and (b) ability to fom pp - dp bond or dp -
dp bond. The other members of the group can form compounds like R 3P = 0 or R3P
= CH2 (R is an alkyl group) where dp - pp bond is present, which nitrogen can't.
Compounds of 'P', 'As' etc. e.g. (C2H5)3P, (C6H5)3 As can act as ligands because of their
ability to form dp - dp bond with transition metals.
7.5 DINITORGEN :
7.5.1 Preparation :
(1) Laboratory Method : Dinitrogen is prepared in the laboratory by treating an aqueous
solution of NH4Cl with NaNO2.
NH4Cl (aq) + NaNO2 (aq) ® N2(g) + 2H2O(l) + NaCl (aq).
Small amount NO and HNO3 are also formed in this reaction. These impurities are
removed by passing the gas through aqueous sulphuric acid containing potassium
dichromate.
(2) From Ammonium dichromate : Thermal decomposition of ammonium dichromate
also produces dinitrogen gas.
(NH4)2 Cr2O7 ¾Heat

¾¾® N2 + 4H2O + Cr2O3.
(3) Thermal decomposition of Sodium or Barium Azide : Very pure dinitrogen is obtained
by the thermal decomposition of sodium or barium azide.
D
2NaN3 ¾¾® 2Na + 3N2.
D
Ba (N3)2 ¾¾® Ba + 3N2.
(4) Commercial method of preparation : Dinitrogen is produced commercially by the
liquefaction and fractional distillation of air. In this method the atmospheric air is first
liquified and then subjected to fractional distillation. The fraction collected at 77.2K
gives liquid nitrogen.
7.5.2 Properties :
Physical properties :
(1) Dinitrogen is a colourless, odourless, tasteless gas and is non-poisonous in nature.
(2) It has two stable isotopes 14N and 15N.
(3) It has very low solubility i.e. 23.2 cm3 per litre of water at 273K and 1 bar pressure.
(4) It has boiling point 77.2K and freezing point 63.2K.
Chemical Properties :
(1) Dinitrogen is rather inert at room temperature because of high bond enthalpy (941.4
kJmol–1) of N º N bond.
(2) Action with metals : With rise in temperature reactivity of dinitrogen increases. It
combines with metals on heating to give the ionic nitrides.
6Li + N2 ¾Heat
¾¾® 2Li3N
3Mg + N2 ¾Heat
¾¾® Mg3N2
(3) Action with non-metals : With non-metals dinitrogen produces covalent nitrides.
(i) With dihydrogen : It combines with hydrogen at about 773K temp and 200
atmospheric pressure in presence of a catalyst to produce NH 3 and the process
is commonly known as Haber's process.
773K
N2(g) + 3H2(g) 2NH3(g).
200 atm
(ii) With dioxygen : It combines with dioxygen at very high temperature (at about
2000K) to form nitric oxide.
N2(g) + O2(g) Heat 2NO(g)

(4) Action with calcium carbide : It reacts with calcium carbide at high temperature to
give calcium cyanamide.
1273K
CaC2(s) + N2(g) CaCN2(s) + C(s)
Calcium carbide Calcium cyanamide
Calcium cyanamide reacts with water to form NH 3.
CaCN2(s) + 3H2O ® CaCO3(s) + 2NH3(g)
Therefore, it is used as a fertilizer under the name nitrolim (CaCN2 + C).
Summary :
D
Li 3N
Li (s)
D
Mg 3N2
Mg (s)
773K/200 atm
N2 NH3
H2 (g)
O2 (g)
NO
2000K
CaC(s)
2
CaCN 2
1273K
7.5.3 Uses :
(1) It is used in the manufacture of ammonia, nitric acid, calcium cyanamide etc.
(2) It produces an inert atmosphere in iron and steel industry.
(3) Dinitrogen acts as an inert diluent in reactive chemicals.
(4) Liquid dinitrogen is used as a refrigerant to preserve biological materials, food items
and in cryosurgery.
COMPOUNDS OF NITROGEN
7.6 PREPARATION, PROPERTIES AND USES OF AMMONIA :
7.6.1 Preparation :
(1) Haber's process : It is the cheapest method for producing ammonia in large scale.
Nitrogen combines with hydrogen according to the equation, N 2 + 3H2 l 2NH3
+ 93.6 kJ. Since the reaction is exothermic, according to Le-Chatelier's principle
favourable conditions for maximum yield are high pressure, low temperature and high
concentration of the reactants. Therefore, an optimum temperature of 500 0C and pressure
of 200 atmosphere is used for maximum yield.
Further, to increase the rate of reaction, finely divided iron containing molybdenum as
promoter is used as the catalyst.
N2 H2
REFRIGERATOR
CATALYST
CHAMBER
R
C RECIRCULATION
PUMP
COMPRESSOR
Fe (CATALYST)
LIQUID AMMONIA
Mo (PROMOTER)
Fig. 7.1 : Haber's process of manufacture of ammonia

(2) Laboratory Process : The ammonia gas is prepared in the laboratory by heating
ammonium chloride with slaked lime or quick lime.
2NH4Cl + Ca(OH)2 ® CaCl2 + 2NH3 + 2H2O
2NH4Cl + CaO ® CaCl2 + 2NH3 + H2O
Ammoniun chloride and solid slaked or quick lime are mixed well in a mortar. The
mixture is taken in a hard glass test tube half filled. The delivery tube is connected to
a drying tower filled up with quick lime. On heating the test tube ammonia gas is
produced.
NH3GAS
NH4Cl + Ca(OH)2
NH
3
CaO
TOWER
Fig. 7.2 : Laboratory process of preparing ammonia
Ammonia is lighter than air and highly soluble in water. Hence, it is collected by
downward displacement of air. For pure ammonia, the gas is collected over mercury.
7.6.2 Properties :
(1) Ammonia is a colourless gas with a characteristic smell.
(2) It is lighter than air.
(3) It is highly soluble in water.
(4) It has high M.Pt. and B.Pt. than expected on the basis of its molecular mass. This is
because the molecules are associated with each other by intermolecular hydrogen
bonding.
Chemical properties :
(1) Basic properties : The solution of ammonia in water is alkaline due to formation of
ammonium hydroxide.
NH3 + H2O ® NH4OH
It turns red litmus blue and reacts with acids to form salts.
NH3 + HCl ® NH4Cl (white fumes)
(2) Reducing properties : Ammonia is a reducing agent. When passed over heated copper
oxide, metallic copper, nitrogen and water vapour are produced.
3CuO + 2NH3 ® 3Cu + N2 + 3H2O
(3) Oxidation : Ammonia burns in atmospheric air or oxygen with a blue flame.
4NH3 + 3O2 ® 2N2 + 6H2O
In presence of platinum gauze at 5000C, nitric oxide is formed.
4NH3 + 5O2 ¾Pt ¾® 4NO + 6H2O
(4) Reaction with halogens : With insufficient amount of chlorine, ammonia produces
nitrogen and hydrochloric acid. Hydrochloric acid reacts with ammonia producing
ammonium chloride.
2NH3 + 3Cl2 ® N2 + 6HCl
6NH3 + 6HCl ® 6NH4Cl
————————————
8NH3 + 3Cl2 ® 6NH4Cl + N2
With excess of chlorine, NCl3 is produced.
NH3 + 3Cl2 ® NCl3 + 3HCl
Nitrogen tri-iodide is an explosive compound prepared by reacting NH3 into excess of
iodine.
(5) Reaction with metals : With alkalimetals metal amide and hydrogen are formed.
2Na + 2NH3 ® 2NaNH2 + H2
(Sodamide)
2K + 2NH3 ® 2KNH2 + H2
(Potassamide)
(6) Reaction with salt solutions : With metal salt solutions, ammonia forms hydroxides.
FeCl3 + 3NH4OH ® Fe(OH)3 + 3NH4Cl
Brown
ZnCl2 + 2NH4OH ® Zn (OH)2 + 2NH4Cl.
(7) Reaction with Lewis Base : Ammonia molecule has a distorted
tetrahedral structure due to presence of a lone pair of electrons on the ..
central nitrogen atom and this lone pair of electrons makes it to behave
N
as a Lewis base. It forms dative bond with electron-deficient molecules
(e.g. BF3) and transition metal cations having vacant d-orbitals thus H H
forming complex compounds. Many such reactions are used for the H
detection of metal ions such as Cu2+, Ag+ etc.
AgCl(s) + 2NH4OH(aq) ® [Ag(NH3)2] Cl(aq) + 2H2O(l)
Diamminesilver (I) chloride
CuSO4(aq) + 4NH4OH(aq) ® [Cu(NH3)4]SO4(aq) + 4H2O(l)
Tetrammine copper(II)sulphate
(8) Reaction with Nessler's Reagent : Ammonia gives a brown precipitate with Nessler's
reagent (an alkaline solution of K2HgI4) due to formation of iodide of Millon's base.
This test is used for the identification of ammonium ion in qualitative analysis.
2K2HgI4 + NH3 + 3KOH ® H2N – Hg – O – Hg – I + 7KI + 2H2O
Nessler's reagent Iodide of Millon's base (Brown ppt)
(9) Self Ionistion : Ammonia can undergo self-ionisation in liquid state due to which it
acts as a good solvent for dissolving many polar compounds and hence helpful for
carrying out many reactions in the non-aqueous medium.
2NH3 NH4+ + NH2–
SUMMARY : H2O
NH4OH
HCl
NH4Cl
CuO
Cu + N2 +H2O
O2
N2 +H2O
O2
NO + H2 O
Pt, 500 0C
NH3
Cl2
NH4 Cl + N2
Cl2
NCl3
excess
FeCl3
Fe (OH)3
ZnCl2
Zn (OH)2
CuSO 4
[Cu(NH3)4 ]SO4
AgCl
[Ag(NH3)2 ]Cl
7.6.3 Uses :
(1) Fertiliser : Ammonia is used in the manufacture of fertilisers like urea, ammonium
sulphate, ammonium nitrate and ammonium phosphate.
(2) Preparation of various compounds : It is used in the manufacture of nitric acid
and sodium carbonate.
(3) Refrigerant : Liquid ammonia is used as a good refrigerant.
(4) Laboratory reagent : It is a valuable reagent in chemical laboratories.
7.7 PREPARATION, PROPERTIES AND USES OF NITRIC ACID :

7.7.1 Preparation :
Ostwald's process of manufacture of Nitric acid :
(i) Principle : A mixture of ammonia and oxygen or air is heated in presence of
platinum catalyst to about 8000C.
4NH3 + 5O2 ¾Pt
¾® 4NO + 6H2O + 21.5 kcal
2NO + O2 ® 2NO2
4NO2 + 2H2O + O2 ® 4HNO3
(ii) Description : A mixture of pure ammonia (1vol.) and dust free air (10 vols.) is
passed through a converter containing platinum catalyst and heated to about 800 0C
(Fig.14.4) Ammonia and oxygen react to form nitric oxide and steam. These gases
are cooled to about 500C by passing through a tower. At this temperature conversion
of nitric oxide to nitrogen peroxide is almost complete. Nitrogen peroxide is then
passed through the absorbing tower where water is sprinkled from the top. It mixes
with nitrogen peroxide to form nitric acid which is collected in the receiver.
WATER
NO + O2
NO2
Pt GAUGE WASTE
GASES
2NO+O2 ABSORPTION
COOLER
TOWER
2NO2
ACID PROOF
FLINT
CONVERTER NO + O2
NH3 + AIR OXIDATION
CHAMBER 60% HNO3
1Vol 10 Vol
Fig. 7.3 : Ostwald's process of manufacture of HNO3

7.7.2 Properties :
Physical : (1) Pure nitric acid is a colourless liquid. The impure acid is yellow due to
dissolved NO2 gas.
(2) The specific gravity of pure acid is 1.52.
(3) The acid is highly corrosive. It produces blisters on the skin which becomes
yellow.
(4) It is hygroscopic and fumes in moist air.
(5) It is soluble in water in all proportions.
Chemical: (1) Acidic properties : It is a strong monobasic acid. It reacts with oxides,
hydroxides and carbonates forming nitrates.
CuO + 2HNO3 ® Cu(NO3)2 + H2O
NaOH + HNO3 ® NaNO3 + H2O
Na2CO3 + 2HNO3 ® 2NaNO3 + H2O + CO2
(i) Oxidising properties : Nitric acid is a powerful oxidising agent because it

produces nascent (atomic) oxygen in the following manner.
2HNO3 ® H2O + 2NO + 3O
(a) With H2S : Nitric acid oxidises hydrogen sulphide to sulphur.

2HNO3 ® H2O + 2NO + 3O
(H2S + O ® H2O + S) x 3
————————————————
2HNO3 + 3H2S ® 2NO + 4H2O + 3S
(b) With PbS : Lead sulphide is oxidised to lead sulphate.

(2HNO3 ® H2O + 2NO + 3O) x 4
(PbS + 4O ® PbSO4) x 3
——————————————————
8HNO3 + 3PbS ® 3PbSO4 + 4H2O + 8NO
(c) With KI : Potassium iodide on treatment with nitric acid liberates iodine.
2HNO3 ® H2O + 2NO + 3O
(2KI + O ® K2O + I2) x 3
(K2O + 2HNO3 ® 2KNO3 + H2O) x 3
————————————————————
8HNO3 + 6KI ® 6KNO3 + 2NO + 3I2 + 4H2O
3. Action of nonmetals : Nitric acid decomposes in presence of nonmetal to give NO 2.

2HNO3 ® H2O + 2NO2 + O
(a) With carbon : Carbon gives carbon dioxide.
(2HNO3 ® H2O + 2NO2 + O) x 2
C + 2O ® CO2
————————————————
4HNO3 + C ® CO2 + 4NO2 + 2H2O
(b) With sulphur : Sulphur is oxidised to sulphur trioxide which reacts with water
producing sulphuric acid.
(2HNO3 ® H2O + 2NO2 + O) x 3
S + 3O ® SO3
SO3 + H2O ® H2SO4
S + 6HNO3 ® H2SO4 + 6NO2 + 2H2O

(Nitric acid oxidises phosphorus to phosphoric acid (H 3PO4), arsenic to H3AsO4
and iodine to iodic acid HIO3)
(4) Action on metals : Except gold and platinum all metals react with nitric acid.
(a) With Iron :
Cold and dilute nitric acid produces ferrous nitrate and ammonium nitrate.
(Fe + 2HNO3 ® Fe(NO3)2 + 2H ) x 4
HNO3 + 8H ® 3H2O + NH3
NH3 + HNO3 ® NH4NO3
———————————————————
4Fe + 1OHNO3 ® 4Fe(NO3)2 + NH4NO3 + 3H2O
Concentrated nitric acid produces ferric nitrate and nitrogen dioxide.
Fe + 3HNO3 ® Fe(NO3)3 + 3H
(HNO3 + H ® NO2 + H2O) x 3
——————————————————
Fe + 6HNO3 ® Fe(NO3)3 + 3NO2 + 3H2O
Iron becomes passive when heated with very concentrated or fuming nitric acid.
(b) With Copper : Dilute nitric acid produces cupric nitrate and nitric oxide.
2HNO3 ® H2O + 2NO + 3O
(Cu + O ® CuO) x 3
CuO + 2HNO3 ® Cu(NO3)2 + H2O) x 3
———————————————————
3Cu + 8HNO3 ® 3Cu(NO3)2 + 2NO + 4H2O
Concentrated nitric acid produces nitrogen dioxide.

2HNO3 ® H2O + 2NO2 + O
Cu + O ® CuO
CuO + 2HNO3 ® Cu(NO3)2 + H2O
——————————————————
Cu + 4HNO3 ® Cu(NO3)2 + 2H2O + 2NO2
(5) Brown Ring Test for Nitrates (NO3–)
This is the confirmatory test for nitrates. About 1mL of the salt solution is taken in a clean
test tube. It is treated with equal volume of Conc. H 2SO4. The resulting solution is cooled under
the tap. Freshly prepared FeSO4 solution is added to it without disturbing the solution. A brown
ring is formed at the junction of two liquids which disappears upon shaking but reappears upon
further addition of FeSO4. NO3– is confirmed. The formation of Brown ring is due to penta-
aquanitroso iron (I) sulphate .
Reactions
NaNO3 + H2SO4 ® NaHSO4 + HNO3
2HNO3 + 6FeSO4 + 3H2SO4 ® 3Fe2 (SO4)3 + 2NO + 4H2O
FeSO4 + NO + 5H2O ® [Fe(H O) NO] SO
2 5 4
penta-aquanitroso iron (I) sulphate

(Brown).
SUMMARY :
CuO Cu(NO3)2
Na2 CO3
NaNO3+CO2+ H2O
H2 S
NO+S + H2O
PbS
PbSO4
KI
KNO3+ NO + I2 + H2O
HNO3 C CO2 + NO2 + H2O
S
H2SO4 + NO2+ H2O
Fe
Fe(NO3)2 + NH4NO3
dil. HNO 3
Fe
Fe(NO3)2 + NO2 + H2O
with Conc. HNO3
Cu
Cu(NO3)2 + NO + H2O
dil.HNO3
Cu Cu(NO3)2 + NO2 + H2O
Conc. HNO3
7.7.3 Uses :
(1) Nitric acid is used in the preparation of aqua regia which is a mixture of conc. HCl
and conc. HNO3 (3:1). Aquaregia can dissolve metals like gold and silver.
HNO3 + 3HCl 2 2H2O + NOCl + 2Cl
Au + 3Cl 2 AuCl3
(2) It is used in the manufacture of fertilisers, artificial silk and explosives like
nitroglycerine, TNT, picric acid etc.
(3) It is used in the purification of gold and silver.
(4) It is extensively used as a laboratory reagent.
(5) It is used in the pickling of stainless steel, etching of metals and an oxidiser in
rocket fuel.
7.8 OXIDES OF NITROGEN :
Nitrogen forms a number of oxides in different oxidation states. The names, formulae,
oxidation states of nitrogen, Resonance structures and Bond parameters are summarised in Table 7.3.
Table 7.3 : Oxides of Nitrogen
Sl. Name Formula Oxidation Resonance Bond
No. states of structures parameters
nitrogen
1. Dinitrogen N2O +1
oxide
[Nitrogen (I)
oxide]
2. Nitrogen NO +2
monoxide
[Nitrogen (II)
oxide]
3. Dinitrogen N2O3 +3
trioxide
[Nitorgen (III)
oxide]
4. Nitrogen NO2 +4
dioxide
[Nitrogen (IV)
oxide
tetroxide
[Nitrogen (IV)
oxide]
pentoxide
[Nitrogen (V)
oxide]
7.9 PHOSPHORUS :
Allotropic forms of phosphorus :
Phosphorus is found in may allotropic forms, among which the white, black and red are
important.
7.9.1 White phosphorus :
(1) It is a white waxy solid with garlic odour and translucent P
nature.
(2) It is poisonous. 60°
P P
(3) It is insoluble in water and soluble in organic solvents like
carbon disulphide, alcohol, ether etc.
(4) White phosphorus is less stable and more reactive. Therefore P
it readily catches fire and gives a greenish glow, the Fig. 7.4
phenomenon being, called as 'chemiluminescence' or White phosphorus
'phosphorescence'.
Reason : The P-P-P bond angle is 60°, which is much smaller than the normal tetrahedral
angle. So the P4 molecule is under strain.
P4(s) + 5O2(g) ¾303K

¾¾ ¾® P4O10(s).
Because of its low ignition temperature it is always kept under water.
(5) It dissolves in boiling NaOH solution in an inert atmosphere giving phosphine gas.
P4 + 3NaOH + 3H2O ® PH3(g) + 3NaH2PO4
Phosphine Sodium hypophosphite
7.9.2 Red Phsophorus :
It is obtained by heating white phsphorus of 573K in an inert atmosphere for several
days.
P4(s) 573K P4(s)

¾¾ ¾ ¾®
CO2 or coal gas Red phosphorus
(1) It is hard crystalline odourless solid with iron grey lustre.
(2) It is non-poisonous in nature.
(3) It is insoluble in water as well as in organic solvents.
(4) Red phosphorus is much less reactive than white phosphorus and does not show
phosphorescence because of its polymeric structure. The chain of P 4 tetrahetrals are
linked together to form the red allotrope which makes it comparatively more stable.
P P P
P P P P P P
P P P
Fig. 7.5 : Red phosphorus
7.9.3 Black Phosphorus :

Black phosphorous has two forms : a - black phosphrus and b - black phosphorus.
a - Black phosphorus :
When red phsphorus is heated in a sealed tube at 803K, a - black phosphorus is obtained.
803K
Red phosphorus a - Black phosphorus.
sealed tube
(1) Black phosphorus can be sublimed in air.
(2) It has opaque monoclinic or rhombohedral crystals.
(3) It does not oxidise in air.
(4) It does not conduct electricity.
b - Black phosphorus :
It is prepared by heating white phosphorus at 473K under a high pressure.
473K
White phosphorus High pressure b - Black phosphorus.
(1) It is the most stable allotrope of phssphorus.

(2) It has a highly polymerised form of phosphorus and has black metallic lustre.
(3) It has sharp M.P. at 860K
(4) It as a layered graphite- like structure in which each phosphorus atom is covalently
bonded to 3 neighbouring phosphorus atoms and is a good conductor of electricity.
7.10 PREPARATION, PROPERTIES AND USES OF PHOSPHINE (PH3) :
Laboratory method of preparation of phosphine:

Yellow phosphorus reacts with sodium hydroxide on heating producing phosphine and
sodium hypophosphite.
P4 + 3NaOH + 3H2O ® 3NaH2PO2 + PH3
About 60 cc. of 30 - 40% NaOH solution is taken in a round bottomed flask. A few
pieces of yellow or white phosphorus are added to the solution followed by 5 cc of ether. A
cork fitted with a delivery tube is tightly fitted to the flask. Ether vapour removes air from the
flask as phosphine explodes in air.
YELLOW
P and
NaOH PH3
Fig. 7.6 : Preparation of Phosphine
The flask is placed on a tripod stand and heated. The gas is collected by the downward
displacement of water. The gas contains diphosphine and hydrogen as impurities. Pure phosphine
can be prepared by heating phosphorus acid.
4H3PO3 ¾ ¾
¾® 3H3 PO4 + PH3 .
Properties :
Physical : (1) It is a colourless gas with a rotten fish smell.
(2) It is heavier than air.
(3) It is slightly soluble in water.
Chemical :
(1) Oxidation : Phosphine burns in air or oxygen producing a white smoke containing
phosphorus pentoxide and metaphosphoric acid.
2PH3 + 4O2 ® P2O5 + 3H2O
P2O5 + H2O ® 2HPO3
(2) With chlorine : Phosphine burns in chlorine producing phosphorus pentachloride.
PH3 + 4Cl2 ® PCl5 + 3HCl
(3) With halogen acids : Phosphine reacts with HI and HBr producing phosphonium
iodide and bromide respectively. With HCl, the reaction does not take place so
easily.
PH3 + HI ® PH4I
PH3 + HBr ® PH4Br
(4) Reducing property : Just as ammonia , it is a reducing gas. It reacts with a
solution of silver salt producing black phosphide and finally the metal.
3AgNO3 + PH3 ® Ag3P (black) + 3HNO3
Ag3P + 3AgNO3 + 3H2O ® 6Ag + 3HNO3 + H3PO3
(5) With N2O : A mixture of phosphine and nitrous oxide in the ratio of 1:2 explodes
when ignited.
2PH3 + 8N2O ® P2O5 + 3H2O + 8N2
SUMMARY :
O2
P2O5 + H2O
Cl2
PCl3 + HCl
HI
PH4I
PH3
HBr
PH4Br
AgNO3
Ag3P
N2O
P2O5 + N2 + H2O
USES : (1) It is used for singnalling in the sea. It is called Holme's signal.
(2) It is used in naval warfare for locating enemy positions on the sea.
7.11 PHOSPHORUS HALIDES :
Phosprorus forms two types of halides, PX3(X=F, Cl, Br, I) and PX5 (X = F, Cl, Br).
7.11.1 Phosphorus trichloride (PCl3)

Preparation :
(1) By passing dry chlorine over heated white phosphorus phosphorus trichloride is obtained.
P4(s) + 6Cl2(g) ® 4PCl3(l)
(2) White phsophorus reacts with thionyl chloride yielding PCl 3
P4(s) + 8SOCl2 ® 4PCl3(l) + 4SO2(g) + 2S2Cl2
Sulphur monochloride
Structure :
In PCl3 the central 'P' atom is sp3 hybridised and contains one lone
pair of electrons. Thus the molecule has pyramidal structure with bond ..
angle 100.4°. P
Cl Cl
Properties :
Cl
Fig. : 7.7
(1) It is a colourless liquid with pungent smell.
(2) It has boiling point 347K and freezing point 161K.
(3) It fumes in moist air.
(1) With water : It reacts violently with water to produce phosphorus acid (H 3PO3) and
hydrochloric acid.
PCl3 + 3H2O ® H3PO3 + 3HCl
(2) With acetic acid and ethyl alcohol : It reacts with organic compounds like acetic
acid, ethyl alcohol etc. and replaces the –OH group in them by –Cl atom, thus producing
their chloroderivatives.
7.11.2 Phosphorus pentachloride (PCl5) :

Preparation :
(1) PCl5 is prepared by the reaction of white phosphorus with excess of dry chlorine.
P4(s) + 10 Cl2(g) ® 4PCl5(s).
(2) Thionyl chloride reacts with phosphorus producing PCl5.
P4 + 10 SO2Cl2 ® 4 PCl5(s) + 10 SO2(g).
Structure : Cl
In PCl5, the central P-atom undergoes sp3d– 240 pm Cl

hybridisation and the molecule has trigonal
bipyramidal structure in gaseous and liquid state.
P 202 pm
The axial bond lengths are 240 pm each being greater Cl
than equatorial bonds of length 202 pm each. This
Cl
is because the two axial P–Cl bonds are repelled by
Cl
3 bond pairs while three equitorial bonds experience
Fig.: 7.8 : Structure of PCl5
repulsion only by two bond pairs.
In the solid state PCl5 exists as ionic solid, [PCl4]+ [PCl6]–, in which the cation [PCl4]+
is tetrahedral and anion [PCl6]– is octahedral.
Properties :
(1) PCl5 is a yellowish white solid.
(2) It has a characteristic pungent smell.
(1) Action of moist air : In moist air it hydrolyses to give POCl3 and gets converted to
phosphoric acid.
PCl5 + H2O ® POCl3 + 2HCl
POCl3 + 3H2O ® H3PO4 + 3HCl
(2) With acetic acid and ethyl alcohol : Like PCl3 it also converts organic compounds
containing –OH group to their chloro derivatives.
C2H5 + PCl5 ® C2H5Cl + POCl3 + HCl
CH3COOH + PCl5 ® CH3COCl + POCl3 + HCl
(3) With metals : Finely divided metals on heating with PCl5 give corresponding chlorides.
Sn + 2PCl5 ® SnCl4 + 2PCl3
Zn + PCl5 ® ZnCl2 + PCl3
7.12 OXOACIDS OF PHOSPHORUS :
Phosphorus forms a number of oxo-acids. The important oxo-acids of phosphorus with
their formula, oxidation state of phosphorus, characteristic bonds and structure are given in
Table 7.4.
In oxoacids phosphorus is tetrahedrally surrounded by other atoms or groups. The
P–H bonds are not ionisable to give H+ ion. only the H atoms attached with oxygen in P–OH
form are ionisable and cause the basicity. The P–H bond H–atoms help in reduction. Thus
hypophosphorous acid reduces AgNO3 to metallic silver.
4AgNO3 + 2H2O + H3PO2 ® 4Ag + 4HNO3 + H3PO4
Table 7.4 : Oxoacids of phosphorus

Sl. Name Formula O.S. of Characteristic Structure
No. Phosphorus bonds and
their number
O
1. Hypophosphorous H3PO2 +1 One P–OH
acid Two P–H 1
P OH
(Phosphinic Acid) One P=O H
2. Orthophosphorous H3PO3 +3 Two P–OH

acid One P–H 2 P
H OH
(Phosphonic Acid) One P=O
OH
O O
3. Pyrophosphorous H4P2O5 +3 Two P–OH

acid Two P–H 2 H
P
O
P
H
Two P=O OH OH
4. Orthophosphoric H3PO4 +5 Three P–OH

P
acid One P=O 3 OH OH
OH
O O
5. Pyrophosphoric H4P2O7 +5 Four P–OH

acid Two P=O 4 OH
P
O
P
OH
One P–O–P OH OH

1. The elements belonging to Group 15 are nitrogen, phosphorus, arsenic, antimony and
bismuth.
2. The general outermost electronic configuration is ns 2np3.
3. Oxidation State : Elements show oxidation states from –3 to +5. +3 oxidation state is
found to be more common in the group due to inert pair effect.
4. Nitrogen differs from other members of the group in behaviour due to its small size, high
electronegativity, non availalility of vacant d-orbitals and capacity to form stable multiple
bond.
5. Pure dinitrogen is obtained by the thermal decomposition of sodium azide NaN 3 or
Barium azide, Ba(N3)2.
6. Dinitrogen is used in the manufacture of ammonia, nitric acid, calcium cyanamide etc.
7. Calcium cyanamide reacts with water to form ammonia. Therefore, it is used as a
fertilizer under the name nitrolim (CaCN 2 + C)
8. Dinitrogen forms oxides in various oxidation states as N 2O, NO, N2O3, NO2, N2O4 and
N2O5.
9. Ammonia, a colourless gas, lighter than air, soluble in water, used in preparation of
fertilisers like urea and ammonium sulphate. Liquid NH 3 is a good refrigerant.
10. Haber's process : N2 + 3H2 2NH3 + 93.6 kJ mole
An optimum temperature of 5000 C and 200 atmospheric pressure is used for maximum
yield. Finely divided iron containing molybdenum as promoter is used as catalyst.
11. Ammonia is prepared in the laboratory by heating NH 4Cl + CaO CaCl2 + 2NH3 +
H2O .
12. The brown precipitate formed by ammonia with Nessler's reagent (alkaline solution of
K2Hg I4) is due to formation of iodide of Millon's base.
13. Nitric acid is a colourless liquid, highly corrosive, hygroscopic, soluble in water, used
in the purification of gold and silver, extensively used as laboratory reagent.
14. Ostwald's Process for manufacture of HNO3.
Pt
4NH3 + 5O2 ¾ ¾
0
® 4NO + 6H O + 21.5 kcal.
2
800 C
2NO + O2 2NO2
4NO2 + 2H2O + O2 4HNO3.
15. In the brown ring test for the detection of NO3– group, Fe2+ acts as a reducing agent and
forms [Fe(H2O)5NO]2+, the brown coloured complex.
16. White phosphorus catches fire readily and burns with a greenish glow. This phenomenon
is called as 'Chemiluminescence' or 'Phosphorescence'. Therefore, white phosphorus is
kept under water.
17. b - Black phosphorus is good conductor of electricity.
18. Phosphine is a colourless gas with rotten fish small, heavier than air, slightly soluble in
water used for signalling in the sea. (Holme's signal)
19. Phosphine (PH3) is prepared in the laboratory by heating yellow phosphorus with NaOH.
P4 + 3NaOH + 3H2O 3NaH2PO2 + PH3
20. Collection of gases
NH3 - downward displacement of air.
PH3 - downward displacement of water.
21. Phsophorus forms halides having common formula PX 3 or PX5 (where X = halogen).
22. In PCl5, the central P - atom is sp3d - hybridised and the molecule is trigonal bipyramidal
in gaseous and liquid state. In solid state it exists as an ionic solid [PCl 4]+ [PCl6]–.
23. Phsophorus forms a number of oxo-acids. The basicity of those oxo-acids depends upon
the number of P–OH groups present.
24. The oxo-acids which have P–H bonds are good reducing agents.
QUESTIONS
A. Very short answer type questions : (1 mark each)

1. Which is the anhydride of nitric acid ?
2. Balance the equation.
Cu + HNO3 ® Cu(NO3)2 + H2O + NO
3. What happens when ammonium chloride is heated with quick lime ?
4. Name two elements of group VA of periodic table.
5. How can you get nitric acid from potassium nitrate ?
6. Which catalyst is used in the manufacture of ammonia in Haber's process ?
7. Which of the following gas is evolved when NH4NO3 is strongly heated ?
(a) NO (b) N2O (c) NH3 (d) N2
8. What substance is used for drying ammonia gas ?
9. Write the formula of nitric anhydride.
10. Phosphine catches fire because of the presence of ——— as impurity in it ?

11. What is producer gas ?
12. Name the catalyst used in the manufacture of nitric acid by Ostwald process.
13. Write the reaction of thermal decomposition of sodium azide.
14. What is the basicity of H3PO4?
B. Short answer type questions (2 marks each) :

1. What happens when ammonia reacts with chlorine ?
2. What happens when ammonia gas is passed through copper sulphate solution ?
Give equations.
3. How ammonia is prepared in the laboratory ?
4. What is the action of conc. HNO3 on copper ? Give equation.
5. Why ammonia is not dried by cocentrated H2SO4 ?
6. Why ammonia gas is not collected by the displacement of water ?
7. What happens when ammonium chloride is heated with slaked lime ?
8. What is the best substance for drying ammonia and why ?
9. What happens when ammonia is passed over red hot copper oxide.
10. State the reaction of conc. HNO3 with sulphur. Give equation.
11. In the ring test for nitrate, which complex compound is formed ?
12. Why ammonia gas is not dried by conc. H2SO4 ?
13. How ammonia gas is tested with Nessler’s reagent ?
14. What happens when very dilute nitric acid reacts with zinc ?
15. Write the equation for the preparation of phosphine.
16. How does magnesium react with very dilute nitric acid ?
17. What happens when phosphine is passed through silver nitrate solution, give
equation.
18. Why does NH3 forms hydrogen bond but PH3 does not ?
19. Give the reasonating structures of NO2 and N2O5.
20. Explain why NH3 is basic while BiH3 is only feebly basic.
21. Nitrogen exists as a diatomic molecule and phosphorus as P 4. Why ?
22. The HNH bond angle is higher than HPH, HAsH and HSbH angles. Why?
(Hint : The decrease in electronegativity down the group leads the bond pairs to
lie close to each other as repulsion is less)
23. Why does the reactivity of nitrogen differs from that of phosphorus?
24. Why nitrogen does not form pentahalide, but phosphorus pentahalide exists?
25. Explain why Bismuth is a strong oxidising agent in the pentavalent state.
26. Explain why stability of +5 oxidation state decreases down the group 15 of the
periodic table.
27. Why does nitrogen shown catenation property less than phosphorus.
28. Why is N2 less reactive at room temperature?
29. Explain why ammonia acts as a ligand?
C. Short answer type questions (3 marks each) :

1. Why is BiH3 the strongest reducing agent among all hydrides of Group-15 elements?
2. Give resonating structure of NO2, N2O5 and N2O.
3. Why does R3P = O exists but R3N = O does not. (R = alkyl group)
4. Give the disproportionation reaction of H3PO3.
5. Arrange the following in the order of increasing bond strength : NH 3, PH3, AsH3,
SbH3, BiH3. Give suitable explanation for your answer.
6. Write the difference between the properties of red phosphorus and white
phosphorus?

1. How is ammonia prepared in the laboratroy? Write with equation what happens
when it reacts with (a) cupric oxide (b) insufficient quantity of chlorine
(c) CuSO4Soln (d) Excess of chlorine.
2. Discuss briefly the principle involved in the Ostwald's process of manufacture of
HNO3. How does conc. HNO3 reacts with iodine and copper?
3. Describe the laboratary method of preparation of phosphine. State three of its
properties with equations.
4. Name important oxides and oxyacids of nitrogen and phosphorus and write their
formulae.
MULTIPLE CHOICE TYPE QUESTIONS

1. Elements of Gr 15 belong to
(a) s - block (b) p - block
(c) d - block (d) f - block
2. The outer electronic configuration of 15 group elements is :
(a) ns2 np1 (b) ns2 np2
(c) ns2 np3 (d) ns2 np4
3. In the reduction of HNO3 to N2O, the number of moles of electrons involved per mole
of HNO3 is
(a) 8 (b) 4
(c) 2 (d) 3
4. Which of the following oxides combines with Fe(II) ions to form a brown complex ?
(a) N2O (b) NO
(c) N2O5 (d) N2O3
5. Which of the following is neutral.
(a) N2O3 (b) N2O4
(c) N2O5 (d) N2O
6. Conc. HNO3 oxidises phosphorus to
(a) H3PO4 (b) P2O5
(c) H2PO3 (d) H4P2O7.
7. Which of the following liberates H2 with nitric acid ?
(a) Zn (b) Cu
(c) Mg (d) Hg
8. Which of the following is least basic ?
(a) NF3 (b) NCl3
(c) NI3 (d) NBr3
9. Which of the following is most explosive ?
(a) NCl3 (b) PCl3
(c) AsCl3 (d) All
10. In the manufacture of safety match sticks we use
(a) White P (b) Black P
(c) Violet P (d) Red P.
11. Which is oxidised in air ? (AFMC 1987)
(a) White P (b) CH4
(c) H2O (d) SO2
12. When Conc H2SO4 in added to dry KNO3, brown fumes are evolved. These fumes are
(a) SO2 (b) SO3
(c) N2O (d) NO2
13. Which of the following has tetrahedral structure ?

(a) NH3 (b) NH4+
(c) [K4[Fe(CN)6] (d) [Ni(CN)4]2–
14. Phosphine is prepared by the reaction of
(a) P and H2SO4 (b) P and NaOH
(c) P and H2S (d) P and HNO3
15. Aquaregia is a mixture of
(a) 3 HCl + 1 HNO3 (b) 3 HNO3 + 1 HCl
(c) H3PO4 + H2SO4 (d) HCl + CH3COOH.
16. With excess of Cl2, ammonia gives
(a) NCl3 (b) HCl
(c) NH4Cl (d) N2O
17. NH3 is a lewis base. It forms complexes with cations. Which one of the following
cations does not form complex with NH3 ?
(a) Ag+ (b) Cu2+
(c) Cd2+ (d) Pb2+
18. Which of the following forms of phosphorus is most stable ?
(a) Red P (b) White P
(c) Black P (d) all are stable
19. FeSO4 forms brown ring with
(a) NO3 (b) NO2
(c) NO (d) N2O3
20. In Birkland and Eyde process, the temperature of electric arc is about ?
(a) 15000 C (b) 40000 C
(c) 30000 C (d) 20000 C
21. The anhydride of HNO2 is
(a) NO (b) N2O3
(c) N2O (d) N2O5
22. Which of the following does not exist
(a) NCl5 (b) AsF5
(c) PF5 (d) SbCl5
23. The gas obtained on heating ammonium nitrite is
(a) N2O (b) N2
(c) N2O3 (d) N2O4
24. The gas not having oxidising and bleaching property is

(a) Chlorine (b) Ozone
(c) SO2 (d) N2O
25. Sequence of acidic character is
(a) SO2 > CO2 > CO > N2O5 (b) SO2 > N2O5 > CO > CO2
(c) N2O5 > SO2 > CO > CO2 (d) N2O5 > SO2 > CO2 > CO
26. Extra pure N2 can be obtained by heating
(a) NH3 and CuO (b) NH4NO3
(c) (NH4)2Cr2O7 (d) Ba(N3)2
27. An inorganic salt (A) is decomposed on heating to give two products (B) and (C).
Compound (C) is a liquid at room temperature and is neutral to litmus while compound
(B) is a colourless neutral gas. Compounds (A), (B) and (C) are
(a) NH4NO3, N2O, H2O (b) NH4NO2, NO, H2O
(c) CaO, H2O, CaCl2 (d) Ba(NO3)2, H2O, NO2
28. With excess Cl2, ammonia forms
(a) nitrogen (b) nitrosyl chloride
(c) ammonium chloride (d) nitrogen trichloride
29. Which statement is wrong for NO ?
(a) It is anhydride of HNO2 (b) Its dipole moment is 0.22D
(c) It forms dimer (d) It is paramagnetic
30. The brown ring test for nitrates depends upon
(a) the reduction of nitrate to nitric oxide
(b) oxidation of nitric oxide to nitrogen dioxide
(c) reduction of ferrous sulphate to iron.
(d) oxidising action of sulphuric acid.
1. b 2. c 3. b 4. b 5. d 6. a
7. c 8. a 9. a 10. d 11. a 12. d
13. b 14. b 15. a 16. a 17. d 18. a
19. c 20. c 21. b 22. a 23. b 24. d
25. d 26. d 27. a 28. d 29. a 30. a
qqq
CHAPTER - 8
GROUP 16 ELEMENTS : OXYGEN FAMILY
Group 16 of the periodic table consists of the normal elements oxygen, sulphur, selenium,
tellurium and polonium. Oxygen and sulphur are the typical non-metals, selenium and tellurium
are metalloids and polonium is a radioactive metal. These are also called 'chalcogens'
(pronounced as kal' - ke - jens) or ore forming elements because many metal ores occur as
oxides and sulphides.
8.1 OCCURRENCE :
Dioxygen, the most vital component of our atmosphere comprises of about 21% of dry
air by volume. It is also the most abundant element in the earth's crust because most of the
elements are available in the form of their oxides, carbonates, sulphates, nitrates etc.
Sulphur comprises of only 0.03 – 0.1% of earth's crust in the form of ores like
(a) Gypsum CaSO4×2H2O (b) Epsom MgSO4×7H2O
(c) Galena PbS (d) Baryte BaSO4
(e) Zinc blende ZnS (f) Copper pyrite CuFeS2
(g) Cinnabar HgS etc.
In volcanoes sulphur is present in the form of hydrogen sulphide gas. Organic materials
like garlic, onion, mustard, wooll, eggs etc. also contain sulphur.
Selenium and Tellurium are present as metal selenides and tellurides in sulphide ores.
In Thorium and Uranium minerals Polonium is present as a decay product.

The general outermost electronic configuration of Group 16 elements is given by
ns2 np4 (Table 8.1).
GROUP 16 ELEMENTS : OXYGEN FAMILY 261
Table 8.1 : Properties of elements of oxygen family

Property O S Se Te Po
Atomic number 8 16 34 52 84
Atomic mass/gmol–1 16 32 78.2 127.6 210
Electronic configuration [He]2s2 [Ne]3s2 [Ar]3d10 [Kr]4d10 [Xe]4f14

2p4 3p4 4s24p4 5s25p4 5d106s26p4
Ionisation Enthalpy 1314 1000 941 869 813

(kJ mol–1)
Electronegativity 3.50 2.58 2.55 2.01 1.76
Atomic radius (Ä) 0.73 1.02 1.16 1.35 1.52
Melting point / K 55 392 a 490 b 723 527
Boiling point / K 90 718 958 1263 1235
a monoclinic form, a grey form.

Atomic radius or size increases from oxygen to polonium. This is due to addition of
electronic shells with increase in atomic numbers.
8.2.3 Ionisation Enthalpy :

Ionisation enthalpy decreases down the group (Table 8.1) due to increase in size. The
elements of this group possess lower ionisation enthalpy values as compared to the Group 15
elements of the same period because of their extra stability due to half filled p-orbitals.
Oxygen is the most electronegative element in the group. Next to fluorine it has the
highest electronegative value among the elements. The electronegativity decreases, hence metallic
character increases from oxygen to polonium.
8.2.5 Physical State :

Oxygen exists as a diatomic gas at room temperature. Sulphur, Selenium, Tellurium
exist as octa atomic solids and polonium is a radioactive metal with a very short half-life.

The four p-electrons in the last orbit are arranged in the three 'p' orbitals as np 2x np1y np1z .
Thus, there are two half-filled 'p' orbitals which are responsible for chemical bonding with
other elements. Thus, they show the properties of normal elements with usual valency of 2 and
maximum valency 6. For oxygen, the –2 oxidation state is predominant. The stability of –2
oxidation state decreases down the group. Thus polonium hardly show –2 oxidation state. As
oxygen is less electronegative than fluorine in OF 2, it has +2 oxidation state. Other elements
show +2, +4, +6 oxidation states, +4, +6 being more common. Stability of +6 oxidation state
decreases down the group while that of +4 oxidation state increases due to inert pair effect.
However, bonding in both +4 and +6 oxidation states is covalent in nature.
8.3.2 Reaction with Hydrogen :
All elements of this group form volatile hydrides of the type H 2R. The stability of the
hydrides diminishes from oxygen to polonium. While water is an odourless liquid, the other
hydrides are offensive smelling gases at ordinary temperature. The liquid character of H 2O is
due to hydrogen bonding in molecules of water. Their acidic character increases from H 2O to
H2Te due to decrease in bond enthalpy.
8.3.3 Reaction with Oxygen :
S, Se and Te form oxides of MO2 and MO3 type.
Ex : SO2, SeO2, TeO2, PoO2, SO3, SeO3 and TeO3
The trioxides are more acidic than dioxides.
8.3.4 Reaction with Halogens :
The elements of this group form a number of halides, a few examples being mentioned
below.
Examples :
O F2O, Cl2O, ClO2, Cl2O7 , Br2O, I3O5 etc.
S S2F2, S2F4, SF6, S2Cl2, SCl2, S2Br2
Se Se2F2, Se2F4, SeF6, Se2Cl2, SeCl4, SeBr2, SeBr4
Te TeF4, TeF6, TeCl2, TeCl4, TeBr2, TeBr4, TeI4
Po PoCl2, PoCl4, PoBr2, PoBr4, PoI4
The stability of the halides decreases in the order F – > Cl– > Br– > I–
All the elements of the group except oxygen form dichlorides and dibromides. Here
the dihalides are formed by sp3 hybridisation and have tetrahederal structure. The monohalides
are dimeric in nature.
Ex : S2F2, S2Cl2, Se2Cl2, Se2Br2 etc. They undergo disproportionation as given below.
2 Se +21 Cl 2 ® Se +4 Cl 4 + 3 Se 0
The tetrafluorides like SF4, SeF4, TeF4 etc. have sp3d hybridisation and have trigonal
bipyramidal structure where one of the equatorial positions is occupied by a lone pair of
electrons. This geometry is also called as "see-saw" geometry.
F F
F F
m
165 p
° F
1 73
pm
S 102° S 1 55
..
F 90°
F F
F F
Fig. 8.1(a) : Structure of SF 4 Fig. 8.1(b) : Structure of SF 6
All hexafluorides have octahedral structures. For example : S in SF 6 is sp3d2 hybridized

and hence has octahedral structure.
8.3.5 Formation of Oxyacids :
S, Se and Te form similar oxyacids. These are formed by the reaction of dioxide or
trioxide with water.
H2SO3 H2SeO3 H2TeO3
H2SO4 H2SeO4 H2TeO4
Thus we see that there is close resemblance among oxygen, sulphur, selenium, tellu-
rium and polonium. Hence, their position in the same group of the periodic table is justified.
8.4 ANOMALOUS BEHAVIOUR OF OXYGEN :

Anomalous behaviour of oxygen is due to
(i) its small size, high electronegativity.
(ii) non-availability of vacant d-orbitals.
(i) Effect of small size : Because of small size and high electronegativity O-atom
carries partial –ve charge in water molecule which leads to hydrogen bonding.
Thus H2O is a liquid, whereas H2S is a gas.
(ii) Absence of d-orbitals : The absence of d-orbitals limits its covalency to four,
whereas other elements may show covalency beyond four.
8.5 DIOXYGEN :
8.5.1 Preparation :
(1) Laboratory Method : Dioxygen can be prepared in the laboratory by the following
methods.
(a) From chlorates, nitrates and permanganates : By heating oxygen
containing salts like chlorates, nitrates and permanganates dioxygen gas is
obtained.
Heat
2KClO3 (s) MnO2 2KCl (s) + 3O2(g)
Potassium chlorate
Heat
2KMnO4(s) K2MnO4(s) + MnO2(s) + O2(g)
Potassium permanganate Potassium manganate
Heat
2KNO3 (s) 2KNO2(s) + O2(g)
Potassium nitrate Potassium nitrate
(b) The oxides of some heavy metals like Hg, Pb, Ag etc. on heating
decompose to liberate dioxygen.
D
2 HgO (s) ¾¾® 2 Hg (l) + O2(g)
D
2 Pb3O4 (s) ¾¾® 6 PbO(s) + O2(g)
D
2 Ag2O (s) ¾¾® 4 Ag(s) + O2(g)
(c) From Hydrogen peroxide : Hydrogen peroxide decomposes in presence

of catalysts such as finely divided Nickel and Manganese dioxide to give
dioxygen.
MnO (s)/Ni
2H2O2 (aq) ¾¾ ¾ ¾
2
¾¾® 2H2O (l) + O2(g)
(d) Electrolysis of water : Electrolysis of acidulated water leads to release of

dihydrogen gas at cathode and dioxygen gas at anode.
2H2O ¾Electrolysis
¾ ¾ ¾ ¾¾® 2H2(g) + O2(g)
(2) Commercial method of preparation : Dioxygen is obtained from liquid air by
the method of fractional distillation. Air free from CO 2 and water vapour is
subjected to liquefaction, followed by fractional distillation. The fraction collected
at 77K is liquid nitrogen. The liquid left over (Boiling point 90K) is dioxygen.
8.5.2 Properties :
(1) Dioxygen is a colourless, odourless and tasteless gas.
(2) Its solubility is about 3.08 cm3 in 100 cm3 of water at 298K, which is responsible
for sustainability of marine and aquatic life.
(3) It liquifies at 90K and freezes at 55K.
(4) Dioxygen has three stable isotopes 16O, 17O and 18O.
(5) Dioxygen is paramagnetic in nature in spite of having even number of electrons
(which can be explained on the basis of Molecular Orbital Theory).
The bond dissociation energy of dioxygen molecule is high (493.4 kJ mol –1) due
to presence of double bond between the atoms. As the reactions with dioxygen are
exothermic in nature which provide sufficient energy to carry out the reaction,
oxygenation process is most common.
(1) Reaction with metals : Dioxygen directly combines with most of the metals
(except noble metals such as gold and platinum) to form their respective oxides.
4 Na (s) + O2 (g) ® 2 Na2O (s).
4 Al (s) + 3O2 (g) ® 2 Al2O3 (s).
Sodium also reacts with dioxygen at 575K to form sodium peroxide.
2 Na (s) + O2(g) ¾575K

¾¾ ¾® Na2O2(s).
Magnesium burns in dioxygen to form magnesium oxide.
2 Mg (s) + O2(g) ¾Heat

¾¾® 2 MgO (s).
(2) Reaction with Non-metals : Dioxygen combines with non-metals (except the
noble gases) and produce the corresponding oxides.
D
C (s) + O2(g) ¾¾® CO2 (g)
D
P4(s) + 5O2(g) ¾¾® 2 P2O5 (g)
D
S(s) + O2(g) ¾¾® SO2(g)
(3) Reaction with compounds : Some compounds are catalytically oxidised by

dioxygen.
2 SO2 (g) + O2(g) ¾V O5

¾® 2 SO3(g)
¾2 ¾
720K, 2atm. pressure
4 HCl (g) + O2(g) ¾700K,

¾¾¾¾¾
CaCl 2
® 2 H2O(g) + Cl2(g)
Uses : (1) Dioxygen is an essentail component for the process of respiration and combustion.
(2) Oxygen cylinders are used in hospitals, high altitude flying and in mountaneering.
(3) Liquid dioxygen with hydrazine is used as a rocket fuel.
(4) It is used in oxy-acetylene torches which provide high temperaure for cutting and
welding purposes.
8.6 CLASSIFICATION OF OXIDES :
As discussed earlier, oxygen reacts with most of the elements of the periodic table and
form binary compounds known as oxides.
These oxides may be classified as :
(I) Simple oxides (e.g.MgO, Al2O3 etc.)
(II) Mixed Oxides (e.g.Pb3O4, Fe3O4 etc.)
(I) Simple Oxides : The oxides in which the element other than oxygen present in
the compound exhibit a single valency are known as simple oxides. Depending
on their nature they may be further classified as :
(a) Acidic oxides, (b) Basic oxides, (c) Amphoteric oxides and (d) Neutral oxides.
(a) Acidic Oxides : The oxide which dissolves in water to give an acid is
termed as acidic oxide.
(e.g. SO2, Cl2O7, CO2, N2O5 etc.)
SO2 (g) + H2O (l) ® H2SO3 (aq)
Sulphurous acid.
Cl2O7 (g) + H2O (l) ® 2 HClO4 (aq)
Perchloric acid
CO2 (g) + H2O (l) ® H2CO3(aq)
Carbonic acid
N2O5 (s) + H2O (l) ® 2 HNO3(aq)
Nitric acid
Generally the oxides of non-metals are acidic in nature. In addition to these, the oxides
of some metals in higher oxidation state also have acidic character. Ex. Mn 2O7, CrO3, V2O5 etc.
Mn2O7 + H2O ® 2HMnO4
Permanganic acid
CrO3 + H2O ® H2CrO4
Chromic acid
(b) Basic Oxides : The oxides which combine with water to give a base are
known as basic oxides (e.g. Na2O, CaO, BaO etc.)
Na2O(s) + H2O(l) ® 2NaOH(aq)
CaO(s) + H2O(l) ® Ca(OH)2(aq)
BaO(s) + H2O(l) ® Ba(OH)2(aq)
Usually the metallic oxides are basic in nature.
(c) Amphoteric Oxides : Some metal oxides exhibit the characteristics of

both acidic as well as basic oxides. They are known as amphoteric oxides.
(e.g. Al2O3, ZnO, PbO etc.)
Al2O3(s) + 6 HCl (aq) + 9 H2O(l) ® 2 [Al (H2O)6]3+ + 6 Cl–
Basic Hexaaquaaluminium (III) ion.
Al2O3(s) + 6NaOH(aq) + 3H2O(l) ® 2Na3 [Al(OH)6] (aq)
Acidic Sodium hexahydroxoaluminate (III)
(d) Neutral Oxides : There are some oxides which are neither acidic nor basic
in nature. Such oxides are known as neutral oxides (e.g. H2O, CO, NO and
N2O)
(II) Mixed Oxides : These oxides consist of two simple metal oxides where the
metal is present in different oxidation state. These oxides exhibit the properties
of both the oxides simultaneously. (e.g. Pb3O4, Fe3O4, Mn3O4 etc.)
Pb3O4
Ex : or + 4 HNO3 ® PbO2 + 2 Pb(NO3)2 + 2H2O
PbO2 × 2PbO
Fe3O4
or + 8 HCl ® 2 FeCl3 + FeCl2 + 4 H2O
Fe2O3 × FeO
8.7 OZONE :
Molecular formula : O3 Molecular mass : 48
Ozone is the active allotrope of oxygen.
8.7.1 Occurrence :
Ozone occurs in minute traces (about 1 part per ten million) in air, especially in sea
air and in some what larger quantities in the upper atmosphere.
8.7.2 Preparation :
Pure ozone is very difficult to prepare. A mixture of ozone with air or oxygen is
generally prepared by the action of silent electric discharge on oxygen
3O2 2O3 D H = + 142 kJ mol–1
Ozone is unstable at ordinary temperature. Hence, ozone should be removed from the
reaction medium immediately to avoid decomposition. Low temperature is used in order to
slow down the rate of decomposition.
Two types of apparatus, viz. the Siemen's ozoniser or Brodie's ozoniser are generally
used for the preparation of ozone in the laboratory.
(i) Siemen's ozoniser : The apparatus in made up of two co-axial glass tubes fused with
each other at one end as shown in the Fig 8.2. The inside of the inner tube and the
outside of the outer tube are covered with tin foils.
A current of dry and pure oxygen is passed through the space between the two
tubes and is subjected to silent electric discharge by connecting the tin-foils to an
induction coil. About 10 percent of oxygen is converted to ozone and the mixture
coming out of the apparatus is ozonised oxygen.
TIN FOIL DRY O2
OZONISED
OXYGEN
TIN FOIL
INDUCTION COIL
Fig. 8.2 Siemen's ozoniser

(ii) Brodie's ozoniser : The apparatus consists of U-shaped glass tube one limb of which
is wider than the other. A narrow glass tube, closed at one end is introduced into the
wide limb and the two are fused together at the open ends, so that an annular space
is left between the two tubes.
OZONISED
OXYGEN
OXYGEN
DILUTE SULPHURIC
ACID
Fig. 8.3 Brodie's Ozoniser
The wide limb is also provided with a side tube. Dilute sulphuric acid is taken in the
inner tube and the whole apparatus is kept immersed in a glass jar containing the same
dilute sulphuric acid as in the inner tube. Two platinum electrodes are introduced, one
in the inner tube and the other in the glass jar.
The two platinum electrodes are connected with terminals of an induction coil,
and a slow stream of pure oxygen is passed through the side tube, thus subjecting the
gas to a series of silent electric discharge. Ozonised oxygen is formed and collected
at the outlet.
N.B.: By (i) Cooling the apparatus to 273K, (ii) Using powerful coil and (iii) avoiding
sparks, 25% of oxygen by weight may be converted into ozone.
Pure ozone : Pure ozone may be obtained by cooling ozonised oxygen in liquid air and
subjecting the condensed deep blue liquid to fractional evaporation. Liquid oxygen evaporates
first (90K), leaving behind less volatile liquid ozone, which may be evaporated (161.1K) and
collected subsequently.
8.7.3 Properties of ozone :
(a) Physical :
1. Ozone is a pale blue gas with a fishy odour.
2. It is heavier than air.
3. It can be condensed at 161.1K to a deep blue explosive liquid.
4. It is slightly soluble in water, but the solubility is more than oxygen. It readily
dissolves in oil of turpentine, which is used as an adsorbent for the gas.
5. Unlike oxygen which is paramagnetic, ozone is diamagnetic.
6. Its concentration above 100 ppm makes breathing uncomfortable resulting
headache and nausea.
(b) Chemical :
1. Stability : Ozone is an unstable gas. Its decomposition to oxygen is a thermodynamically
favourable process as DH = –ve and DS +ve for it thus making DG = –ve. Hence the
high concentration of ozone is dangerously explosive.
2. Oxidising agent : Ozone is a powerful oxidising agent because it readily undergoes
decomposition to produce atomic oxygen.
O3 ® O2 + O
(i) With metals : Ozone reacts with all the metals except gold and platinum producing
oxides. Mercury loses its mobility and forms mercurous oxide which sticks to
glass. This is called tailing of mercury.
O3 ® O2 + O
2Hg + O ® Hg2O
———————————
2Hg + O3 ® Hg2O + O2
Silver is oxidised to silver oxide.
O3 ® O2 + O
2Ag + O ® Ag2O
———————————
2Ag + O3 ® Ag2O + O2
(ii) With lead sulphide : Lead sulphide (black) is oxidised to lead sulphate (white).
[O3 ® O2 +O ] x 4
PbS + 4O ® PbSO4
————————————
PbS + 4O3 ® PbSO4 + 4O2
(iii) With potassium iodide : It oxidises potassium iodide to iodine.
O3 ® O2 +O
[KI + H2O ® KOH + HI] x 2
2HI + O ® H2O + I2
————————————————
2KI + H2O + O3 ® 2KOH + I2 + O2
When ozone reacts with an excess of KI solution buffered with a borate buffer
(pH 9.2) iodine is liberated quantitatively which can be titrated against a standard
solution of sodium thiosulphate (Na2S2O3). This reaction is used for quantitative
estimation of ozone.
(iv) With halogen acids : It oxidises halogen acids to halogens.
O3 ® O2 +O
2HCl + O ® H2O + Cl2
——————————————
2HCl + O3 ® Cl2 + H2O + O2
(v) With sulphur dioxide : It oxidises sulphur dioxide to sulphur trioxide.

O3 ® O2 +O
SO2 + O ® SO3
——————————
SO2 + O3 ® SO3 + O2
(vi) With stannous chloride : It oxidises acidified stannous chloride to stannic
chloride.
O3 ® O2 +O
[SnCl2 + 2HCl + O ® SnCl4 + H2O] x 3
———————————————————
3SnCl2 + 6HCl + O3 ® 3 SnCl4 + 3H2 O
(vii) With potassium ferrocyanide : It oxidises potassium ferrocyanide to potassium
ferricyanide
O3 ® O2 +O
2K4 [Fe (CN)6] + H2O + O ® 2K3 [ Fe (CN)6 ] + 2KOH
——————————————————————————
2K4 [Fe (CN)6] + H2O + O3 2K3 [ Fe (CN)6 ] + 2KOH + O2
(ix) With ferrous sulphate : It oxidises acidified ferrous sulphate to ferric sulphate
O3 ® O2 + O
2FeSO4 + H2SO4 + O ® Fe2 (SO4)3 + H2O
———————————————————––––––––––
2FeSO4 + H2SO4 + O3 ® Fe2 (SO4)3 + H2O + O2
(x) With potassium manganate : It oxidises a solution of potassium manganate
(green) to potassium permanganate (pink).
O3 ® O2 + O
2K2MnO4 + H2O + O ® 2KMnO4 + 2KOH
—————————————––––––––––——————
2K2MnO4 + H2O + O3 ® 2KMnO4 + 2KOH + O2
(xi) With moist iodine : It oxidises moist iodine to iodic acid.
[ O3 ® O2 + O ] x 5
I2 + 5O ® I2O5
I2O5 + H2O ® 2HIO3
———————————————————
I2 + 5O3 + H2O ® 2HIO3 + 5O2
3. Reducing agent : When ozone reacts with peroxides such as hydrogen peroxide and
barium peroxide, both the reactions undergo reduction with the liberation of oxygen.
H2O2 + O3 ® H2O + 2O2
BaO2 + O3 ® BaO + 2O2
4. Formation of ozonised compounds : It reacts with unsaturated organic compounds

containing double bonds, such as ethylene, to form addition products called ozonides.
CH2= CH2 + O3 ®
CH2 CH2
Ethylene
Ethylene ozonide
5. Bleaching agent : Ozone acts as a bleaching agent. The atomic oxygen that it liberates
on decomposition, oxidises colouring matter to colourless compounds. Thus, it can
bleach vegetable matter, silk, starch, wax and oils.
6. Depletion of ozone layer : The oxides of nitrogen (nitric oxide in particular) combine
rapidly with ozone and destroy the molecules of ozone.
NO(g) + O3(g) ® NO2(g) + O2(g)
The nigrogen oxides emitted from supersonic jet aeroplanes might be slowly
depleting the protective ozone layer in the upper atmosphere because of this reaction.
Freons present in aerosol sprays and used as refrigerants also cause depletion of
ozone layer.
Summary :
O2
Hg, Ag
Hg 2O, Ag2O
PbS PbSO4
KI I2
HCl
Cl2
SO2
SO3
SnCl2
SnCl4
K 4[ FeCN ) 6 ]
O3 K3 [Fe (CN)6 ]
FeSO4
Fe2(SO4)3
I2
HIO3
K 2 MnO4
KMnO4
BaO 2
BaO
CH 2 = CH2
Ethylene ozonide
[O 2 + O ]
Bleaching agent
NO(g)
NO2(g) + O2(g). Depletion of ozone layer
Tests :
1. Ozone can be detected by its sharp characteristic odour (fishy odour).
2. It turns starch iodide paper blue.
3. It turns benzidine paper brown and tetramethyl base paper violet.
4. It produces tailing of mercury.
5. It blackens metallic silver.
6. It cannot decolourise acidified potassium permanganate solution.
8.7.4 Uses : Ozone is used :
1. As a germicide for sterilisation of drinking water.
2. For bleaching silk, ivory, wax and oils.
3. As an oxidising agent.
4. For purifying air especially in under-ground railways, mines, crowded places such as
cinema halls.
5. In the manufacture of synthetic camphor and artiticial silk.
8.7.5 Structure of ozone :
Ozone is not para-magnetic. Hence, all the electrons are paired. The three atoms are
at the apices of an equilateral triangle. It has got sp 2 hybridisation. The bond angle between
O-O-O is 116.5-0 and O-O bond length is 1.28AO . The structure is a resonance hybrid of two
main forms.
0
8A
1.2
116.50
...... .. ..
8.8 SULPHUR :
Allotropic forms of sulphur : Sulphur exists in a number of allotropic forms. Also
a number of allotropic forms of sulphur containing 6-20 sulphur atoms per ring have been
synthesized in the past two decades. Two important allotropic forms of sulphur are :
(a) Rhombic sulphur (µ - Sulphur)
(b) Monoclinic sulphur (b - Sulphur)
(a) Rhombic sulphur (µ - Sulphur) is prepared by dissolving roll sulphur in carbon
disulphide solvent and then evaporating the solution. The octahedral crystals separated out in
this process are rhombic sulphur. It is the most stable allotrope at room temperature.
It is yellow in colour
Its M.P. is 385.8K and has specific gravity 2.06
It is insoluble in water. But dissolves to some extent in alcohol, benzene and ether.
It is readily soluble in carbondisulphide.
(b) Monoclinic sulphur (b - Sulphur) is parepared by melting rhombic sulphur in a
china dish and then cooling it till crust is formed. Two holes are made in crust and the
remaining liquid is poured out. On removing the crust, colourless needle shaped crystals of
monoclinic sulphur are found.
The melting point of b - Sulphur is 393K. At 369K µ - Sulphur changes to b - Sulphur.
Below 369K b - Sulphur changes to µ - Sulphur. This particular 369K temperature is called
transition temperature because both Rhombic and Monoclinic sulphur co-exist at that
temperature.
Above 369K
Rhombic Monoclinic sulphur..
Sulphur
Below 369K
Both these allotropes have S8 molecules packed to give different crystal structures. The
S8 ring in both the forms is puckered and has a crown shape (Fig. 8.4)
C 20 S S
4p
m
107°
S S
S
S S
Fig. 8.4
Cyclo-S6 is another allotropic form of sulphur where six no. of sulphur atoms are
arranged in chair form.
S
205.7 pm
S S
°
1 02 .2
S S
Fig. 8.5 S
Above 1000K sulphur exists as S2 molecule in its vapour state and is paramagnetic in
nature. This is because two unpaired electrons are present in two antibonding p* orbitals like
that of O2 molecule (MO Theory).
8.9 SULPHUR DIOXIDE :

Molecular formula : SO2 Mol. mass : 64
Occurrence : Sulphur dioxide is present in volcanic gases, in the springs of volcanic
districts and in the air of urban and industrial area, where it is produced when coal containing
sulphur compounds is burnt.
Preparation :
1. Synthesis : Sulphur dioxide may be prepared synthetically by burning sulphur in
oxygen or air.
S(s) + O2(g) ® SO2(g)
2. Laboratory method :
(i) Principle : Sulphur dioxide is prepared by heating conc. sulphuric acid with
copper turnings.
Cu + 2H2SO4 ® CuSO4 + 2H2O + SO2
Description : Copper turnings are taken in a round bottomed flask fitted with a thistle
funnel and a delivery tube bent twice at right angles (Fig.8.6).The flask is clamped to a stand
and placed on a wire gauze.
Conc. H2SO4
Thistle Funnel
Clamp Cu +
Conc.H2SO4
Gas Jar
Flask
Wire
Gauze
Burner
Tripod
Stand
Fig. 8.6 Preparation of SO2
Concentrated sulphuric acid is poured through the thistle funnel so that the end of the
funnel dips in the acid. On heating the flask sulphur dioxide is evolved.
(iii) Collection : The gas is heavier than air and soluble in water, so it is collected
in gas jars by the upward displacement of air.
(iv) Purification : The gas is dried by passing through concentrated sulphuric acid.
3. Other methods : SO2 can be prepared :

(i) From sulphites and bisulphites : It can be prepared by the action of dil. HCl
or dil. H2SO4 on metallic sulphite or bisulphite at ordinary temperature.
CaSO3 + 2HCl ® CaCl2 + H2O + SO2
(ii) From sulphuric acid : It may be prepared by heating metals like copper, mercury,
silver etc. and non-metals like carbon, sulphur etc. with conc. sulphuric acid.
Hg + 2H2SO4 ® HgSO4 + 2H2O + SO2
C + 2H2SO4 ® 2H2O + CO2 + 2SO2
S + 2H2SO4 ® 2H2O + 3SO2
(iii) Manufacture : On a large scale, sulphur dioxide is prepared.
(a) By burning crude sulphur in air.
S + O2 ® SO2
(b) By roasting iron pyrites in air.
4FeS2 + 11O2 ® 2Fe2O3 + 8SO2
Properties of SO2 :
(a) Physical
1. It is a colourless gas with suffocating smell of burning sulphur and is poisonous.
2. It is readily soluble in water. About 80 litres of the gas dissolve in one litre of water
at ordinary temperature.
3. It may be easily liquified to a colourless liquid which boils at 263K and freezes at
198K.
(b) Chemical :
1. Stability : Sulphur dioxide is thermally very stable. It dissociates into sulphur trioxide
and sulphur by electric spark (1473K) or on strong heating.
3SO2 ® 2SO3 + S
2. Combustibility : The gas neither burns nor ordinarilly supports combustion.
3. Acidic nature.
(i) It is highly soluble in water and its solution is acidic due to the formation of
unstable sulphurous acid.
SO2 + H2O H2SO3
(ii) Reaction with basic oxides and alkalis :
It reacts with basic oxides and alkalis forming sulphites.
CaO + SO2 ® CaSO3
2NaOH + SO2 ® Na2SO3 + H2O
Na2SO3 + SO2 (excess) + H2O ® 2NaHSO3
(iii) Reaction with lime water : It turns lime water milky. With excess of gas,
milkiness disappears. Insoluble calcium sulphite is converted to soluble calcium
bisulphite.
Ca(OH)2 + SO2 ® CaSO3 + H2O
CaSO3 +H2O + SO2 ® Ca (HSO3)2
4. As reducing agent : In presence of moisture, it acts as a strong reducing agent. This
is due to liberation of nascent hydrogen as per the following potential equation.
SO2 + 2H2O ® H2SO4 +2H
Similarly, it absorbs oxygen in presence of an oxidising agent :
SO2 + H2O + O ® H2SO4
Since SO2 loses electrons during a chemical reaction, hence it is a reducing agent.
SO2 + 2H2O ® SO42– + 4H+ + 2e
Hence, under all the conditions it acts as a powerful reducing agent.
(i) With ferric salts
(a) SO2 reduces ferric chloride solution to ferrous chloride.
SO2 + 2H2O ® H2SO4 + 2H
2FeCl3 + 2H ® 2FeCl2 + 2HCl
(b) Ferric sulphate is reduced to ferrous sulphate in solution.
SO2 + 2H2O ® H2SO4 + 2H
Fe2(SO4)3 + 2H ® 2FeSO4 + 2H2SO4
–––––––––––––––––––––––––––––––––––––––––
Fe2 (SO4)3 + SO2 + 2H2O ® 2FeSO4 + 2H2SO4
(ii) With potassium permanganate : It decolourises the pink colour of acidified
potassium permanganate solution in cold.
2KMnO4 + 3H2SO4 ® K2SO4 + 2MnSO4 + 3H2O + 5O
5SO2 + 5O + 5H2O ® 5H2SO4
———————————————————————————
2KMnO4 + 5SO2 + 2H2O ® K2SO4 + 2MnSO4 + 2H2SO4
(pink) (colourless)
(iii) With potassium dichromate : It reduces acidified solution of potassium
dichromate (orange) giving a green solution due to the formation of chromic
sulphate.
K2Cr2O7 + 4H2SO4 ® K2SO4 +Cr2 (SO4)3 + 4H2O + 3O
3SO2 + 3O + 3H2O ® 3H2SO4
––––––––––––––––––––––––––––––––––––––––––––––––
K2Cr2O7 + H2SO4 + 3SO2 ® K2SO4 + Cr2(SO4)3 + H2O
(orange) (green)
(iv) With halogens : It reduces halogens to halogen acids in presence of moisture

X2 + SO2 + 2H2O u 2HX + H2SO4 (X = Cl, Br, I)
(v) With potassium iodate : It reduces potassium iodate to iodine.
2KIO3 + 5SO2 + 4H2O ® 2KHSO4 + 3H2SO4 + I2
5. As oxidising agent : It acts as an oxidising agent because it is reduced to sulphur with
some reducing agents. It can also be explained on the basis of ion - electron method
since it gains electrons during a chemical reaction. SO 2 + 4H+ + 4e ® S + 2H2O
(i) With magnesium : When a piece of burning magnesium wire is introduced to
a jar of sulphur dioxide it forms magnesium oxide and fine particles of sulphur
are deposited on the walls of the jar.
2Mg + SO2 ® 2MgO + S
(ii) With hydrogen sulphide : It reacts with H2S to give sulphur
2H2S + SO2 ® 3S + 2H2O
(iii) With hydrogen iodide : It reacts with HI to give iodine.
4HI + SO2 ® 2H2O + S + 2I2
6. As an antichlor : It is known as antichlor since it destroys the properties of chlorine.
SO2 + Cl2 + 2H2O ® H2SO4 + 2HCl
7. As an unsaturated compound (addition reactions)
Sulphur is hexavalent but only four valencies of sulphur are satisfied in SO 2 and the
remaining two valencies of sulphur remains unsatisfied. This makes SO 2 an unsaturated
compound.
(i) It reacts with chlorine in presence of sunlight forming sulphuryl chloride.
SO2 + Cl2 ® SO2Cl2
(ii) It forms an addition product with sodium peroxide.
Na2O2 + SO2 ® Na2SO4
(iii) In presence of platinum, vanadium pentoxide or manganese sulphate as catalyst,
it combines with oxygen to form sulphur trioxide.
2SO2 + O2 ® 2SO3
8. As bleaching agent : In the presence of moisture it possesses strong bleaching properties.
It decolourises vegetable colouring matters to colourless reduction products. On standing
in air, the colourless reduced product is re-oxidised by atmospheric oxygen to regain
its original colour. It bleaches due to reduction and the bleaching is temporary.
SO2 + 2H2O ® H2SO4 + 2H
Coloured substance + H ® Colourless (reduction product)
air ¯
Coloured
Summary Electric spark

SO3 + S
H2O
HH 2SO3
CaO
CaSO
CaSO 3
NaOH
Na
Na 2SO3
Ca(OH) 2
FeCl 3 CaSO
CaSO 3, (excess) Ca (HSO 3)2
FeCl
FeCl 2
KMnO4 (H2SO4 )
MnSO
MnSO 4
K2Cr 2O7 (H2SO4)
Cr
Cr 2 (SO4)3
SO2 X2
HX
KIO 3
II 2
Mg
MgO
MgO
H2S
SS
HI
II 2
Cl 2
SO
SO 2Cl2
Na2O2
Na
Na 2SO4
O2
SO
SO 3
(Catalyst)
Bleaching action
Bleaches
Bleachesby
byreduction
reduction
Tests : I. It can be detected by its characteristic suffocating smell of burning sulphur.

2. It turns acdified potassium dichromate solution green.
3. It decolourises acidified potassium permanganate solution.
4. It turns lime water milky.
Uses : 1. In the manufacture of sulphuric acid.

2. As bleaching agent.
3. As a disinfectant and germicide.
4. As a refrigerent.
5. As an antichlor.
Structure :
The sulphur dioxide molecule is inverted V-shaped with bond angle of 119.5 0.
S
o o
119.50
8.10 SULPHURIC ACID (H2SO4 ) :

Molecular formula : H2SO4 Molecular mass : 98
Occurrence : Free sulphuric acid occurs in traces in rain water. Some mineral springs
also contain this acid.
Methods for the preparation :
1. By the action of water on sulphur trioxide. It is formed by dissolving sulphur
trioxide in water.
SO3 + H2O ® H2SO4
2. By the action of H2O2 on SO2. It is formed by the action of sulphur dioxide on
hydrogen peroxide
SO2 + H2O2 ® H2SO4
3. Laboratory method :
(i) Chemicals required :
(a) Sulphur dioxide (c) Air
(b) Nitric oxide (d) Steam or water
(ii) Principle : Since sulphur trioxide is the anhydride of sulphuric acid, the latter
can be prepared by the action of water on suphur trioxide.
H2O + SO3 H2SO4
When sulphur dioxide and oxygen (or air) are mixed with nitrogen peroxide in pres-
ence of steam or water, a series of reactions takes place at the end of which sulphuric acid is
produced.
Nitrogen peroxide oxidises sulphur dioxide to sulphur trioxide and gets itself reduced
to nitric oxide. Sulphur trioxide reacts with water to produce sulphuric acid.
NO2 + SO2 ® SO3 + NO
SO3 + H2O ® H2SO4
Nitric Oxide, thus formed, again combines with oxygen of the air producing NO 2. This
NO2 oxidises further quantity of SO2 into SO3, which reacts with water to produce more of
H2SO4.
2NO + O2 ® 2NO2
Thus, there is no loss of nitric oxide, and the reactions go on in a cycle. A small
amount of oxide of nitrogen can convert a relatively large quantity of SO 2 into H2SO4. Nitric
oxide acts here as a 'carrier', for it carries oxygen from the air to sulphur dioxide.
(iii) Description : A large flask fitted with a rubber cork through which five glass
tubes are inserted is taken. Four of these tubes reach near the bottom of the flask,
while the fifth is a short one and acts as an exit tube. (Fig.8.7) Air is introduced
through the first tube into the flask and then nitric oxide is passed through the
second tube by connecting it with a Woulfe's bottle in which the gas is generated
by the action of moderate concentrated nitric acid on copper till red fumes are
formed. Sulphur dioxide is prepared in another flask by the action of conc.
H2SO4 on copper and the gas is passed through the third tube. The red fumes,
first formed (NO2) disappears. At this stage steam is passed through the fourth
tube. Steam reacts with SO3 producing sulphuric acid which collects at the bot-
tom of the flask as an oily liquid.
SO EXIT
2 AM
STE
NO 2
AIR
Fig. 8.7 Preparation of H2SO4

Manufacture of sulphuric acid The two common methods are
(a) Chamber process
(b) Contact process
The principle of manufacture of sulphuric acid by Chamber's process is same as that
of the laboratory mehod.
Principle of manufacture of H2SO4 by Contact process
Materials required :
(a) Sulphur dioxide
(b) Air
(c) Platinised asbestos or finely divided platinum or vanadium pentoxide.
Plantinised asbestos :
It is asbestos dipped into platini chloride solution and then taken out and strongly
heated, when a deposit of finely divided platinum on asbestos is obtained.
Principle :
When a mixture of pure and dry sulphur dioxide and oxygen (1:7) is passed over
platinised asbestos or finely divided platinum or vanadium pentoxide (V 2O5) the gases combine
to form sulphur trioxide.
2SO2 + O2 2SO3 + 45, 200 Cal.
The reaction is reversible and exothermic.
Conditions of the process :
1. The mixture of SO2 and air must be free from (i) dust, (ii) sulphur particles, (iii)
arsenious oxide, etc for they poison the catalyst.
2. According to Le-Chatelier's prinicple, the favourable conditions for the formation of
sulphur trioxide is :
(i) Excess of oxygen or air
(ii) High pressure
(iii) Low temperature
The optimum temperature and pressure condition is 450 0 – 5000C and 1.5 – 1.7
atmospheric pressure.
Sulphur trioxide dissolved in H2SO4 to obtain oleum or fuming sulphuric acid. This
gives on dilution with water sulphuric acid of desired concentration.
SO3 + H2SO4 H2S2O7
H2S2O7 + H2O 2H2SO4.
Properties of sulphuric acid :

Physical :
1. It is a colourless, odourless, syrupy liquid.
2. The concentrated acid fumes in the moist air.
3. The acid boils at 3390C and freezes at 10.50C.
4. Its specific gravity is 1.85.
5. It is miscible in water in all proportions with evolution of heat.
6. It is a good conductor of electricity.
7. It is highly hygroscopic and absorbs water vapour.
Chemical :
The chemical properties of sulphuric acid may be discussed under the following headings.
(1) As an acid, (2) As a dibasic acid, (3) As an oxidising agent, (4) Action on metals,
(5) As a desiccating agent, (6) As a dehydrating agent, (7) As a sulphonating agent,
(8) As less volatile than nitric or hydrochloric acids and (9) Action of heat.
1. As an acid : It turns blue litmus red. On adding water it dissociates as follows :
H2SO4 H+ + HSO4–
HSO4– H+ + SO42–
It reacts with bases like oxides, hydroxide and carbonates of metals to form salts.
CaO + H2SO4 CaSO4 + H2O
2NaOH + H2SO4 Na2SO4 + 2H2O
MgCO3 + H2SO4 MgSO4 + CO2 + H2O
2. As dibasic acid : It is a strong dibasic acid and it forms two series of salts i.e. normal
salt (Na2SO4) and acid salt (NaHSO4) with NaOH.
NaOH + H2SO4 NaHSO4 + H2O
2NaOH + H2SO4 Na2SO4 + 2H2O
3. As an oxidising agent : It acts as an oxidising agent because it takes up electrons.
H2SO4 2H+ + 2SO42–
SO42– + 4H+ +2e SO2 + 2H2O
H2SO4 + 2H+ + 2e SO2 + 2H2O

The oxidising action can also be explained by the potential equation as it evolves
atomic oxygen.
H2SO4 H2O + SO2 + O
(i) It oxidises carbon and sulphur to their oxides.
C + 2H2SO4 CO2 + 2SO2 + 2H2O
S + 2H2SO4 3SO2 + 2H2O
(ii) Hydrogen sulphide is oxidised to sulphur.
H2S + H2SO4 2H2O + SO2 + S
(iii) Iodides and bromides are oxidised to iodine and bromine respectively.
KI + 2H2SO4 K2SO4 + SO2 + 2H2O + I2
2KBr + 2H2SO4 K2SO4 + SO2 + 2H2O + Br2
Hydrobromic and hydriodic acids are also oxidised to the corresponding halogens.
2HX + H2SO4 SO2 + 2H2O + X2 (X = Br, I)
4. Action on metals :
(i) Dilute acid reacts with Zn, Fe etc (metals which are above hydrogen in the
electrochemical series) liberating hydrogen.
Zn + H2SO4 ZnSO4 + H2
(ii) Metals like copper, lead etc react with conc. H 2SO4 producing sulphur dioxide.
Cu + 2H2SO4 CuSO4 + 2H2O + SO2
5. As a desiccating agent : Conc. H2SO4 is used as a desiccating agent for acidic gases
(chlorine, carbon dioxide) because it has strong affinity for water.
6. As dehydrating agent : The concentrated acid acts as a dehydrating agent and it
removes water from compounds. It brings about chemical change.
(i) Charring of cane sugar.
C12H22O11 + H2SO4 12C + [ 11H2O + H2SO4]
(ii) Reaction with oxalic acid :
COOH
| + H2SO4 CO + CO2 + [H2O + H2SO4]
COOH
(iii) Reaction with formic acid :

HCOOH + H2SO4 CO + [H2O + H2SO4]
(iv) Reaction with ethyl alcohol :
0
C2H5OH + H2SO4 ¾160 ¾¾
C
¾®
CH2 = CH2 + [H2O + H2SO4]
7. As sulphonating agent : Concentrated H2SO4 is used in the sulphonation of benzene.
C6H6 + HOSO3H C6H5SO3H + H2O
Benzene Sulphuric acid Benzene sulphonic acid
8. As less volatile than HNO3 and HCl :
Conc. H2SO4 is less volatile than HNO3 or HCl and hence used in the preparation of
these acids from metal nitrates and chlorides.
2NaCl + H2SO4 Na2SO4 + 2HCl
2KNO3 + H2SO4 K2SO4 + 2HNO3
9. Action of heat : When heated, gives sulphur dioxide and oxygen.
2H2SO4 2H2O + 2SO2 + O2
Fuming sulphuric acid : When sulphur trioxide is dissolved in conc H2SO4, Pyro-
sulphuric acid is formed. This is known as fuming sulphuric acid.
H2SO4 + SO3 H2S2O7

Precipitation of insoluble salts of sulphates : Calcium, strontium, barium and lead
salt solutions gives insoluble sulphates with dilute sulphuric acid.
M (NO3)2 + H2SO4 MSO4 ¯ + 2HNO3.
Summary :
H 2O
H+ + SO4–2
C aO
CaSO4
N aO H
NaHSO4and Na2SO4
M gC O3
MgSO4
C
CO2
S
SO2
H 2S
S
KI
I2
HX
H2SO4 X2 + SO2
(X = B r, I)
Zn
ZnSO4 + H2O
Cu
CuSO4 + SO2
C 1 2H 2 2O 1 1
C + H 2O
C 6H 6
C6H5SO3H
Na Cl
HCl
K N O3 HNO3
SO3
H2S2O7
SO2 + H2O + O2
Tests : 1. Conc. H2SO4 gives SO2 when heated with copper. The gas turns acidified dichro-
mate paper green.
2. Sulphuric acid gives white precipitate with barium chloride solution which is
insoluble in mineral acids.
3. It gives white precipitate with lead nitrate solution.
Uses : 1. For the manufacture of calcium superphosphate and ammonium sulphate which
are important fertilisers.
2. In the refining of petroleum.
3. In the manufacture of HNO3, HCl, etc.

4. In the manufacture of paints, dyes, drugs, disinfectants, explosives, textiles and
rayon.
5. In the lead storage batteries.
6. As a dehydrating and desiccating agent. It is also an important laboratory reagent.
8.11 OXO-ACIDS OF SULPHUR :

Sulphur forms a number of oxoacids. The molecular formula and structure of impor-
tant oxoacids are given below.
Table - 8.2
Sl.No. Name Molecular formula Structure
..
1. Sulphurous acid H2SO3 S

HO O
OH
2. Sulphuric acid H2SO4 S

HO O
OH
O
3. Peroxomonosulphuric H2SO5 S
O O O H
acid or Caro's acid OH
O O
4. Peroxodisulphuric acid H2S2O5 S S

O O O O
OH OH
O O
5. Pyrosulphuric acid (Oleum) H2S2O7 S S

O O O
OH OH
S
6. Thiosulphuric acid H2S2O3 S

HO O
OH
7. Dithionic acid H2S2O6

HO OH
1. Elements of oxygen family : Oxygen, sulphur, selenium, tellurium and polonium.

2. Electronic configuration : The general electronic configuration in the outer most orbit
is ns2np4.
3. Dioxygen can be prepared in the laboratory by heating KClO3 in presence of MnO2.
4. Liquid dioxygen with hydrazine is used as a rocket fuel.
5. Dioxygen combines with elements to gives oxides, classified as simple and mixed
oxides. In mixed oxides the metal is present in different oxidation states and also
exhibit the properties of both the oxidation states simultaneously.
6. Ozone (O3) is the active allotrope of oxygen. It is pale-blue unstable gas, powerful
oxidising agent, reducing agent, bleaching agent and diamagnetic in nature. The bleaching
action is due to its oxidising property.
7. Ozone is prepared in the laboratory in Siemen's Ozoniser or Brodie's Ozoniser. Pure
ozone may be obtained by cooling ozonised oxygen in liquid air and subjecting the
condensed deep blue liquid to fractional evaporation.
8. Structure of Ozone : The three atoms are at the apices of an equilateral triangle. It
has sp2 hybridisation. O – O – O bond angle is 116.500 and O – O bond length in 1.28
A0.
9. Ozone reacts with mercury forming mercurous oxide which sticks to the glass surface
and it is called 'tailing of mercury'.
10. Sulphur exists in a number of allotropic forms of which µ - and b - forms are most
important. At 369 K (transition temperature) both these forms co-exist.
11. Above 1000K sulphur exists as S2 molecule which is paramagnetic in nature.
12. Sulphur dioxide (SO2) is a colourless gas having smell of burning sulphur, acidic, acts
both as reducing and oxidising agent. It acts as a bleaching agent only in presence of
moisture. The bleaching is due to reduction and temporary.
13. Sulphur dioxide (SO2) is prepared in the laboratory by the action of conc H 2SO4 on
copper turnings.
Cu + 2H2SO4 CuSO4 + 2H2O + SO2.
The gas is collected by upward displacement of air, purified by passing through conc
H2SO4.
14. Sulphur dioxide is inverted V–shaped with bond angle of 119.50.
15. Sulphuric acid (H2SO4) is a colourless, odourless syrupy liquid, highly hygroscopic
in nature. It acts as an oxidising agent, dehydrating agent and sulphonating agent.
16. Sulphuric acid (H2SO4) is prepared in the laboratory by the action of water on
sulphur trioxide.
H2O + SO3 H2SO4.
SO3 is the anhydride of sulphuric acid. It is prepared by the action of nitrogen peroxide
on sulphur dioxide.
NO2 + SO2 SO3 + NO.
17. Sulphuric acid is manufactured by Contact process.
2SO2 + O2 2SO3 + 45,200 Cals.
SO3 + H2SO4 H2S2O7
H2S2O7 + H2O 2H2SO4.
Platinised asbestos or finely divided Pt or V2O5 acts as catalyst. The optimum temperature
and pressure condition is 4500–5000C and 1.5–1.7 atmospheric pressure.
18. Fuming sulphuric acid : SO3 is dissolved in conc. H2SO4 to form fuming sulphuric
acid.
H2SO4 + SO3 H2S2O7.
QUESTIONS
A. Very short answer type questions (1 mark each) :
1. Complete the following reactions :
C2H4 + O2 ® –––––– + ––––––
4 Al + 302 ® ––––––
2. Give one reaction in which SO2 behaves as a reducing agent.
3. What is the basicity of sulphuretted hydrogen ?
4. What happens when a paper soaked in lead acetate solution is shown in H 2S gas ?
5. Name one catalyst which is used in the manufacture of sulphuric acid by contact
process.
6. What is the action of SO2 with H2S ?
7. Name two elements of Group 16 of periodic table.
8. Write the electronic configuration of second element of group 16 of the periodic table.
9. Name two allotropic modifications of sulphur.
10. What is the bond angle in the molecule of sulphur dioxide ?
11. Why SO2 gas cannot be collected over water ?

12. What is the colour change observed when SO2 is passed through acidified K2Cr2O7
solution ?
13. Name the catalyst used in the manufacture of Sulphuric acid by contact process.
14. Which form of sulphur shows paramagnetic behaviour ? What happens when SO 3 is
passed through water ?
15. Conc. H2SO4 chars paper, wood and sugar because it removes –––––– from them.
16. Which oxide of oxygen family is amphoteric in nature ?
17. Whether Sulphur dioxide is a lewis base or acid ?
18. What is the shape of Ozone molecule.

1. What happens when SO2 is passed through lime water ? Give equations.
2. Why oxygen is a gas, whereas sulphur is a solid ?
3. Water is a liquid while hydrogen sulphide is a gas at room temperature. Give reasons.
4. What is the action of ozone on lead sulphide ? Give equation.
5. What happens when hydrogen peroxide reacts with ozone ? Give equation.
6. What happens when H2S is passed through aqueous solution of ZnCl2. Give equation.
7. What is allotropy ? Give example.
8. Write with equation what happens when dilute sulphuric acid is added to sodium
carbonate.
9. Why is hydrogen sulphide not dried by concentrated sulphuric acid ?
10. Why does sulphur dioxide exhibit bleaching action only in presence of water ?
11. What is the action of ozone on acidified ferrous sulphate ? Give equation.
12. (a) What gas is produced when conc. H2SO4 reacts with common salt at room
temperature ? Write equation.
(b) Write the eqn. for the reaction that takes place in stages when soild NaCl is
heated with conc H2SO4
13. Give one reaction in which SO2 behaves as a reducing agent. Give equation.
14. Why is ozone not collected over mercury ?
15. What happens when conc. H2SO4 is added to formic acid ? Give equation.
16. What happens when sulphuretted hydrogen is passed through chlorine water ? Give
equation.
17. What is the action of conc. H2SO4 on Potassium bromide ? Give equation.
18. Complete the equation given below and make it a balanced one.
SnCl2 + HCl + O3
19. What happens when SO2 is passed through sulphuretted hydrogen dissolved in water ?
Give equation.
20. Explain the bleaching action of Sulphur dioxide.
21. Why does ozone acts as a powerful oxidising agent?
22. How is the presence of SO2 detected ?
23. List the important sources of sulphur.
24. H2S is less acidic than H2Te. Why ?
25. How is SO2 an air pollutant ?
26. What happens when SO2 is passed through sulphuretted hydrogen dissolved in water ?
Give equation.
27. Write the Lewis structure of sulphuric acid molecule.
28. Write the structure and formula of Caro's acid.
C. Short answer type (3 marks each) :

1. Write the conditions to maximize the yield of H 2SO 4 by Contact process.
What happens when sulphur dioxide is passed through an aqueous solution of Fe (III)
salt ?
2. Arrange the hydrides of oxygen family in decreasing order of their bond angle? Explain.
3. SF6 exists while OF6 does not. Explain.
4. What happens when SO2 gas is passed through lime water first slowly and then in
excess?
5. Explain why bleaching action of SO2 is temporary?
6. What are amphoteric oxides ? Explain their amphoteric behaviour with suitable
examples.
7. What happens when ozone is passed through KI solution?
D. Long Questions (7 marks each) :

1. Write notes on preparation and any two properties and uses of SO 2.
2. How ozone is prepared ? State three chemical properties.
3. Give a comparative account of Group 16 elements (Oxygen family) of periodic table.
4. How is ozone prepared ? Show with equation how does it react with - (i) Lead
sulphide, (ii) Hydrogen peroxide and (iii) Potassium iodide solution.
5. How is sulphur dioxide prepared in the laboratory ? State its two physical and three
chemical properties with equations.
6. Describe any one method of preparation of ozone. Discuss its reaction with I 2, KMnO4
and ethylene.
7. Give the laboratory method of preparation of SO 2. How does it react with acidified
KMnO4 and K2Cr2O7 solution ? What is the cause of bleaching action of SO 2 ?
8. How are the following prepared in the laboratory ?
(a) O3 (b) SO2
9. What happens when ? Write equations.
(a) Copper reacts with conc. H2SO4
(b) Na2CO3 solution is evaporated with excess of SO2.
10. How Ozone is prepared ? How does it react with
(a) Potassium iodide solution,
(b) SnCl2 solution (acidified). Why the presence of Ozone in the atmosphere is essential ?
11. How is Ozone prepared ? Show with equation how does it react with
(a) KI solution (b) hydrogen peroxide and (c) lead sulphide.
1. Group 16 elements are

(a) s - block elements (b) p - block elements
(c) d- block elements (d) f - block elements
2. Which of the following has the maximum catenation property.
(a) S (b) Se
(c) Po (d) Te
3. Most abundant element in earth crust is
(a) O (b) Se
(c) Po (d) Te
4. Sulphur molecule is
(a) S2 (b) S4
(c) S6 (d) S8
5. Bleaching action of SO2 is due to
(a) Oxidation (b) Reduction
(c) Hydrolysis (d) Its acidic nature
6. SO2 oxidises
(a) Mg (b) K2Cr2O7
(c) KMnO4 (d) All
7. Which is not correct in case of H2SO4

(a) Reducing agent (b) Oxidising agent
(c) Sulphonating agent (d) Highly viscous
8. Which dissolves in H2SO4 to give oleum
(a) SO2 (b) SO3
(c) S2O (d) H2S
9. Oil of Vitriol is
(a) H2SO4 (b) H2SO3
(c) H2S2O7 (d) H2S2O8
10. Which of the following would quickly absorb oxygen
(a) Alkaline solution of Pyrogallic acid (b) Conc. H2SO4
(c) Lime water (d) Alkaline solution of CuSO4
11. Oxygen will react with each of the following elements readily, except
(a) P (b) Na
(c) S (d) Cl
12. O3 reacts with KI solution to produce
(a) Cl2 (b) I2
(c) IO3 (d) HI
13. A gas which cannot be collected over water is
(a) N2 (b) O2
(c) SO2 (d) PH3
14. When SO2 is passed over which of the solution, it turns green
(a) K2Cr2O7 (b) H2SO4
(c) P2O5 (d) SO3
15. Anhydride of H2SO4 is
(a) HSO4 (b) SO2
(c) SO3 (d) H2S2O3
16. How many unpaired electrons are present in an atom of configuration Is 22s22p4
(a) 2 (b) 3
(c) 1 (d) 6
17. SO2 is dehydrated by
(a) CaO (b) Conc H2SO4
(c) P2O5 (d) Anly CaCl2
18. In Which of the following reactions does SO2 act as an oxidising agent.
(a)A cidified K M nO 4 (b) Acidified K2Cr2O7
(c) Acidified C2H5OH (d) H2S
19. Which will liberate H2 gas from dilute H2SO4
(a) Cu (b) Al
(c) ZnO (d) Ag
20. The Hybridisation of sulphur in H2SO4 is
(a) Sp (b) Sp2
(c) Sp3 (d) Sp3d2
21. Ozone reacts with
(a) C2H4 (b) C2H2
(c) C6H6 (d) All
22. There is no S-S bond in
(a) S2O42– (b) S2O52–
(c) S2O72– (d) S2O32–
23. Formula of rhombic sulphur is
(a) S2 (b) S
(c) S4 (d) S8
24. Which oxide on heating gives oxygen
(a) HgO (b) Na2O
(c) BaO (d) MgO
25. Ozone is manufactured by
(a) Siemen's Ozoniser (b) Brodie's Ozoniser
(c) Siemen's and Malkes Ozoniser (d) All
26. The values of oxidation number of S in S8, S2F2 and H2S are respectively:
(a) –2, +1 and –2 (b) 0, +1, –2
(c) –2, –1 and +2 (d) 0, +1, +2
27. Ozone is tested by
(a) Ag (b) Hg
(c) Zn (d) Au
28. When SO2 is passed through a solution of H2S in water.
(a) H2SO5 is produced (b) H2SO3 is produced
(c) Sulphur percipitates is produced (d) None of the above
29. Which of the following is known as king of chemicals.

(a) H2SO4 (b) HNO3
(c) NaOH (d) NH4OH
30. Which of the following hydrides of oxygen family shows the lowest boiling point ?
(a) H2O (b) H2S
(c) H2Se (d) H2Te
ANSWERS TO MULTIPLE TYPE QUESTIONS
1. b 6. a 11. d 16. a 21. d

2. a 7. a 12. b 17. b 22. c
3. a 8. b 13. c 18. d 23. d
4. d 9. a 14. a 19. b 24. a
5. b 10. a 15. c 20. c 25. d
26. b 27. b 28. c 29. a 30. b
qqq
GROUP 17 ELEMENTS : HALOGEN FAMILY 295
CHAPTER - 9
GROUP 17 ELEMENTS : HALOGEN FAMILY
Group 17 of the periodic table consists of the normal elements fluorine, chlorine,
bromine, iodine and astatine. Among these astatine is radioactive. Fluorine, chlorine, bromine
and iodine are very reactive and closely related family of elements, known as halogens. All
of these are p-block elements. There are seven electrons in the outermost shell and are arranged
in group 17 of the periodic table. Since they are reactive, they do not occur free in nature. The
word 'halogen' has come from two greek words (i) halos (sea salt), (ii) genes ( to produce).
These elements show a marked resemblance and possess a regular gradation in their properties.
It justifies their inclusion in the same group of the periodic table.
9.1 OCCURRENCE :
Fluorine is extremely reactive and hence does not occur in free state. It is widely
found in the combined state as fluorides. The important minerals are : (i) Fluorspar, CaF 2.
(ii) Cryolite, Na3AlF6 (iii) Fluorapatite, CaF2.3Ca3(PO4)2
It is also present in small amounts as fluoride in plant ash, soil, sea water, bones and
teeth of animals.
Chlorine does not occur in the free state. It is largely found in combination with various
metals. Common salt or rocksalt (NaCl) is the most important chloride which occurs in sea
water, lakes and in rocks. Other minerals like Sylvine (KCl), Carnallite (KCl × MgCl2 × 6H2O),
Chlorapatite [3Ca3(PO4)2. CaCl2], Horn silver (AgCl) etc. are also good sources of chlorine. In
combination with hydrogen, it forms an important constituent of the gastric juice.
Bromides and Iodides of sodium, potassium, magnesium and calcium are also present in
sea water. Seaweeds contain iodine upto 0.5%. Chile salt petre contains iodine in the form of
sodium iodate upto 0.2%.
1. Electronic configuration : The general electronic configuration in the outermost orbit
(n) is ns2 np5. Each element has seven electrons in its outermost or valence shell.
Element At. No. Electronic configuration

F 9 Is2 2s2 2p5
Cl 17 1s2 2s2 2p6 3s2 3p5
Br 35 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5
I 53 Is2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5
At 85 Is2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 6s2 6p5
2. Molecular state : Halogens form diatomic molecules.

3. Mono electrovalency : Being short of one electron of the stable octet, they readily
react with alkali metals which possess an easily detachable single electron in the
outermost orbit (ns1) and are thus monovalent in electrovalent compounds.

Size of the atom, atomic mass, density, melting point and boiling point, atomic radius,
atomic volume and vander Waals' forces of attraction increase regularly with rise in atomic
number. Fluorine and chlorine are gases at ordinary temperature. Bromine is reddish brown
fuming liquid and iodine, violet solid.
The Group 17 elements have seven electrons in their valence shell. Their outermost
electronic configuration is given by ns 2 np5 which is one electron short of the next noble gas.
Table 9.1 Physical properties of the Halogens
Property Fluorine Chlorine Bromine Iodine
Atomic number/ 9 17 35 53
g.mol–1
Atomic mass 19 35.5 80 127
Electronic [He]2s2 2p5 [Ne]3s2 3p5 [Ar] 3d10 [Kr]4d10
configuration 4s24p5 5s25p5
Physical state Gas Gas Liquid solid
0
M.P ( C) – 218.5 – 101 – 7.2 114
B.P (0C) – 188 – 34.6 59.5 185.2
Density (in liquid 1.1 1.16 2.95 3.76
state) (gm per c.c )
Colour of vapour Pale yellow Greenish yellow Orange-red Violet
Colour of liquid Yellow Amber Yellow Reddish brown Shining dark
solid
Atomic radius (A0) 0.72 0.99 1.14 1.33
Ionic radius (X–) (A0) 1.33 1.84 1.96 2.20

Atomic volume (c.c.) 17.1 18.7 23.5 25.7
Electronegativity 4.0 3.0 2.8 2.5
Electron affinity 81 83 77 71
(kcal / mole)
Ionisation potential 401 300 273 241
(kcal / mole)
Oxidation states –1 –1, + 1, + 3 –1, +1, + 3, –1, +1, + 3,
+ 4, + 5, + 6, + 4, + 5, + 6, + 4, + 5, + 6,
+7 +7

The halogens have the smallest atomic radii in their respective periods because the
effective nuclear charge is maximum. Atomic radius increases from fluorine to iodine, as new
quantum shells are added to each element when we move gradually from top to bottom along
the group.
9.2.3 Ionisation enthalpy :
Ionisation enthalpy of the halogens are very high indicating that they have very small
tendency to lose electrons. The value decreases from fluorine to iodine, as expected. In case
of iodine, the value is comparatively low. This enables the iodine atom to lose an electron and
form I+ ion.
The halogens have very high values of electronegativity. Fluorine is the most
electronegative element in the periodic table. The values decrease as we move down the group
from fluorine to iodine indicating a gradual decline in the non-metallic character. The last
element iodine shows some metallic character also. For example, it forms in a few cases a
positive ion and has a metallic lustres.
9.2.5 Stability :
The stability of their molecules X2 decreases with increase of atomic mass. Thus, at
0
1200 C while fluorine is not dissociated at all, chlorine is slightly dissociated, bromine is
dissociated to the extent of 6%, iodine is highly dissociated.
9.2.6 Colour :
Halogen molecules are coloured (due to absorption of visible light). Fluorine absorbs
violet (high energy) and iodine absorbs yellow light (lower energy). Thus, they are yellow and
violet respectively. Similarly we can account for the greenish yellow colour of chlorine and
orange red colour of bromine. The colour deepens with the increase in atomic number (with
the change in the state of aggregation).
9.2.7 Non-metallic character :

On account of high electronegativities, all the halogens are non-metallic in character.
The non-metallic character, however, decreases as we move down the group.
9.2.8 Electron affinity :
All the elements have high electron affinities. Therefore, they have a strong tendency
to gain an electron to acquire noble gas configuration (ns 2np6). Chlorine has the highest
electron affinity which decreases gradually as we move down the group from chlorine to
iodine. The electron affinity of fluorine is lower than that of chlorine. This lower value is due
to the small size of the fluorine atom. The addition of an extra electron in fluorine atom
produces a high electron density in a relatively compact 2p–subshell and, therefore, there is
strong electron electron repulsion. Hence, fluorine has lesser tendency to accept extra electron,
that is, electron affinity is low.

9.3.1 Oxidation states :
All the halogens have the configuration ns2np5 in the valency shell, in the ground state.
These elements, therefore, tend to gain or share one electron to acquire noble gas configuration.
Hence, they show an oxidation state of –1 or +1, depending upon whether the element with
which they combine is less electronegative or more electronegative than the halogen. Thus, in
hydrogen halides (HF, HCl, HBr and HI) all the halogens are in oxidation state of –1 and
in fluoro compounds (ClF, BrF, and IF) and also in the oxy compounds (HClO, HBrO and
HIO), chlorine, bromine and iodine are in oxidation state of +1.
Since fluorine is the most electronegative element, it always exhibits an oxidation
state of –1. It does not exhibit any positive oxidation state. Also, fluorine has no d - orbitals
in its valency shell and hence it cannot have any excited states. Consequently, it does not
exhibit any higher oxidation states.
The other halogens exhibit higher positive oxidation states of +3, +4, +5, +6 and +7
as well because they have vacant d-orbitals in their valency shell which allow for early
excitation of d-as well as p- and s- electrons which is explained below :
Halogen atom ns np nd
in ground state
(Other than fluorine) One unpaired electron account
for –1 or +1 oxidation state.
First excited state Three unpaired electrons account
for +3 oxidation states.
Second excited state Five unpaired electrons account
for +5 oxidation state.
Third excited state Seven unpaired electrons account
for +7 oxidation state
9.3.2 Reactivity :
Halogens are very reactive. Fluorine is the most reactive. The reactivity decreases as
we move down the group. Fluorine is highly reactive because of low energy of F - F bond,
small size of atom or ions, high electronegativity and also due to very powerful oxidising
power.
9.3.3 Combination with hydrogen :
All combine with hydrogen to form their hydracids. The reactivity decreases from
fluorine to iodine. Fluorine reacts in dark, chlorine reacts in sunlight, bromine reacts on
heating, while iodine reacts only in the presence of catalyst .
H2 + X2 2HX (X = F, Cl, Br, I)
The acidic strength of these acids varies in the order : HI > HBr > HCl > HF. This is
due to increase in bond (H – X) dissociation enthalpy in the order HI < HBr < HCl < HF.
9.3.4 Reaction with water :
The reactivity with water decreases from fluorine to iodine. Fluorine reacts with water
violently in dark forming O2 and O3. Chlorine and bromine react with water to form
corresponding hydrohalic and hypohalous acids. The reaction of iodine with water is non-
spontaneous.
X2 + H2O ¾Sunlight
¾¾® HX + HXO
(X2 = Cl2 or Br2)
2F2 + 2H2O 4H+ + 4F– + O2
9.3.5 Oxidising action :

On account of electron affinites, the halogens have a strong tendency to gain electrons
and thus they act as strong oxidising agents. It decreases from fluorine to iodine. Fluorine is
the strongest oxidising halogen which oxidises other halide ions in solution or even in the solid
phase. In general, a halogen oxidises halide ions of higher atomic number.
1 X + e– X–
2 2
9.3.6 Reaction with oxygen :

Halogens combine with oxygen to form oxides. But most of these oxides are unstable
in nature. Fluorine forms two compounds OF2 and O2F2 with oxygen out of which only OF2
is thermally stable at 298K. These oxides are called oxygen fluorides rather than oxides of
fluorine because fluorine is more electronegative than oxygen. O 2F2 is a strong fluorinating
agent and oxidises plutonium to PuF6. This reaction of O2F2 is employed for removing plutonium
in the form of PuF6 from spent nuclear fuel.
Chlorine with oxygen forms oxides like Cl2O, ClO2, Cl2O6 and Cl2O7. These compounds
are highly reactive and tend to explode. ClO2 is used as a bleaching agent for paper pulp and
textiles.
Bromine forms oxides bearing formula Br 2O, BrO2 and BrO3. These oxides exist only
at low temperature being unstable at higher temperatures. They are very powerful oxidising
agents.
I2O4, I2O5, I2O7 are the oxides of iodine available in the form of solids. I 2O5 is a good
oxidising agent and is used for estimation of CO.
9.3.7 Displacement reactions :
It decreases with rise in atomic number. Fluorine displaces all other halogens from
their salts while iodine cannot do so at all.
2NaCl + F2 2NaF + Cl2
2 KBr + F2 2KF + Br2
2 KI + F2 2KF + I2
9.3.8 Reaction with metals :
As halogens are highly electronegative elements and metals are highly electropositive
elements, they react to form electrovalent compounds. Their ionic character decreases in the
order MF > MCl > MBr > MI
2Na + X2 2NaX (X = F, Cl, Br, I)
9.3.9 Formation of interhalogen compounds :
The halogens combine with each other to form interhalogen compounds.
9.3.10 Reaction with nonmetals :
Halogens also combine with a number of non-metals like S, P, etc. The reactivity
decreases from fluorine to iodine. For example, sulphur forms hexafluoride (SF 6) with fluorine,
tetrachloride (SCl 4) with chlorine, dibromide (SBr2) with bromine and there is no reaction
between sulphur and iodine.
The similarity and gradation in their properties justifies the inclusion of all the four
halogens in the same group of the periodic table.
9.4 ANOMALOUS BEHAVIOUR OF FLUORINE :

Fluorine because of its small size and high electronegativity shows anomality in its
behaviour in comparison to other halogens. The low F–F bond dissociation enthalpy and non-
availability of d-orbitals in valence shell are also reasons for its anomalous behaviour. Some
of the consequences of its anomalous behaviour are as follows :
(1) Fluorine is most reactive of all the halogens and has a much higher electrode potential
than those of other halogens. Most of the reactions of fluorine are exothermic as it
forms strong bond with other elements.
(2) Fluorine does not show higher oxidation states (positive or negative) because of the
absence of d-orbitals in its valence shell.
(3) Due to small atomic size and high electronagativity hydrogen bonding is observed in
some fluorine compounds. HF is a liquid with boiling point 293K and is a weak acid
because of hydrogen bonding.
(4) Fluorine has the highest electrode potential. So it is the strongest oxidising agent
among all the halogens. It can act as oxidising agent among all the halogens. It can
oxidise most of the other elements, including some of the noble gases (Kr, Xe).
Due to such special properties of fluorine, it is usually called as super halogen.
9.5 CHLORINE :
Symbol : Cl At.No. 17 At.mass : 35.5
Mol.formula : Cl2 Mol.mass : 71
Preparation :
All the methods for the preparation of chlorine involve the oxidation of chloride ion
either by chemical or electrolytic method.
1. By oxidation of hydrochloric acid : The oxidising agents which can be used are MnO2,
PbO2, KMnO4, K2Cr2O7, NaClO, O3 etc.
(i) MnO2 oxidises HCl producing MnCl2, H2O and chlorine.
MnO2 + 4HCl MnCl2 + 2H2O + Cl2
However, a mixture of common salt and concentrated H 2SO4 is used in place of
HCl.
4 NaCl + MnO2 + 4 H2SO4 MnCl2 + 4 NaHSO4 + 2 H2O + Cl2
(ii) PbO2 oxidises HCl forming PbCl2, H2O and Cl2
PbO2 + 4HCl PbCl2 + 2H2O + Cl2
(iii) KMnO4 oxidises HCl producing MnCl2, KCl, H2O and Cl2 in cold.
2KMnO4 + 16HCl 2 MnCl2 + 2KCl + 8H2O + 5Cl2
(iv) K2Cr2O7 also oxidises HCl producing CrCl3, KCl, H2O and Cl2.
K2Cr2O7 + 14HCl 2CrCl3 + 2KCl + 7H2O + 3Cl2
(v) Sodium hypochlorite (NaClO) and Ozone (O3) can also oxidise HCl producing
chlorine gas.
NaClO + 2HCl NaCl + H2O + Cl2

O3 + 2HCl O2 + H2O + Cl2
In the laboratory, chlorine can be prepared adopting the methods (i), (iii) and (iv).
2. By heating any chloride with Conc. H2SO4 in presence of MnO2
When a mixture of NaCl and MnO2 in heated with Conc. H2SO4, chlorine is formed.
Conc. H2SO4 produces HCl from the chloride which is subsequently oxidised by MnO 2 to
chlorine.
2NaCl + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + 2H2O + Cl2
This method is also employed for the preparation of chlorine in the laboratory.
3. Electrolytic Method : Commercially, Chlorine is produced by the electrolysis of
concertrated solution of sodium chloride (brine). Chlorine is obtained as a by-product in
the manufacture of NaOH and sodium from sodium chloride.
Electrolysis
2NaCl + 2H2O H2 + Cl2 + 2NaOH
At the anode : 2Cl— ® Cl2 + 2e (oxidation)
At the cathode : 2H2O + 2e ® H2 + 2OH—(reduction)
Electrolysis
2NaCl (fused) 2Na + Cl2
Laboratory methods of preparation : The following methods are usually followed in
the laboratory for the preparation of chlorine.
(i) By the action of HCl on KMnO4
This is a convenient method for the preparation of chlorine in the laboratory. It consists of
the addition of cold concentrated HCl to solid potassium permanganate.
2KMnO4 + 16HCl ® 2MnCl2 + 2KCl + 8H2O + 3Cl2
The apparatus is shown in CONC
HCL
Fig. 9.1
A small quantity of KMnO4
in taken in a flat bottom flask fitted
with a dropping funnel and a delivery
tube. HCl is added drop by drop from
Powdered CHLORINE
this funnel when greenish yellow gas KMnO4 GAS
is evolved. Chlorine, prepared by this
method may contain HCl gas.
Therefore, it is passed through water
to remove HCl gas and then through Water Conc H2SO4
Conc. H2SO4 to remove water vapour Fig 9.1 Laboratory preparation of chlorine
Finally, dry and pure chlorine is collected in a jar by upward displacement of air. This method
yields chlorine without heating.
(ii) By heating a mixture of NaCl and MnO2 with Conc.
H2SO4
This method is commonly adopted in the laboratory for
the preparation of chlorine. A mixture of NaCl and MnO2 in taken
in a round bottom flask fitted with a thistle funnel and a delivery
tube. The flask is clamped to a stand (Fig 9.2) Concentrated H2SO4
is added through the thistle funnel and the flask is heated gently.
Chlorine is evolved. To purify the gas, it is passed through water
to remove HCl gas and then through Conc. H2SO4 to remove
water vapour. Finally, the gas is collected by the upward Fig 9.2 Laboratory preparation
of chlorine
displacement of air.
heat
2NaCl + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + 2H2O + Cl2
Pure Chlorine : Pure chlorine can be obtained by heating dry platinic chloride (PtCl 4) or
gold chloride (AuCl3) in a hard glass tube.
374 0C 582 0C
PtCl4 PtCl2 + Cl2 Pt + 2Cl2
175 0 C 1850C
2AuCl3 2AuCl + 2Cl2 2Au + 3Cl2
Manufacture of chlorine :
Chlorine gas is manufactured in large scale by the following process.
(1) Deacon's process : In this process, hydrogen chloride gas is oxidised by atmospheric
oxygen in the presence of CuCl2 as catalyst at 723K.
CuCl , 723K
4 HCl + O2 ¾¾ ¾2¾ ¾ ¾® 2Cl2 + 2 H2O
(ii) Chlorine gas is also obtained by the electrolysis of concentrated solution of NaCl (brine).
In this method chlorine gas is liberated at the anode and sodium metal is liberated at
cathode.
During the manufacture of sodium metal by electrolysis of fused NaCl in Down's process,
Cl2 gas is also obtained as a by-product.
At anode : Cl– Cl + e–
2 Cl Cl2
At cathode : Na+ + e– Na
PROPERTIES
Physical Properties :
1. Chlorine is a greenish-yellow gas with pungent suffocating smell.
2. It is heavier than air.
3. It can be liquefied by cooling under pressure (b.p. 239K). On further cooling, it solidifies
to a pale yellow solid.
4. It is poisonous and affects mucous membrane if inhaled.
5. It is fairly soluble in water and the aqueous solution is called chlorine water, which
looks yellow.
Chemical properties : Chlorine is neither combustible nor a supporter of combustion.
1. Reaction with water and alkalies
(a) Chlorine is fairly soluble in water. The aqueous solution, known as chlorine water contains
a mixture of hydrochloric and hypochlorous acid.
Cl2 + H2O HCl + HClO
The solubility of chlorine increases in presence of OH — ions. In alkaline solution, H3O+
ions are removed by OH— ions as water molecules and the hydrolysis goes to completion.
(b) When passed through cold dilute alkali solution, it forms chlorides and hypochlorites.
2NaOH + Cl2 NaCl + NaClO + H2O
2KOH + Cl2 KCl + KClO + H2O
When the alkali solutions are hot and concentrated, chlorates are formed.
6 NaOH + 3Cl2 5 NaCl + NaClO3 + 3H2O
(Sod.chlorate)
6 KOH + 3Cl2 5KCl + KClO3 + 3H2O
(Pot.chlorate)
When chlorine is passed over dry slaked lime, bleaching powder is obtained.
2 Ca(OH)2 + 2 Cl2 Ca(OCl)2 + CaCl2 + 2H2O
(Slaked lime) (Bleaching Powder)
The composition of bleaching power is Ca(OCl)2×CaCl2×Ca(OH)2×2H2O.
Red hot quicklime (CaO) reacts with dry chlorine forming calcium chloride and oxygen.
2CaO + 2Cl2 2CaCl2 + O2
2. Reaction with other elements : It combines with all nonmetals except nitrogen, oxygen,
carbon and inert gases.
(a) Reaction with hydrogen : Chlorine combines with hydrogen in presence of light (not in
dark) with explosion forming HCl.
H2 + Cl2 2HCl
Turpentine (C10H16) burns in chlorine forming HCl and carbon.
C10H16 + 8Cl2 10 C + 16HCl
(b) Reaction with other non-metals : Boron, sulphur, phosphorus (red) etc. combine with
chlorine when heated forming their respective chlorides.
2B + 3Cl2 2BCl3
(Boron trichloride)
S8 + 4Cl2 4S2Cl2
(Disulphur dichloride)
P4 + 6Cl2 4PCl3
(Phosphorus trichloride)
Yellow phosphorus immediately catches fire in chlorine.
(c) Reaction with metals : Alkali metals burn brilliantly in chlorine. Iron, copper, aluminium,
zinc, magnesium etc form their respective chlorides when heated in chlorine.
2Na + Cl2 2NaCl
2 Fe + 3Cl2 2FeCl3
Cu + Cl2 CuCl2
2Al + 3Cl2 Al2Cl6
Zn + Cl2 ZnCl2
Mg + Cl2 MgCl2
3. Reaction with ammonia : Chlorine reacts with ammonia under two different conditions.
(i) When ammonia is in excess, the products are nitrogen and ammonium chloride.
2NH3 + 3Cl2 N2 + 6HCl
6NH3 + 6HCl 6NH4Cl
—————————————
8NH3 + 3Cl2 N2 + 6NH4Cl
(ii) When chlorine is in excess, the products are nitrogen trichloride and HCl.
NH3 + 3Cl2 NCl3 + 3HCl
4. Oxidising property : Chlorine, in presence of moisture is a good oxidising agent. As
discussed earlier, chlorine oxidises many metals to their respective chlorides.
(i) It oxidises H2S to S. either as such or in aqueous solution.
H2S + Cl2 2HCl + S
In aq. soln., Cl2 + H2O HCl + HClO
HClO HCl + O
H2S + O H2O + S
———————————
Cl2 + H2S 2HCl + S
(ii) In presence of water, chlorine oxidises sulphur dioxide to sulphuric acid.

SO2 + 2H2O + Cl2 H2SO4 + 2HCl
(iii) It also oxidises sulphites to sulphates and precipitates sulphur from sodium thiosulphate.
Na2SO3 + H2O + Cl2 Na2SO4 + 2HCl
Na2S2O3 + H2O + Cl2 Na2SO4 + 2HCl + S
(iv) Chlorine oxidises ferrous chloride to ferric chloride and ferrous sulphate to ferric sulphate
in presence of H2SO4.
2FeCl2 + Cl2 2FeCl3
2FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2HCl
(v) Chlorine oxidises HBr to Br2, HI to I2 and itself reduced to hydrogen chloride. It liberates
iodine from an aqueous solution of KI.
2HBr + Cl2 2HCl + Br2
2HI + Cl2 2HCl + I2
2KI + Cl2 2KCl + I2
5. Bleaching property : In presence of moisture, chlorine acts as a bleaching agent. Chlorine
reacts with water forming HCl and HClO (hypochlorous acid). HClO being unstable
decomposes giving nascent oxygen which is responsible for its bleaching properties. The
bleaching action takes place by oxidation. Dry chlorine does not bleach.
Cl2 + H2O HCl + HClO
HClO HCl + O
————————————
Cl2 + H2O 2HCl + O
Coloured matter + Nascent oxygen Colourless matter..
The bleaching action of chlorine is permanent. The delicate articles should not be bleached
with chlorine though wood pulp and cotton fibres are bleached by chlorine.
6. Addition reactions : Chlorine forms addition products with SO2, CO and unsaturated
hydrocarbons.
SO2 + Cl2 SO2Cl2
(Sulphuryl chloride)
CO + Cl2 COCl2
(Carbonyl chloride or phosgene)
C2H4 + Cl2 C2H4Cl2
(Ethylene) (Ethylene chloride)
7. Substitution reaction : With saturated hydrocarbons, chlorine forms a number of
substitution products in presence of sunlight. Thus, methane, CH 4 reacts with Cl2 in
presence of sunlight giving a number of products.
CH4 + Cl2 —— HCl + CH3Cl

(methyl chloride)
CH3Cl + Cl2 —— HCl + CH2Cl2
(methylene chloride)
CH2Cl2 + Cl2 —— HCl + CHCl3
(chloroform)
CHCl3 + Cl2 —— HCl + CCl4
(carbon tetrachloride)
Summary :
H2
HCl
B
BCl3
S
S2Cl2
P PCl3
Metal
Metal chloride
H2O
HCl + HClO, 2HCl + [O]
NaOH
NaClO + NaCl + H2O
(Cold)
NaOH
NaClO3 + NaCl + H2O
hot.conc
Ca(OH)2
CaOCl2.H2O (bleaching power)
dry
NH3
(Excess) N2 + NH4Cl
NH3
Cl2 NCl3 + HCl
(less)
H2 S
HCl + S
SO2+H2O
H2SO4
HX
HCl + X2 (X=Br,I)
SO2
SO2Cl2
CO
COCl2
C2 H4
C2H4Cl2
SO32-
SO42–
S2O32-
SO42– + S
FeCl2
FeCl3
FeSO4+H2 SO4
Fe2 (SO4)3 + HCl
CH4
CH3Cl + CH2Cl2 + CHCl3 + CCl4
aq.KI KCl + I2
Uses of chlorine : It is used

(i) in the manufacture of bleaching powder.
(ii) as a bleaching agent for cotton fabrics, paper, and rayon.
(iii) in the purification of drinking water.
(iv) as a germicide and disinfectant.
(v) as an oxidising agent.
(vi) in the manufacture of chlorates, hypochlorites, chloroform, carbon tetrachloride and a
number of synthetic organic compounds.
(vii) for the manufacture of poisonous gases like phosgene (COCl 2), tear gas (CCl3 . NO2) and
mustard gas (Cl-C2H4-S-C2H4-Cl).
(viii) In the extraction of platinum and gold.
9.6 HYDROGEN CHLORIDE (HYDROCHLORIC ACID) :

Mol. formula : HCl Mol. mass : 36.5
Occurrence : Hydrogen chloride is occasionally found in the gases emitted from
volcanoes. It is also present in the gastric juices. The salts of the acid occur plentifully in
nature. Hydrochloric acid is obtained by dissolving hydrogen chloride gas in water.
Preparation :
1. Synthesis : HCl can be prepared from its elements by exposing a mixture of equal
volumes of hydrogen and chlorine to sunlight.
H2 + Cl2 ® 2HCl
2. From metal chlorides : When metal chlorides react with conc. H2SO4, hydrogen
chloride gas is obtained.
BaCl2 + H2SO4 ® BaSO4 + 2HCl
3. Laboratory method : Hydrogen chloride gas is prepared in the laboratory by heating
sodium chloride with concentrated sulphuric acid.
NaCl + H2SO4 ¾420K
¾¾ ¾® NaHSO4 + HCl
NaCl + NaHSO4 ¾823K

¾¾ ¾® Na2SO4 + HCl
Conc. H2SO4
Conc. H2SO4
+
SALT
Conc. H2SO4
Fig. 9.3 Lab. preparation of hydrogen chloride

Sodium chloride is taken in a round-bottomed flask which is fitted with thistle funnel
and a delivery tube. Conc. sulphuric acid is added through the thistle funnel so that the end
of the thistle funnel dips under the liquid. Hydrogen chloride gas is evolved (more on heating)
and is collected in gas jars by upward displacement of air. The gas can be dried by bubbling
it through conc. sulphuric acid before it is collected. It cannot be dried by using phosphorus
pentoxide or quick lime since it reacts with these compounds.
2P2O5 + 3HCl 3 HPO3 + POCl 3
Metaphosphoric acid phosphorus oxychloride
CaO + 2HCl CaCl2 + H2O
Hydrochloric acid : Hydrogen chloride gas is highly soluble in water and the resulting
solution is called hydrochloric acid. A saturated solution of hydrogen chloride in water is the
concentrated hydrochloric acid.
Properties :
A. Physical :
1. It is a colourless gas with pungent suffocating odour. The gas fumes in moist air.
2. It is heavier than air and on cooling liquifies to a colourless liquid (B.P 189K) and on
further cooling it is converted to solid (Freezing point 159K).
3. It is highly soluble in water and the solution is a strong acid, hydrochloric acid. It
forms constant boiling (azeotropic) mixture containing 22.2% of the acid and boiling
at 383K. A solution of hydrochloric acid cannot, therefore, be concentrated beyond
22.2% by boiling.
4. When inhaled it attacks mucous membrane.
B. Chemical :
Hydrogen chloride in the gaseous state is essentially covalent. In aqueous solution, it
ionises and acts as acid, hydrochloric acid (K a = 7 x 108)
H2O + HCl H3O+ + Cl–
The solution is strongly acidic and turns blue litmus red. The gas neither is combustible
nor supports combustion.
1. Acidic Properties :
(i) Hydrochloric acid reacts with most of metals, such as zinc, magnesium, iron, tin
and sodium forming metal chlorides and hydrogen gas.
Zn + 2HCl ZnCl2 + H2 , Fe + 2HCl FeCl2 + H2
Liberation of hydrogen prevents the formation of ferric chloride.
(ii) It reacts with bases i.e. metal oxides, hydroxides, carbonates etc. to form metal
chlorides.
CaO + 2HCl CaCl2 + H2O
NaOH + HCl NaCl + H2O
Na2CO3 + 2HCl 2NaCl + H2O + CO2
NaHCO3 + HCl NaCl + H2O + CO2
Na2SO3 + 2HCl 2NaCl + H2O + SO2
2. Action of salts : HCl decomposes the salts of weaker acids like sulphides, sulphites,
thiosulphates, and nitrites. The corresponding chlorides are formed with the evolution
of different gases.
FeS + 2HCl FeCl2 + H2S
ZnSO3 + 2HCl ZnCl2 + H2O + SO2
Na2S2O3 + 2HCl 2NaCl + H2O + S + SO2
2NaNO2 + 2HCl 2NaCl + H2O + NO + NO2
3. Precipitation reactions : HCl forms insoluble chlorides with soluble salts of Ag, Pb,
Hg (Ous).
AgNO3 + HCl AgCl + HNO3
(white)
Pb (NO3)2 + 2HCl PbCl2 + 2HNO3
(white)
Hg2 (NO3)2 + 2HCl Hg2Cl2 + 2HNO3
(white)
4. Reaction with fluorine : Since fluorine is more electronegative than chlorine, it displaces
chlorine from hydrochloric acid.
2HCl + F2 2HF + Cl2
5. Reaction with ammonia : It produces dense white fumes of ammonium chloride with
ammonia.
NH3 + HCl NH4Cl
6. Reactions as reducing agent : It acts as a reducing agent in presence of strong

oxidising agents such as MnO2 , PbO2 , Pb3O4 (red lead), KMnO4, K2Cr2O7, NaClO, O3
etc. In all the reactions chlorine is the product.
(i) MnO2 + 2HCl MnCl2 + H2O + O

2HCl + O H2O + Cl2
——————————————————
MnO2 + 4HCl MnCl2 + 2H2O + Cl2
(ii) PbO2 + 4HCl PbCl2 + 2H2O + Cl2
(iii) Pb3O4 + 6HCl 3PbCl2 + 3H2O + O

2HCl + O H2O + Cl2
———————————————————
Pb3O4 + 8HCl 3PbCl2 + 4H2O + Cl2
(iv) 2KMnO4 + 6HCl 2KCl + 2MnCl2 + 3H2O + 5O

10HCl + 5O 5H2O + 5Cl2
———————————————————————
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2
(v) K2Cr2O7 + 8HCl 2KCl + 2CrCl3 + 4H2O + 3O

6HCl + 3O 3H2O + 3Cl2
——————————————————————––
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 7H2O + 3Cl2
(vi) NaClO NaCl + O

2HCl + O H2O + Cl2
————————————————
NaClO + 2HCl NaCl + H2O + Cl2
(vii) O3 O2 + O
2HCl + O H2O + Cl2
—————————————
2HCl + O3 H2O + O2 + Cl2
7. Formation of aquaregia : A mixture of concentrated hydrochloric acid and concentrated
nitric acid in the ratio 3:1 is called aquaregia, It dissolves even noble metals like gold
and platinum.
Au + 4H+ + NO3– + 4Cl– AuCl4– + NO + 2H2O
3Pt + 16H+ + 4NO–3 + 18 Cl– 3PtCl62– + 4NO + 8H2O
Summary :
H2O
H3O+Cl–
Zn
H2
Metal oxide
Metal chloride
hydroxide
Salts of
Metal chloride + different gases
Weak acids
AgNO 3 , Pb(NO 3)2

HCl White precipitate of chlorides
& Hg 2 (NO 3)2
F2
Chlorine
NH3
NH4Cl
(reducing property)
Cl2
Oxidising agent
HCl + HNO3 (3:1) Aquaregia
Uses : Hydrochloric acid is used :

1. As a laboratory reagent.
2. In the preparation of chlorine, chlorides and aquaregia.
3. For cleaning iron sheets during tin plating and galvanisation.
4. In the manufacture of dyes and in textile industry.
5. For extraction of glue from animal tissue and bones.
6. In medicine.
7. In the manufacture of glucose. (from corn starch)
Tests :
1. HCl gas fumes in moist air and forms dense white fumes of NH4Cl with ammonia.
2. Chlorine is evolved when HCl gas is passed through a heated tube containing
MnO2.
3. Solution of HCl in water
(i) Turns blue litmus red and

(ii) Gives a white precipitate with AgNO3 solution. The precipitate, AgCl, is insoluble
in nitric acid, but readily dissolves in dilute ammonium hydroxide.
AgNO3 + HCl AgCl + HNO3
AgCl + 2NH4OH [AgNH3)2] Cl + 2H2O
9.7 OXOACIDS OF HALOGENS :

Halogenes form different oxo-acids commonly known as
(a) Hypohalous acid (b) Halous acid
(c) Halic acid and (d) Perhalic acid (Table 9.2)
Due to high electronegativity and small size, fluorine forms only one oxoacid, HOF
known as fluoric (I) acid or hypofluorous acid. The other halogens form several oxoacids.
Most of these oxoacids can not be isolated in pure state. They are stable only in aqueous
solutions or in the form of their salts. The oxoacids of halogens are given in Table 9.2 and their
structures are given in Fig. 9.3.
Table 9.2 : Oxoacids of Halogens

Halic (I) acid HOF HOCl HOBr HOI
(Hypohalous acid) (Hypofluorous (Hypochlorous) (Hypobromous (Hypolodous
acid) acid) acid) acid)
Halic (III) acid – HOCIO – –

(Halous acid) – (chlorous acid) – –
Halic (V) acid – HOCIO2 HOBrO2 HOIO2
(Halic acid) – (chloric acid) (bromic acid) (iodic acid)
Halic (VII) acid – HOCIO3 HOBrO3 HOIO3
(Perhalic acid) – (perchloric acid) (perbromic acid) (periodic acid)
Fig. 9.4 : The structure of oxoacids of chlorine

O H H
H Cl
O O
Hypochlorous acid
Cl Cl
O O O O O
H Cl O O
Chlorous acid Chloric acid Perchloric acid

9.8 INTERHALOGEN COMPOUNDS OR INTERHALOGENS :

9.8.1 Each halogen combines with every other halogen to form compounds amongst
themselves. These are known as interhalogens or interhalogen compounds. In naming the
compounds, the less electronegative element is mentioned first. These are generally covalent
compounds.
1. Interhalogens of the type XY (Diatomic interhalogens)
Preparation : These are prepared by the direct combination of the halogens.
I2 + F2 ¾228K
¾¾ ¾® 2IF
I2 + X2 2IX (X = Cl, Br)
Cl + F ¾523K
2 2 ¾¾¾® 2ClF
Properties : The properties of these interhalogens lie between those of the parent
halogens. However, they are more reactive than the halogens concerned. Because, the bond
energy of X – Y bond is less than the bond energy of X – X or Y – Y bond.
(i) These compounds readily convert metals into metal halides.
XY + 2M MX + MY
ClF + 2Na NaCl + NaF
(ii) On hydrolysis, they give oxy-halides and hydrides of the more electronegative
halogen.
XY + H2O HOX + HY (Y is more electronegative)
(iii) They add to double bond forming dihalocompounds.
– CH = CH – + XY – CHX – CHY –
2. Interhalogens of the type XY3 (Tetra-atomic interhalogens)
Three atoms of one halogen combine with one atom of another halogen to form these
type of compounds. Some of the known compounds of this type are ClF 3, BrF3 and ICl3.
These compounds are generally prepared by the direct combination of the elements
under suitable conditions. Among these, ClF3 is most reactive.
Cl2 + 3F2 ¾473

¾¾ -573K
¾¾ ¾® 2ClF3
Br2 + 3F2 ¾N
¾
¾ 2
® 2BrF3
I2 + 3Cl ¾373K
¾¾ ¾® 2ICl3
3. Interhalogens of the type XY5 (Hexa–atomic interhalogens)
Five atoms of one halogen combine with one atom of another halogen to form these
type of interhalogens. The stable compounds are ClF 5, IF5 and BrF5 .
These are generally prepared by the direct fluorination of the element or the lower
fluorides.
Cl2 + 5F2 ¾623K
¾¾ ¾® 2 ClF5
250 atm.
excess F
Br2 + 5F2 ¾ ¾¾¾¾ ¾® 2 BrF5
> 423K
excess F2
I2 + 5F2 ¾¾¾¾¾¾ ¾® 2IF5
4. Interhalogens of the type XY7 (Octa-atomic interhalogens)

Seven atoms of one halogen combine with one atom of another halogen to form this
type of interhalogen. Only one compound, IF7 of this type is formed. The reason for the
formation of this compound lies in the large size of iodine atom and very small size of fluorine
atom.
Iodine haptafluoride, IF7, is formed by heating iodine pentafluoride with fluorine
at 623K – 673K
IF5 + F2 IF7
9.8.2 Properties of Interhalogen Compounds :
Some properties of interhalogen compounds are summarised in the Table 9.3
Table 9.3 : Some properties of Interhalogen Compounds
Type Formula Physical state and colour Structure
XY CIF Colourless gas –
BrF pale brown gas –
IFa detected spectroscopically –
BrClb Gas
ICl Ruby red solid (a-form)
Brown red solid (b-form)
IBr black solid
XY3 CIF3 colourless gas Bent T-shaped

BrF3 yellow green liquid Bent T-shaped
IF3 yellow powder Bent T-shaped (?)
ICl3C orange solid Bent T-shaped (?)
XY5 IF5 colourless gas but Square

solid below 77K pyramidal
BrF5 colourless liquid Square pyramidal
CIF5 colourless liquid Square pyramidal
XY7 IF7 colourless gas Pentagonal bipyramidal
a
Very unstable; bThe pure solid is known at room temperature; CDimerises as Cl-bridged dimer (I2Cl6)
(1) As halogen atoms have small electronegativity difference between each other, the
interhalogen compounds are covalent in nature.
(2) They are volatile solids or liquids at 298K except ClF, BrF, ClF 3, IF5 and IF7 which are
gases at room temperature (Table 9.3)
(3) Due to absence of unpaired electrons these compounds are diamagnetic in nature.
(4) Their physical properties are intermediate between those of constituent halogens.
However, their melting points and boiling points are a little higher than expected due
to some polarity associated with these molecules.
(5) Interhalogen compounds are more reactive than halogens (except fluorine), because
X–X' bond in interhalogens is weaker than X–X bond in halogens except F–F bond.
The sequence of reactivity of various interhalogen compounds decrease in the order:
CIF3 > BrF5 > IF7 > ClF > BrF3 > IF5 > BrF > IF3 > IF
(6) (a) The compounds of the type XY on hydrolysis give halide ion of smaller halogen
and a hypohalite derived from the larger halogen.
XY + H2O HY + HOX
ICl + H2O HCl + HOI (Hypoiodous acid)
(b) The interhalogen compounds of the type XY3 also yield halide ion of smaller
halogen on hydrolysis and a halate is formed, where as XY 7 type compounds
yield perhalate anion derived from larger halogen along with halide ion of the
smaller halogen.
9.8.3 Structure of Interhalogen Compounds :
The molecular structure of Interhalogen compounds can be explained on the basis of
VSEPR theory.
(a) XY3 type : These compounds involve sp3d hybridization of central atom X and
hence have trigonal bipyramidal geometries or are T-shaped. (Fig. 9.4)
Ex : Structure of ClF3
2 5 0
3s 3p 3d
Cl (Ground state)
2 4 1
3s 3p 3d
Cl (Second Excited state)
F
sp3d-hybridisation
F The central Cl atom is surrounded by three bond pairs
Cl and two lone pairs of electrons. These electron pairs occupy the
corners of a trigonal bipyramid. The two lone pairs occupy the
.. equatorial positions to minimise lonepair-lonepair and the bond
F
(Fig. 9.4 : Bent T-shaped structure of ClF 3
pair-lonepair repulsions which are greater than the bond-pair-bond pair repulsions. The axial
fluorine atoms bend towards the equatorial fluorine in order to minimise the lone pair-lone pair
repulsions. So the molecule has a bent T-shape.
(b) XY5 type : All interhalogen compounds of the type XY5 involve sp3d2 hybridization
of the central halogen atom X and hence have distorted octahedral (square pyramidal)
geometry due to single lone pair electrons around the central atom.
Ex : Structure of BrF5
2 5 0
4s 4p 4d
Br (Ground State)
2 3 2
4s 4p 4d
Br (Excited state)
sp3 d2 hybridisation
F
F
F
Br
The molecule has square-pyramidal geometry
F
.. F
(Fig. 9.5 : Structure of BrF5)

(c) XY7 type : The interhalogen compounds of this type involve sp 3d3 hybridization of the
central halogen atom X and have pentagonal bipyramidal geometry.
1 3 3
Ex : Structure of IF7 : 5s 5p 5d
Electronic structure of I
(in the third excited state) sp3 d3 hybridisation
F F
I Fig. 9.6 : Pentagonal bipyramidal

F
structure of IF7
F
F
F
9.8.4 Uses of Interhalogen compounds :

(1) They are used as non-aqueous solvents.
(2) They act as fluorinating agents. ClF3 and BrF3 are used for the production of UF6
in the enrichment of 235U.
U + 3ClF3 UF6 + 3ClF
9.9 PSEUDOHALIDE IONS AND PSEUDOHALOGENS :

The ions consisting of two or more electronegative atoms of which atleast one is
nitrogen and have properties similar to those of halide ions are called pseudohalide ions.
These pseudohalide ions also form dimeric molecules, like the halide ions. These
dimers are called pseudohalogens as they show properties similar to those of halogens. A few
examples of pseudohalide ions and pseudohalogens are given below :
Pseudohalides Pseudohalogens
Cyanide, CN– Cyanogen (CN)2
Thiocyanate, SCN– Thiocyanogen (SCN)2
Cyanate, OCN– Oxycyanogen (OCN)2
Cyanamide ion (NCN2–), fulminate ion (ONC–) and azide ion (N3–) are examples of a
few other pseudohalide ions.
1. Elements of Halogen family : Fluorine, chlorine, bromine, iodine and astatine

(radioactive).
2. Electronic configuration : The general electronic configuration in the outermost orbit is
ns2np5.
3. Oxidation states : Fluorine exhibits only –1 oxidation states. In addition to these status
higher positive oxidation states of +3, +4, +5, +6 and +7 are also exhibited.
4. O2F2 is a strong fluorinating agent. It is employed for removing plutonium from spent
nuclear fuel, as it oxidise plutonium to PuF 6.
5. ClO2 is as a bleaching agent for paper pulp and textiles.
6. Br2O, BrO2 and BrO3 are the oxides of bromine unstable at higher temperature and are
powerful oxidising agents.
7. I2O5 is a good oxidising agent and is used for estimation of CO.
8. Fluorine shows anomality in its behaviour due to (a) its small size, (b) high
electronegativity, (c) low F-F bond dissociation enthalpy and (d) non-availability of d-
orbital in valence shell.
9. HF is a liquid and also a weak acid because of intermolecular hydrogen bonding.
10. Fluorine is usually called as super halogen.
11. Chlorine is a greenish yellow, pungent, suffocating poisonous gas fairly soluble in
water. It combines with several metals and nonmetals except nitrogen, oxygen, carbon
and inert gases. It is prepared by the oxidation of hydrochloric acid, heating an electrovalent
chloride with conc H2SO4 in presence of MnO2 or by electrolysis of concentrated
sodium chloride solution.
4 HCl + MnO2 MnCl2 + 2H2O + Cl2.

2 KMnO4 + 16 HCl 2 MnCl2 + 2KCl + 8H2O + 5Cl2.
2 NaCl + 3H2SO4 + MnO2 2 NaHSO4 + MnSO4 + 2H2O + Cl2.
Moist chlorine acts as an oxidising and bleaching agent. Bleaching action of chlorine is
due to oxidation and it is permanent.
12. Hydrochloric acid is a colourless gas with pungent odour, highly soluble in water,
heavier than air. It acts as a reducing agent in presence of strong oxiding agent.
13. Aquaregia is a mixture of concentrated HCl and concentrated HNO 3 in the ratio 3 : 1.
It dissolves noble metals like gold and platinum.
3 HCl + HNO3 NOCl + 2H2O + 2Cl.
14. Hydrogen chloride gas is prepared in the laboratory by heating NaCl with conc H 2SO4.
NaCl + H2SO4 NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl (on heating)

15. HCl gas is collected by upward displacement of air, and dried by bubbling it through
Conc. H2SO4.
16. Interhalogen compounds or Interhalogens are compounds of one halogen with every
other halogen. These are generally covalent compounds and are more reactive than
halogens.
17. The interhalogen compounds of XY3 type have sp3d hybridisation and possess bent T-
shaped structure, of XY5 type have sp3d2 hybridisation and square pyramidal structure
and of XY7 type sp3d3 hybridisation showing pentagonal bipyramidal structure.
18. Halogens form oxo-acids commonly known as
(a) Hypohalous acid (b) Halous acid (c) Halic acid and (d) Perhalic acid.
19. The nuclear fuels like Uranium-235, are enriched by fluorinating agents.
QUESTIONS
A. Very short answer type questions (1 mark each)

1. Give any two uses of fluorine
2. HF is less volatile than HCl. Why is it so ?
3. What happens when HCl gas is passed through concentrated solution of sodium chloride ?
4. Arrange the halogen hydrides in the increasing order of bond lengths.
5. Among the hydracids of halogens which is the weakest ?
6. Which of the halogens forms hydrogen bond ?
7. Name an element which can belong both to Group I and Group 7 of the periodic table.
8. Which is the most electronegative element in the periodic table ?
9. Which halogen shows only one oxidation number in its compounds ?
10. Give the electronic configuration of chlorine atom.
11. Which halogen does not exhibit the oxidation state of +1
12. Arrange the following in order of increasing electronegativity.
Cl, I, F, Br
13. Arrange the following in order of increasing size. Cl, Cl +, Cl–
14. Which hydracid of halogen has the highest bond energy ?
15. What is the oxidation number of oxygen in OF2 ?
16. What is the role of MnO2 in the preparation of Cl2 from HCl.
17. Which is the strongest of the halogen acids ?
18. Write two uses of ClO2.
19. What is the shape of IF7 molecule ?
20. BrF3 or ClF5, which has bent T-shaped structure ?
21. Name two poisonous gases which can be prepared from chlorine gas.
B. Short answer type questions (2 marks each)

1. Electron affinity of fluorine is less than that of chlorine, why ?
2. What happens when NaCl is heated with K2Cr2O7 and conc. H2SO4 ?
3. Glass apparatus are not used for isolation and storing of fluorine. Why ?
4. Why is the boiling point of hydrofluoric acid abnormally high ?
5. Why is HF a liquid where as other hydrides of halogens are gases ?
6. Between the acids HBr and HI which is more easily oxidised ? Give reasons.
7. Explain on the basis of electronic configuration why fluorine and chlorine are put in 17
group of periodic table.
8 What happens when chlorine water is added to potassium iodide solution in small
quantity ? Give equation.
9 What happens when H2S is passed into chlorine water ?
10. Why Hydrogen fluoride is a liquid where as other Hydrogen halides are gases ?
11. Explain what happens when HCl gas is passed through concentrated NaCl solution.
12. Arrange F2, Cl2, Br2, I2 in the increasing bond dissociation enthalpy. Justify your answer.
13. Why are halogens coloured ?
14. HCl reacts with finely divided Iron forming ferrous chloride and not ferric chloride.
Why?
15. Arrange HF HCl, HI, HBr in the increasing order of their acidity. Justify your answer.
C. Long questions (3 Marks each)

1. What happens when Cl2 reacts with hot concentrated NaOH. Show with equation that,
this is a disproportionation reaction.
2. Why are halogens strong oxidising agents ? Name the strongest oxidising halogen.
3. Explain why fluorine forms only one oxoacid HOF.
4. Give the reasons for anomalous behaviour of fluorine.
5. How can you prepare Cl2 from HCl and HCl from Cl2 ? Write reactions only.
6. What happens when :
(a) NaCl is heated with conc. H2SO4 in presence of MnO2
(b) Cl2 gas is passed into the aqueous solution of NaI.
7. Write the reactions of F2 and Cl2 with water.
8. Predict the products obtained due to hydrolysis of ICl, ClF 3 and IF7.
9. Fluorine never acts as the central atom in polyatomic interhalogen compounds.
D. Long questions (7 Marks each)

1. Give a comparative account of Group 17 elements of periodic table.
2. Write notes on the general characteristics of halogens.
3. Write two methods of preparation of Chlorine ? Discuss its reaction with metals & non-
metals. Write two of its uses.
4. What happens when ? Write equations.
(a) Dry slaked lime reacts with Cl2.
(b) NH3 reacts with excess Cl2
5. Write notes on hydrides of halogens.
1. The electronic configuration of halogen is

(a) ns2 (b) ns2np3
(c) ns2np5 (c) ns2np4
2. Which of the following shows only one oxidation state ?
(a) F (b) Cl
(c) Br (d) I
3. Most electropositive halogen is
(a) F (b) Cl
(c) Br (d) I
4. The smallest atom is
(a) F (b) Cl
(c) Br (d) I
5. Fluorine doesn't show positive oxidation state due to absence of
(a) p - orbitals (b) d - orbitals
(c) s - orbitals (d) None
6. Bromine gas turns starch iodine paper
(a) Blue (b) Red
(c) Yellow (d) Colourless
7. Halogen having highest bond energy
(a) F2 (b) Cl2
(c) I2 (d) Br2
8. Bleaching powder is
(a) CaClO3 (b) CaClO
(c) CaOCl2 (d) Ca(OCl)2
9. Which of the following statement is correct
(a) Br2 is more reactive than Cl2 (b) I2 is more reactive than Br2
(c) Cl2 is insoluble in water (d) Iodine is solid
10. Sea weeds are important source of
(a) Fe (b) I2
(c) Cl2 (d) Br2
11. Among the C-X bond (where X = Cl, Br, I) the correct bond energy is
(a) C – Cl > C – Br > C – I (b) C – I > C – Cl > C – Br
(c) C – Br > C – Cl > C – I (d) C – I > C – Br > C – Cl
12. The strongest oxidising element is

(a) F (b) Cl
(c) Br (d) I
13. Which of the following has the highest molar heat of vaporisation
(a) HF (b) HCl
(c) HBr (d) HI
14. Which of the following radicals can bring about the highest oxidation state of a transition
metal
(a) F– (b) Cl—
(c) Br— (d) I—
15. The halogen that is most readily reduced is
(a) Chlorine (b) Bromine
(c) Iodine (d) Fluorine
16. Which of the following has greatest reducing power
(a) HCl (b) HI
(c) HF (d) HBr
17. The halogen that is most easily reduced is
(a) F2 (b) Cl2
(c) Br2 (d) I2
18. Oxidising action increases from left to right in the following order
(a) Cl < Br < I < F (b) Cl < I < Br < F
(c) I < F < Cl < Br (d) I < Br < Cl < F
19. The no. of electrons in a halogen in its outermost orbit in comparision with corresponding
noble gas is
(a) One electron less (b) One electron more
(c) Two electrons less (d) Two electrons more
20. Tear gas is
(a) COCl2 (b) CaOCl2
(c) NH3 (d) CCl3NO2
21. The element present in combined state in laminaria stenophylla is
(a) Bromine (b) Iodine
(c) Fluorine (d) Chlorine
22. The compounds used as refrigerants are
(a) NH3 (b) CCl4
(c) CF4 (d) CF2Cl2 (e) CH2F2
23. Which of the following displaces Br2 from an aqueous solution containing bromide ion.
(a) Cl2 (b) Cl–
(c) I2 (d) I3–
24. Which of the following compounds exists?
(a) KHCl2 (b) KHF2
(c) KHBr2 (d) KHI2
25. Which of the followin has the highest reducing power?
(a) HCl (b) HI
(c) HBr (d) HF
26. Structure of IF5 is
(a) Linear (b) Pentagonal bipyramidal
(c) Bent T-shaped (d) Square pyramidal
ANSWERS TO MULTIPLE TYPE QUESTIONS
1. c 6. c 11. a 16. b 21. b 26. d

2. a 7. b 12. a 17. a 22. a, d
3. d 8. c 13. a 18. d 23. a
4. a 9. d 14. a 19. a 24. b
5. b 10. b 15. d 20. d 25. b
qqq
GROUP 18 ELEMENTS : NOBLE GASES 325
CHAPTER - 10
GROUP 18 ELEMENTS : NOBLE GASES

(ZERO GROUP ELEMENTS)
10.1 INTRODUCTION :
The elements helium, neon, argon, krypton, xenon and radon are included in the zero
group of the periodic table. All these elements are monoatomic gases. Except helium, which
has 1s2 electronic configuration, all other elements have eight electrons (ns 2np6) in their outermost
shell. All these gases except radon are found in atmosphere in traces and hence they are called
rare gases. Radon is radioactive and is obtained from radioactive disintegration of radium.
These gases are called inert gases or noble gases, because they are relatively unreactive.
However, recently some of the inert gases are found to form compounds under suitable
conditions. The electronic configurations of these elements account for their high degree of
chemical inertness in ordinary chemical reactions.
10..2 OCCURRENCE :
(i) Atmosphere : All the noble gases except radon are present in the atmospheric air. The
relative abundance of these gases in atmosphere is given in Table - 10.1
TABLE - 10.1
Relative abundance of Noble gases in Atmosphere
Element (Symbol) Percentage by Volume

Helium (He) – 5.2 x 10–4
Neon (Ne) – 1.8 x 10–3
Argon (Ar) – 9.3 x 10–1
Krypton (Kr) – 1.4 x 10–4
Xenon (Xe) – 8.7 x 10–6
It may be noted that Argon is the most abundant noble gas.

(ii) Natural gas : Natural gas contains about 2–7% helium.
(iii) Minerals : Minerals like monazite sand, pitch blende, thorianite and clevite contain
helium. Small amounts of helium and argon are also found in some mineral springs.
(iv) Sun : Helium is also found is sun's atmosphere where it is formed from hydrogen by
nuclear fusion.
(v) Radioactive element : Radon is produced in the radioactive decay of radium.
10.3 POSITION OF INERT GASES IN THE PERIODIC TABLE :
The inert gases were not known during Mendeleef's time when the original classification
of element was proposed. Moreover, the existence and discovery of such elements, devoid of
chemical activity could not be visualised at that time and no space was provided for these
elements in the periodic table though several vacant places were left for elements to be
discovered. Basing on the critical analysis of the periodic table, Juliot Thomson suggested that
there must be a chemically inert group of elements between highly electronegative halogens
(Group 17) and highly electropositive alkali metals (Group 1). After the discovery of the inert
gas elements, the new group was introduced into the periodic table as zero group.
The electronic configurations of these elements are considered to be most stable which
account for their inertness.
The electronic configurations are –
He (2) ® 1s2
Ne (8) ® 1s2, 2s2, 2p6
Ar (18) ® 1s2, 2s2, 2p6, 3s2, 3p6
Kr (36) ® 1s2, 2s6, 2p2, 3s2, 3p6, 3d10, 4s2, 4p6
Xe (54) ® 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2, 4p6, 4d10, 5s2, 5p6
Rn (86) ® 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2, 4p6, 4d10, 4f14, 5s2, 5p6, 5d10, 6s2, 6p6
which suggest that these elements have saturated shells. Therefore, they have no tendency
either to lose or gain or share electrons with atoms of other elements. In other words, their
valency or combining capacity is zero. Hence, they are placed in zero group.
TABLE - 10.2
Some Physical Properties of Noble Gases
Property He Ne Ar Kr Xe Rn
Atomic Numer 2 10 18 36 54 86
Atomic mass/g-mol–1 4.00 20.18 39.95 83.80 131.30 222.00
Electronic 1s2 [He] 2s2 [Ne] 3s2 [Ar]3d10 [Kr]4d10 [Xe]4f14

Configuration 2p6 3p6 4s24p6 5s25p6 5d106s26p6
Ionisation 2372 2080 1520 1351 1170 1037

Enthalpy/kJ.mol–1
Electron gain 48 116 96 96 77 68

enthalpy/kJ.mol–1
0
Atomic radios ( A ) 1.20 1.60 1.90 2.00 2.20 -
M.P/K 0.9 24 84 116 161 202
B.P/K 4.2 27.1 87.4 120.3 165.2 211
Though these elements are chemically inactive, their reactivity increases with the increase
in the atomic number. This is because of the fact that the ionisation potential decreases as we
go down the group (Table - 10.2) The decrease in the ionisation potential makes the electron
available for chemical reaction.
10.4 PROPERTIES OF ZERO GROUP ELEMENTS :

The general trend in the physical properties of inert gas elements are given in Table-
10.2. All these elements are colourless and odourless gases.
10.4.1 Monoatomic nature :

These gases exist as monoatomic gases. This has been established from the specific
heat ratio (Cp/Cv) for all inert gases which has been found to be 1.66 (theoretical value of all
monoatomic gases). Other physical constansts such as refractive index, dielectric constant etc.
also confirm their monoatomic character. This is because the atoms of inert gas elements have
saturated shells and they have no tendency to combine amongst themselves.
10.4.2 Solubility in water :

Noble gases are slightly soluble in water. Neon and Argon gases are more soluble in
water than nitrogen. The solubility in water increases from He to Rn. Noble gases are soluble
in water because polar water molecule induces dipole in those molecules. As water molecule
is polar in nature when it comes near a noble gas atom, it induces a dipole in the noble gas
atom by polarizing its symmetrical electron cloud. This induced dipole interacts with the
dipole of water molecule and hence the noble gas dissolves (Fig. 10.1). On moving from He
to Rn the size of the noble gas increases and also the extent of polarization of it, resulting in
the increase of the dipole-induced dipole interaction or extent of solubility in water. They are
slightly soluble in water. Neon and argon are more soluble in water than nitrogen.
Noble Gas
d+ d+
H H
d d
- -
d- d+
d+ d+
H H
Polar water Distorted Symmetrical
molecule electron electron
cloud cloud
Fig 10.1 : Polarization of noble gas by polar water molecules
10.4.3 Liquefaction of the Noble Gases :

On account of weak van der Waals force of attraction existing in these gases, these
are relatively difficult to be liquified. However, they can be liquified and solidified at very low
temperature. Liquefaction of these gases increases from helium to xenon, since the vander
Waals forces increase in the same order. For the same reason, the boiling points and melting
points of these gases are very low and increase with the increase in the atomic number. The
m.p (0.9K) and b.p. (4.2K) of helium are the lowest of any known element.
10.4.4. Ionisation Enthalpy :
As already discussed, the outermost shells have stable electronic configuration and
therefore the ionisation energies are very high. They decrease with increase in atomic number.
Thus, the reactivities increase due to availability of electrons for chemical reaction. The
outermost electrons in Kr and Xe are away from the nucleus and therefore less firmly held.
Thus, Krypton and Xenon can combine with highly electronegative elements like oxygen or
fluorine which has strong tendency to attract electrons towards itself and leaves Krypton and
Xenon with a net positive charge.
10.4.5 Electron Affinity :
The stable electronic configurations of these elements do not allow them to accept
electrons. Hence, they have zero electron affinity.
10.4.6 Atomic radii :

Noble gases are monotomic. They have only van der Waals radii (not the covalent
radii). So in a period the atomic radius of the noble gas present in it is largest. The atomic
radii increase with the increase in atomic numbers from Helium to Radon, because new shells
are added.
10.4.7 Adsorption by activated charcoal :

All noble gases are adsorbed by activated charcoal at low temperature. The capacity
of adsorption increases with increase in atomic mass. Helium has the minimum adsorption
capacity.
Each of these noble gases has a characteristic spectrum by which it can be easily
identified.
These elements are fairly good conductors of heat and electricity. The thermal
conductivity of helium is very high at room temperature (even much higher than copper).
Unusual Properties of liquid Helium

It is observed that if the temperature is lowered below 2.1K, a new form of helium,
called He (II) is formed. He (I) boils vigorously, but if the temperature is lowered to 2.1K, the
boiling stops and the liquid continues to vanish. He (II) is superconductive and therefore does
not boil vigorously and only evaporates. When He (II) is poured in a beaker to a level much
below the top, it rises up the wall against gravity and passes over the top and flows down
outside. It solidifies at 0.9K and 25 atmospheric pressure.
10.5 CHEMICAL PROPERTIES :

The inert gas elements have stable electronic configuration. However, under suitable
conditions elements like xenon and krypton have been found to react chemically and the
reactivity increases with increase in atomic number. That is why, the inert gases are now called
noble gases. Highly electronegative elements such as oxygen and fluorine are capable of
forming compounds, because chemical reactivity of noble gases involves loss of electrons.
Xenon, having the least ionisation energy forms a large number of compounds. Krypton forms
only a few number of compounds, but with difficulty. Helium, neon and argon do not form
compounds.
Platinum hexafluoride, PtF6 is a powerful oxidising agent which is capable of oxidising
molecular oxygen forming an ionic compound O +2 P tF 6- . This observation led to suggest
that xenon which has almost same ionisation potential can form similar compounds. In 1962,
Bartlett could isolate similar type of compound, Xe +(PtCl6)– by the reaction of xenon with
platinum hexachloride at room temperature.
A few compounds of xenon, especially the fluorides are discussed below.
FLUORIDES OF XENON
A number of fluorides of xenon have been prepared and studied. They are XeF 2, XeF4
and XeF6.
1. Xenon difluoride, XeF2 :
Preparation : It is prepared
(i) by heating a mixture of xenon and fluorine in the ratio 1:3 in a nickel tube at
673K. On cooling the vapour, xenon difluoride is obtained as a colourless solid.
Ni - tube
Xe + F2 XeF2
673K
(ii) by photochemical combination of xenon and fluorine under the influence of
mercury vapour.
Mercury vapour
Xe + F2 XeF2
(iii) by reaction of xenon with excess amount of O2F2 at 155K.
Xe + O2F2 ¾155K
¾¾ ¾® XeF2 + O2
PROPERTIES
Physical : Xenon difluoride is a colourless, crystalline solid and melts at 300K. It is the
least volatile of all the fluorides of xenon.
Chemical :
(i) With hydrogen : It reacts with hydrogen forming xenon and hydrogen fluoride.
XeF2 + H2 ® Xe + 2HF
(ii) With water : It oxidises water to oxygen and hydrogen chloride to chlorine.
2XeF2 + 2H2O® 2Xe + 4HF + O2
XeF2 + 2HCl ® Xe + 2HF + Cl2
(iii) With PF5 : XeF2 reacts with fluorine ion acceptors like PF 5,
SbF5 to form cationic species.
XeF2 + PF5 ® [XeF]+[PF5]–
Uses : (i) It is an effective fluorinating agent.
(ii) Xenon can be prepared from it (by reactions with H 2 and H2O)
Structure : XeF2 molecule has a linear structure (F–Xe–F) which can be explained in the
light ofhybridisation.
5s 5p 5d
The electronic configuration of
-¯ -¯ -¯ -¯
Xe atom in the ground state :
and in the excited state : -¯ -¯ -¯ - -

sp 3d hybridisation
Xe atom in the hybridised state : -¯ -¯ -¯ - - OR Xe
Five sp3d hybrid orbitals
After hybridisation, they form five sp 3d hybrid orbitals with three orbitals having lone
pairs and two, having one electron each, which overlap with 2p orbitals of fluorine and form
two Xe–F sigma bonds.
F F
Thus, the molecule assumes a
linear shape as shown in Fig. 10.2 ·· ·· OR ···Xe··
Xe ·
·· F
F
Fig. 10.2 : Linear structure of XeF2
2. Xenon tetrafluoride, XeF4
Preparation – It is prepared
(i) by passing electric discharge through a mixture of xenon and fluorine at 193K
and 2-15mm pressure.
Electronic discharge
Xe + 2F2 XeF4
193K
2-15 mm press.
(ii) by heating a mixture of xenon and fluorine in molecular ratio 1:10 to 673K under
6 atmospheric pressure in a nickel vessel for a few hours and cooling the vapour
immediately.
Nickel vessel
Xe(g) + 2F2(g) XeF4(s)
400 0 C, 6 atm. Press.
PROPERTIES
Physical – It is a colourless crystalline solid which melts at 100 0C and sublimes on
heating. It is quite stable in pure and dry state and can be stored in a nickel vessel. It dissolves
in liquid HF without any chemical reaction.
Chemical :
(i) With hydrogen : XeF4 reacts with hydrogen liberating xenon.
XeF4 + 2H2 ® Xe + 4HF
(ii) With water : It reacts with water forming a highly explosive compound XeO 3
2XeF4 + 3H2O ® Xe + XeO3 + 6HF + F2
(iii) With potassium iodide : It oxidises KI to I2
4KI + XeF4 ® Xe + 4HF + 2I2
(iv) With sulphur tetrafluoride : Xenon tetrafluoride fluorinates sulphur tetrafluoride to
sulphur hexafluoride.
2SF4 + XeF4 ® Xe + 2SF6
(Sulphur hexafluoride)
(v) With SbF5 : It reacts with fluoride ion acceptors like antimony pentafluoride to form
cationic species.
XeF4 + SbF5 ® [XeF3]+ [SbF6]–
Uses
(i) For the preparation of xenon.
(ii) As a fluorinating agent.
Structure : Xenon tetrafluoride molecule has a square planar structure which can be
explained in terms of sp3d2 hybridisation.
5s 5p 5d
Xenon atom in its ground state : -¯ -¯ -¯ -¯
-¯ -¯ - - - -
In the excited state : sp 3 d 2 hybridisation
- - -
Xe
Xe atom in sp3d2 hybridised state : -¯ -¯ - - - - OR
- -
Six sp3d2 hybrid orbitals -
After hybridisation, they form six sp3d2 hybrid F F ··

F F
orbitals with two hybrid orbitals containing lone pairs
in axial positions and four hybrid orbitals centaining Xe OR Xe
one electron each in equitorial position which overlap
F F
with 2p orbitals of 4F atoms forming sigma bonds. F F
··
The molecule assumes square planar structure. (Fig. Fig. 10.3 : Square planar
10.3) structure of XeF4 molecule.
3. Xenon hexafluoride, XeF6

Preparation : It is prepared
(i) by heating a mixture of xenon and fluorine in molecular ratio 1:20 to 523K –
573K under 50 atmospheric pressure in a nickel vessel. The yield is about 95%.
Ni-vessel
523K – 573K
Xe + 3F2 XeF6
50 atm. press
(ii) by the direct interaction of XeF4 with O2F2 at 143K
XeF4 + O2F2 ¾143K¾¾ ¾® XeF6 + O2
PROPERTIES :
Physical : Xenon hexafluoride is a colourless crystalline solid which melts at 322.5K
giving a yellow liquid. It is volatile.
Chemical :
(i) With hydrogen : XeF6 reacts with H2 liberating xenon.
XeF6 + 3H2 ® Xe + 6HF
(ii) With moisture : Slow hydrolysis of xenon hexafluoride by atmospheric moisture
gives solid XeO3.
XeF6 + 3H2O ® XeO3 + 6HF
Small quantity of water brings about partial hydrolysis of XeF 6 producing a
colourless liquid containing xenon oxyfluoride, XeOF4.
XeF6 + H2O ® XeOF4 + 2HF
Complete hydrolysis forms XeO3 as the final product.
XeF6 + 3H2O ® XeO3 + 6HF
(iii) With HF : XeF6 veacts with HF and forms [XeF5]+[HF2]– which is appereciably
ionised.
XeF6 + HF ® [XeF5]+[HF2]– ® [XeF5]+ + [HF2]–
(iv) With silica : It reacts with silica readily and hence can not be stored in glass
vessels.
2 XeF6 + SiO2 ® 2XeOF4 + SiF4
(silica)
(v) With Alkali metal fluorides : It reacts with fluoride ion donors like alkali metal
fluorides to form fluoroanions.
XeF6 + MF ® M+ [XeF7]– (M = Na, K, Rb or Cs
Uses : (i) As an oxidising agent, it oxidises hydrogen to HF, HCl to Cl2 and NH3 to N2.
(ii) As an effective fluorinating agent.
F
Structure : F F
The structure of XeF6 is a controversial issue. The Xe

molecule is believed to have distorted octahedral
structure in gaseous state. (Fig 10.4) This can be explained F F
by sp3d3 hybridisation in Xe atom in the molecule. F
Fig. 10.4 : Distorted
octahedral shape of
XeF6 molecule.
4. Xenon trioxide (XeO3)
Preparation : It is prepared by hydrolysis of XeF4 and XeF6 with water
6 XeF4 + 12 H2O ® 4 Xe + 2XeO3 + 24 HF + 3O2
XeF6 + 3 H2O ® XeO3 + 6 HF
..
Properties :
(1) It is a colourless explosive solid. The xenon atom is sp 3 Xe
hybridised and the molecule has a pyramidal structure (Fig. O O
10.5)
O
(2) It acts as a powerful oxidising agent. It oxidises Pu 2+ to Fig. 10.5 Structure
Pu4+ in the presence of H+ ions. of XeO3
3 Pu2+ + XeO3 + 6H+ ® 3Pu4+ + Xe + 3 H2O
(3) Xenon trioxide reacts with aqueous alkali to form the hydrogen xenate ion,
HXeO4–. HXeO4– slowly undergoes disproportionation to give xenon and perxenate
ion, XeO64–, which is a powerful oxidising agent.
XeO3 + OH– ® HXeO4–
Hydrogen xenate ion
2 HXeO4– + 2OH– ® XeO64– + Xe + O2 + 2 H2O
Perxenate ion
5. Xenon oxyfluorides :
Preparation : Partial hydrolysis of XeF6 give oxyfluorides, XeOF4 and XeO2F2.
XeF6 + H2O ® XeOF4 + 2HF
XeF6 + 2H2O ® XeO2F2 + 4HF
Properties : O
(1) XeOF4 is a colourless volatile liquid. Here the central
F F
'Xe' atom is sp3d2 hybridised and it has a square
pyramidal structure. Xe
F F
..
Fig. 10.6 : Structure
of XeOF4
F
(2) XeO 2F 2 (Xenon dioxydifluoride) has trigonal
bipyramidal structure. Here the 'Xe' atom is sp 3d O
hybridised. Xe
..
O
F
Fig.: 10.7 Structure
of XeO2F2
10.6 USES OF NOBLE GASES :
Of all the noble gases only helium and argon are plentily and easily available. The uses
are due to their chemical inertness and low boiling points. Some important uses of the noble
gases are given below.
Uses of Helium :
1. Filling airships and balloons : In lightness, helium is next to hydrogen. Being non-
inflammable and light, it is used for filling weather balloons and airships. For this
purpose 85% helium and 15% hydrogen is usually used. Helium is also used for
inflating the tyres of big aeroplanes.
2. Relief in respiratory diseases : A mixture of helium and oxygen is used in the
artificial breathing of asthma patients. This keeps the breathing steady. Helium is also
used for the treatment of some respiratory diseases.
3. Respiration of sea divers : The mixture of helium and oxygen (20:80) is used for
respiration by sea divers. The air proves harmful, because nitrogen of the air dissolves
in the blood at high water pressure when the diver is in the deep sea. When he comes
out to the surface, the pressure suddenly decreases and the dissolved nitrogen from the
blood escapes in form of bubbles and gives a painful sensation, called bends.
4. Gas thermometer : Helium is used for filling gas thermometers, used for low
temperature measurement.
5. Welding of metals : It is used for providing inert atmosphere is the welding of metals
and alloys.
6. Production of low temperature : Liquid helium (b.p. 4.2K) is used as a cryogenic
fluid for producing low temperature required for research work.
7. Space programme : It is used as a pressuring agent in rockets to expel liquid oxygen
and liquid hydrogen.
8. Clinical diagnosis : It is used to produce and sustain powerful super condcuting
magents which form essential part of NMR spectrometers and MRI (Magnetic
Resoanance Imaging) systems used for clinical diagnosis.
Uses of Neon :
1. Production of coloured glow : Neon is used in discharge lamps and tubes to produce
brilliant coloured glow, often used for advertising purposes since neon lights are visible
from long distances. Mixed with mercury vapour, neon produces blue or green colour.
2. Beacon light : Neon light can penetrate through fog and mist. Therefore neon signs
are used in beacon lights for ships and aeroplanes.
3. Electrical devices : Neon is used in certain protective electric devices like voltage
stabilisers, current rectifiers etc.
Uses of Argon :
1. Electric bulbs and radio valves : A mixture of argon with 15% nitrogen is filled in
electric bulbs to increase the life of filaments. It is also used for filling radio valves.
2. Production of inert atmosphere : Argon is also used for producing inert atmosphere
in welding and in metallurgy of certain metals which are easily oxidised.
3. Coloured glow : A mixture of argon and mercury vapour produces blue or green
colour in the discharge tubes.
Uses of Krypton and Xenon :
These gases are used for filling electric bulbs and tubes. They are better than argon for
this purpose.
Uses of Radon :
1. Treatment of cancer : Radon, being radioactive is used in the treatment of cancer and
radiotherapy for treatment of malignant growths and non-healing wounds.
2. Industry : It is used for locating the defects in steel castings.
1. Zero group of the periodic table comprises of elements like helium, neon, argon, krypton,
xenon and radon.
2. These elements are called rare gases, inert gases or noble gases.
3. The outermost shell of all these elements are fully saturated. Except helium, others have
the general outermost electronic configuration ns 2np6.
4. Although present in a very small quantity, atmospheric air is the main source of these
elements except radon, which is obtained by the radioactive disintegration of radium.
Argon is the most abundant noble gas.
5. The mixture of rare gases is obtained from dry air or liquid air and separated by physical
and chemical methods.
CP
6. The inert gas elements are monoatomic. ( = 1.66 )
CV
7. The atomic radii, boiling points, melting points, and the capacity of being adsorbed
increase with increase in atomic number.
8. The electron affinity of these elements is zero. The ionisation potential is very high and
decreases with increase in atomic number.
9. Noble gases are soluble in water because of polarization of their molecules by the dipole
interaction of polar water molecules.
10. Inert gases find a large number of applications because of their unique properties.
11. The ionisation potential of xenon being less compared to other inert gases, it can form
compounds with highly electronegative elements like oxygen and fluorine. Krypton forms
relatively less number of compounds than xenon.
12. The most important fluorides of xenon are XeF 2, XeF4 and XeF6. They are stable XeF2
has a linear structure. XeF4 has a square planar structure and XeF6 has a distorted
octahedral structure in the gaseous state.
13. XeO3 is payramidal in shape where the Xe atom is sp3 hybridised. Xenon oxyfuorides
i.e. XeOF4 and XeO2F2 have square pyramidal and trigonal bipyramidal structures
respectively.
QUESTIONS
(A) Very short answer type questions (1 mark) :

1. Why sea divers use a mixture of helium and oxygen instead of air for respiration ?
2. What lamp is used as beacon lights for ships and aeroplanes ?
3. Two of the following are inert gases. Identify them.
Oxygen, Neon, Nitrogen and Helium
4. Why the noble gases, in general, are chemically inert ?
5. Which are of the following inert gases is the most abundant in air ?
Ne, Ar, Kr, He
6. Why argon is monoatomic ?
7. Which gas is used in beacon lights ?
8. The most abundant noble gas present in the atmosphere is ————
9. Give one use of xenon tetrafluoride.
10. Why zero group elements do not form diatomic molecules ?
11. Give the electronic configuration of argon atom.
12. Write any one use of xenon difluoride.
13. Which of the noble gases is radioactive ?
14. Which noble gas is used for treatement of cancer.
15. Show the product that is formed by the interaction of xenon with excess of O 2F2 at 155K.
16. Give any two uses of xenon tetrafluoride.
17. Write two uses of Helium.
18. Write the electronic configuration of krypton.
19. Write the structure of XeO2F2 molecule.
20. Write the shape of xenon difluoride.
21. Which of the following noble gases is used in weather balloons
i) He, ii) Xe, iii) Ne, iv) Kr
22. Why has it been difficult to study the chemistry of radon ?
(B) Short answer type questions (2 marks each) :

1. Explain why neon is monoatomic.
2. Mention one use of each of four noble gases.
3. Chemical activity of noble gases vary in the group, how ?
4. Give a brief account of the preparation, properties and structure of XeF 6
5. Which inert gas contains less than eight electrons in its outer shell ? What is its atomic
number ? Write down its electronic configuration.
6. The inert gas molecules are monoatomic. Why it is so ?
7. Write the electronic configuration of krypton, Why is it inert ?
8. Name the zero group elements and give their atomic numbers.
9. Give a method of preparation of xenon tetrafluoride.
10. Give the shapes of Xenon di and tetrafluorides.
11. Why do Noble gases have low boiling points ?
12. Noble gas atoms have highest atomic radius than other elements present in that period.
Why ?
13. Amongst all noble gases only xenon is known to form compounds with oxygen and
fluorine. Given reasons.
14. Which compound led to the discovery of noble gases ? How?
(C) Short Questions (3 marks each) :
1. Xenon forms fluorides easily. Explain in two or three sentences.
2. Give the hybridisation of Xe in XeF2, XeF4 and XeOF4.
3. Write down the structure of XeO4 and XeF4
4. Complete the following chemical equations :
(a) ®
XeF2 + PF5
(b) XeF4 + H2O ®
(c) XeF4 + O2F2 ®
5. Write the hybridization and also draw the melecular structure of
(a) XeO3
(b) XeOF4
(c) XeO2F2
(D) Long Questions (7 Marks each) :
1. Write a short account of the fluorides of xenon stating their preparation and properties.
2. Why the zero group elements are also known as inert gases ? Which inert gas contains
less than eight electrons in its outer shell ? Give the preparation of Xenon tetrafluoride.
3. Name the zero group elements and give their atomic numbers. How xenon difluoride is
prepared and what is its use ?
4. On the basis of electronic configuration discuss the position of inert gases in the periodic
table.
5. How will you account for the formation of Xenon fluorides ? Give the preparation and
structures of xenon difluoride and xenon tetrafluoride.
MULTIPLE CHOICE QUESTIONS
1. Noble gas used in radiotherapy is

(a) Kr (b) Ar
(c) Rn (d) Xe
2. Deep sea divers respirate in a mixture of
(a) oxygen and argon (b) oxygen and helium
(c) oxygen and nitrogen (d) oxygen and hydrogen.
3. Shape of XeF4 is
(a) Linear (b) trigonal pyramidal
(c) pyramidal (d) square planar
4. Which of the following is not correct about the rare gases ?
(a) They are used to provide inert atmosphere in many chemical reactions.
(b) They are sparingly soluble in water.
(c) They form diatomic molecules
(d) Some of them are used for advertising signboards.
5. The first noble gas compound obtained was
(a) XeF2 (b) XePtF6
(c) XeF4 (d) XeO2F2
6. The valency of noble gas is
(a) zero (b) one
(c) two (d) three
7. Which of the following noble gases is the least polarisable ?
(a) He (b) Ne
(c) Kr (d) Xe
8. Which of the following fluorides of xenon is impossible ?
(a) XeF2 (b) XeF3
(c) XeF4 (d) XeF6
9. The outermost shell of the elements of inert gases in characterised by
(a) ns2np6 (b) ns2np5
(c) ns2np4 (d) ns2np3
10. The coloured discharge tubes for advertisement contain
(a) Xenon (b) Helium
(c) Argon (d) Neon
11. Monazite on heating gives.

(a) Ra (b) Ar
(c) He (d) Ne
12. The maximum number of compounds are formed by
(a) He (b) Xe
(c) Kr (d) Ne
13. The inert gas abundantly found in atmosphere is
(a) Xe (b) Kr
(c) Ar (d) He
14. Which of following is called stranger gas ?
(a) Kr (b) Xe
(c) He (d) Ne
15. Which of the following rare gases shows least ionisation potential ?
(a) Ar (b) Kr
(c) He (d) Xe
16. The noble gas which behaves abnormally in liquid state is.
(a) Xe (b) Ne
(c) He (d) Ar
17. Which of the following liquids can climb up the wall of the glass vessel in which it is
placed ?
(a) Alcohol (b) Liquid He
(c) Liquid N2 (d) Water
18. The compound that attacks pyrex glass is
(a) XeF2 (b) XeF4
(c) XeF6 (d) None
19. How many lone pairs are associated with xenon difluoride ?
(a) 1 (b) 2
(c) 3 (d) 4
20. In XeO3 molecule Xe atom shows which hybridisation.
(a) sp3 (b) sp3d
(c) d3sp2 (d) sp3d2

E 1. (c), 2. (b), 3. (d), 4. (c), 5. (b), 6. (a), 7. (a) 8. (b),
9. (a), 10. (d), 11. (c), 12 (b), 13. (c), 14. (b) 15. (d). 16. (c).
17. (b), 18. (c). 19. (c). 20. (a).
qqq
UNIT - VIII
d and f - BLOCK ELEMENTS
CHAPTER - 11
d- BLOCK ELEMENTS : TRANSITION ELEMENTS
11.1 TRANSITION METALS :

A transition metal may be defined as one that has an incomplete inner d-orbital. A transition
metal is also called a transition element or a d-block element.
— —
The general electronic configuration of transition elements is (n-1)d1 10 ns1 2, whereas
— — —
the general electronic configuration of representative elements is ns1 2 or ns1 2 ns2 np1 6.
In the case of d-block (transition) elements, electrons are added successively to the
inner d-orbitals.
The elements are called transition elements (Table 11.1) as they are placed between the s-
and p-block elements and their properties represent a transition between the highly reactive
electropositive elements of the s-block and the electronegative elements of the p-block.
TRANSITION ELEMENTS
d - BLOCK
3 4 5 6 7 8 9 10 11 12
21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn
39Y 40Zr 41Nb 42Mo 43Tc 44Ru 45Rh 46Pd 47Ag 48Cd
57La 72Hf 73Tn 74W 75Re 76Os 77Ir 78Pt 79Au 80Hg
Sg Bh Hs Mt Ds
89Ac 104Rf 105Ha 106
/106 107
/107 108
/108 109
/109 110
/110
Table : 11.1 Position of transition elements in the periodic table

d - BLOCK ELEMENTS : TRANSITION ELEMENTS 343
As shown above (Table 11.1) the d-block elements belong to groups 3 to 7, 8 and 11 to 12 of the
periodic table.
These transition elements are present in the periodic table in four series.
Table : 11.2 Series of transition elements
Series Number Element present Electronic

of elements configuration
— —
1st Series (3d Series) 10 Sc21(Scandium) to Zn30 (Zinc) [Ar]3d1 104s1 2
— —
2nd Series (4d Series) 10 Y39(Yttrium) to Cd40 (cadmium) [Kr]4d1 105s1 2
3rd Series (5d Series) 10 La57(Lanthanum), Hf72(Hafnium)

— —
to Hg80 (Mercury) [Xe]4f145d1 10 6s1 2
4th Series Ac89 (Actinium),Rf104 and

— —
(6d incomplete series) newly discovered elements, [Rn]5f14 6d1 10 7s1 2
At.No. 105-110
Just after the transition element Lanthanum La 57 ([Xe]4f05d16s2) (Table.11.2), the

next transition element is Hafnium Hf 72 [Xe]4f145d26s2. The elements occurring just after
Lanthanum is Cerium, Ce 58([Xe]4f25d06s2). A series of 14 elements from Ce 58 to Lu71,
Lutetium ([Xe]4f145d16s2) ae called as 1st series of inner transition elements or f-block
elements. These are known as Lanthanides or 4f-block elements. The 2nd series of inner
transition elements are elements occurring just after the transition element Actinium,
Ac 89.These are the actinides or 5f-block elements beginning with Thorium, Th 90
([Rn]5f 06d 27s 2) and ending till now in Lawrencium, Lw 103([Rn]5f 146d 17s 2). Inner
transition elements contain incomplete 4f and 5f orbitals respectively in addition to their
incomplete (n-1)d orbitals. Inner transition elements are special type of transition elements.
There are three transition series of elements (Table 11.2). The 1st series or 3d series
begins with the element Scandium, Sc 21 ([Ar]3d14s2) and ends with the element Zinc, Zn 30-
([Ar]3d104s2). The 2nd series or 4d series begins with the element Yttrium, Y 39 ([Kr]4d15s2)
and ends with the element Cadmium, Cd 48 ([Kr]4d105s2). The 3d series begins only with
Lanthanum, La57, ([Xe]4f05d16s2),and then begins with Hafnium, Hf 72 ([Xe]4f145d26s2)
and ends with the element Mercury, Hg 80 (Xe]4f145d106s2). The elements Zn, Cd and Hg
remain at the end of 3d,4d and 5d series respectively whose atoms have completely filled d-
orbitals for which they are non-transitional.
The first transition series :

The first transition series or 3d-series is present in the 4th period of the periodic
table (Sc21 to Cu29). Zn30 ([Ar]3d104s2) remains at the end of the series whose atom has
completely filled 3d-orbital for which it is non-transitional.
Table : 11.3 The outer electronic configurations of the atoms

and ions of the first transition series
Elements Atomic Outer E. C Ions and their outer E.C

number Ions E.C Ions E.C
Scandium (Sc) 21 3p63d14s2 Sc3+ 3p6(non-

transitional)
Titanium (Ti) 22 3p63d24s2 Ti2+ 3p63d2 Ti3+ 3p63d1
Vanadium(V) 23 3p63d34s2 V2+ 3p63d3 V3+ 3p63d2
Chromium (Cr) 24 3p63d54s1 Cr2+ 3p63d4 Cr3+ 3p63d3
Manganese (Mn) 25 3p63d54s2 Mn2+ 3p63d5 Mn3+ 3p63d4
Iron (Fe) 26 3p63d64s2 Fe2+ 3p63d6 Fe3+ 3p63d5
Cobalt (Co) 27 3p63d74s2 Co2+ 3p63d7 Co3+ 3p63d6
Nickel (Ni) 28 3p63d84s2 Ni2+ 3p63d8
Copper (Cu) 29 3p63d104s1 Cu2+ 3p63d9 Cu+ 3p63d10
(non-
transitional)
Zinc (Zn) 30 3p63d104s2 Zn2+ 3p63d10 (non-

transitional)
Based on experimental evidence the outer electronic configurations of chromium

and copper are 3d 54s 1 and 3d 104s 1 respectively. It may be noted that the electronic
configuration of chromium and copper unlike the others, show a single electron in the 4s
orbital. This is due to the additional stability gained by the atom when the d-orbital is exactly
half-filled (in the case of chromium) or completely filled ( in the case of copper).Accordingly
one of the 4s electrons shifts to the 3d orbital in the atoms of chromium and copper.
11.2 GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS :
Transition elements are solid metals hard,malleable and ductile. They have relatively
high densities, high melting points and high boiling points. These properties indicate that
the atoms in these elements are held together by strong metallic bonds. Such metallic bonds
are even present in their molten states. The properties of transition (d-block) elements are
intermediate between the properties of s and p block elements.
Table : 11.4 Properties of elements of the first transition metal series
Element
Property Sc Ti V Cr Mn Fe Co Ni Cu
Atomic mass 45.00 47.88 50.95 52.00 54.94 55.85 58.93 58.69 63.54
Atomic radius, A0 1.64 1.47 1.35 1.29 1.26 1.26 1.25 1.24 1.28
Ionic radius,A0 M2+ — 0.80 0.73 — 0. 90 0.85 0.80 0.76 0.69
M3+ 0.69 0.63 0.62 0.62 0.63 0.63 0.56 — —
1st.Ionisationenergy
kJmol—1 635 659 650 654 713 762 759 736 745
Density g.cc—1 3 4.5 6.0 6.9 7.4 7.9 8.7 8.9 8.9
Melting point, K 1200 1660 1710 1600 1260 1535 1490 1450 1083
Boiling point,K 2730 3260 3450 2660 2150 3000 2900 2730 2600
1. Atomic radii :
The atomic radii of the transition elements of a particular series decrease slightly
with increase in atomic number. In the case of these elements, the electrons are added
successively to the inner (n-1)d orbitals and these electrons screen the outer ns electrons
from the nucleus. The effective nuclear charge thus increases slightly. Therefore, there is a
slight decrease in atomic radii.
In the first transition series the atomic radius value increases from Ni (1.24) to Cu
(1.28). This is due to increased force of repulsion between added electrons which overcome
effective nuclear charge (nuclear attraction force).
2. Ionisation enthalpy :
Ionisation enthalpies of transition elements increase across a transition series with
increase in atomic number. This trend is, however, not regular. This is because though the
nuclear charge increases, the screening effect of added electrons also increases. These two
effects almost cancel each other. Ionisation enthalpies are in between s- and p- block elements
and these elements are less electropositive than s-block elements.
Zinc, cadmium and mercury have comparativly higher ionisation enthalpy values,
because they have stable outer electronic configuration, (n-1)d10ns2.
There is a general increase in the second ionisation enthalpy as the atomic number
increases. The exception is manganese.
The second ionisation enthalpy of Cr and Cu involves the removal of one electron
from the 4s orbital and another electron from the half-filled and completely filled 3 d-orbital
respectively. The half-filled and filled orbitals have extra stability associated with them.
Therefore, the second ionisation enthalpy of these elements are relatively larger. Eventhough
transition elements form ionic compounds, the tendency is less than the s-block elements. In
higher valency state, there is also a tendency for covalent bond formation.
3. Metallic properties :
Transition elements are all hard metals except mercury which is a liquid.These
elements are harder and more brittle than s-block elements.
The atoms in these elements are held together by strong metallic bonds. The strength
of such metallic bonding depends upon the interaction between the electrons in the outermost
shell. In general, the greater the number of valence electrons available, the stronger is the
bond. Further electrons in the d-orbitals form stronger metallic bonds. In transition elements,
a minimum of three electrons, (n-1)dx ns2 are available for interaction with other atoms for
the metallic bond formation.Again greater the number of unpaired electrons greater is the
strength of the bond. In the first transition series Cr is very hard having five unpaired d-
electrons. In the case of Zn 30 (3d104s2), the metal is not hard because there is complete
pairing of 3d electrons. In the third transition series Hg 80(5d106s2)having complete pairing
of 5d electrons exists as a liquid. These metals are, as expected, good conductors of heat and
electricity.
4. Denisities, melting and boiling points :

The high densities of transition elements are due to their relatively small atomic
radii. The densities of the first transition series elements increase across the period with the
increase in atomic number.
Transition elements have high melting and boiling points. The high melting and boiling
points are due to strong inter-atomic bonding which invloves the participation of both 4s and
3d electrons.
5. Variable oxidation states :
Transition elements show more than one oxidation states in their compounds. The
oxidation states shown by the first transition series are given in (Table9.5)The most usual
oxidation states are indicated as bold.
Tabe : 11.5 Different oxidation states of elements
of first transition series
Elements Sc Ti V Cr Mn Fe Co Ni Cu
Oxidation states +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4
+5 +5
+6 +6 +6
+7
Transition metals have their valence electrons in two different sets of orbitals ns and
(n-1)d which have nearly the same energies. All these elements use their two ns electrons
and thus show +2 oxidation states. When oxidation states are greater than +2, the unpaired
(n-1)d electrons are involved in bonding in addition to the ns electrons. The elements thus
show +3 and higher oxidation states besides +2 oxidation state. Scandium has exclusively
an oxidation state of +3. In the case of tansition elements the oxidation states vary by one
unit whereas in some of the p-block elements variable oxidation states marked by a difference
of two units. This is due to the inert pair effect. Thallium shows oxidation states +1 and +3
and lead has two oxidation states +2 and +4.
The element manganese exhibits six number of oxidation states from +2 to +7 in its
oxides MnO, Mn2O3, and MnO2 and Mn2O5. In manganate, MnO2- - —
4 and permanganate, MnO4

its oxidation states are +6 and +7 respectively.
6. Formation of coloured compounds :

Majority of transition metal compounds are coloured. In contrast the compounds of
s-and p-block elements are often colourless or are generally not strongly coloured.
When a compound absorbs light of a particular wavelength,it is able to promote and
electron from one energy level to another higher energy level.
If E1 is the energy associated with the electron in one energy level and E 2, the energy
associated with the elctron in the higher energy level, then E 2- E1= D E i.e. energy of absorbed
c
light or radiation. Since D E = hn =h , the energy of absorbed radiation is inversely
l
proportional to the wavelength l .
Coloured substances such as compounds of transition elements absorb in the visible
region 4000–7500A0or longer wavlength. Colourless substancees such as compounds of s–
and p– block elements absorb in the u.v(ultraviolet) region below 4000A 0 or shorter
wavelength.
The compounds of transition metals are coloured due to the presence of unpaired d-
electrons in the partly filled d- orbitals of the metal. Here the light radiation is absorbed in
the visible region ( l =4000 –7500 A0 ) with a fairly small energy to promote d– electron to
a higher energy level within the d- orbital, resulting d– d transitions of electrons. The colour
of the compound is complementary to the observed colour. CuSO 4.5H2O is blue in colour
since it absorbs orange colour from visible light ( l =6000 – 6500A0 ) and emits the
complementary colour blue ( blue is complementary to orange).
Relation between absorbed and observed colours
Wave length (A0) Absorbed colour Observed

complementary colour
4000- 4500 violet yellow
4500-5000 blue orange
5000- 5500 green red
5500- 6000 yellow violet
6000- 6500 orange blue
6500- 7000 red green
The compounds of Sc3+ (3d0 4s0) and Zn2+( 3d10 4s0 ) are colourless because they do
not contain any unpaired d-electron .
In case of s- and p- block elements, there may not be a d- orbital, if any one is
completely full. For such elements there cannot be any d-d transition of electrons. However,
s or p electron can be promoted to a higher energy level provided the element receives much
greater energy corresponding to wavelengths of ultraviolet region. Here there is no absorption
of radiation from the visible region. Therefore compounds of s- and p-block elements do
not appear coloured in the visible region.
Table : 11.6 Colour shown by some hydrated transition metal ions.
Ion Outer electronic No. of unpaired Colour

Configuration electrons
Sc3+ 3d0 0 Colourless

Ti3+ 3d1 1 Purple
V3+ 3d2 2 Green
Cr3+ 3d3 3 Violet
Mn+ 3d4 4 Violet
Mn2+ 3d5 5 Pink
Fe3+ 3d5 5 Yellow
Fe2+ 3d6 4 Green
Co2+ 3d7 3 Pink
Ni2+ 3d8 2 Green
Cu2+ 3d9 1 Blue
Cu+ 3d10 0 Colourless
Zn2+ 3d10 0 Colourless
7. Formation of Complex compounds :

Transition metal ions have greater tendency to form complexes in contrast to s– and p–
block elements.This is because the transition metals have (i) small size of highly charged cations
and (ii) vacant inner d–orbitals of approximately the same energy to accept lone pairs of
electrons donated by the groups called ligands and (iii) high effective nuclear charge in the
cation.
In a complex, a central atom or ion is surrounded by a number of other atoms, ions or

molecules called ligands. The bonding between ligand and the transition metal ion can be either
predominantly electrostatic or predominantly covalant.In many cases the attachment of ligands
to the central metal atom or ion is by coordinate covalent bonds. The number of attached ligands
is called coordination number (C.N) of the central metal atom or ion. The complex is said to be
unstable if the ligands are easily removed. If it is difficult to remove the ligands from the complex,
then the complex is stable one.
Complex ions such as cuprammine ion, [Cu(NH3)4]2+ (tetramminecopper (II) ion),
ferrocyanide ion, [ Fe(CN)6]4 (hexacyanoferrate(II) ion) and ferricyanide ion,[Fe(CN) 6]3
— —
(hexacyanoferrate (III)) are well known.

In the complex tetrammine copper (II) sulphate,[ Cu (NH 3)4]SO4 the complex ion is
tetrammine copper (II) cation, [Cu(NH 3)4]2+ . Here four ammonia molecules are bonded to the
central Cu2+ by coordinate covalent bonds.Each ammonia molecule donates a lone pair of electrons
located on its nitrogen atom to the Cu2+ ion.Ammonia molecules are called as ligands and are
neutral in nature.
2+ 2+
H N: :NH3 H N: :NH3
3 3
SO42 —
H3N: :NH3 H3N: :NH3
Tetrammine copper ( II ) sulphate Tetrammine copper ( II ) cation

Since ammonia is a neutral ligand, the charge 2+ on Cu is transferred on to the total
complex ion indicated by square bracket. In this complex, the complex ion is a cation and thus
the complex is called a cationic complex. In this complex, the coordination number of Cu 2+ is 4.
In the complex potassium ferrocyanide, K 4 [Fe(CN)6] (IUPAC name: Potassium
hexacyanoferrate (II)), the complex ion is hexacyanoferrate(II) ion, [Fe(CN) 6]4 .
—
CN 4—
:
NC: :CN
NC: :CN
:
CN
Hexacyanoferrate (II) anion
Since the complex ion is an anion the complex is called an anionic complex. In the
complex the coordination number of Fe 2+ is 6.
In the complex diammine silver chloride [Ag(NH 3)2]Cl, the complex ion is
[ H N: ® Ag ¬ :NH ]+
3 3
Diamminesilver (I) cation.

diammine silver(I) cation. two ammonia molecules are coordinated to the Ag + and hence the
coordination number of Ag + is 2.
9. Paramagnetism :
Transition metals and their compounds are paramagnetic in nature i.e. they are attracted
by magnetic field. Paramagnetism arises due to the presence of unpaired d- electrons. These
electrons can be regarded as spinning around their axes, just as an electric current through a
wire generates a magnetic moment. Magnetic moment due to electron spin is given by meff =
n( n + 2) where n = number of unpaired electrons.A substance become strongly paramagnetic
if it contains more number of unpaired electrons.Mn 2+ (3d5 4s0 ) and Fe3+ (3d5 4s0 )are most
paramagnetic, whereas Sc 3+ (3d10 4s0 )and Zn2+ (3d10 4s0 ) are diamagnetic in nature. A
diamagnetic (non-magnetic) substance is repelled by a magnetic field. In such cases, the
paired electrons possess opposite spins and cancel the magnetic moments.
In the case of Fe, Co and Ni the spins of the unpaired electrons are much
pronounced.As a result, these elements are much more paramagnetic than the rest of the
elements. These element are called ferromagnetic which means that they can be magnetised.
10. Catalytic activity :
Many transition metals and their compounds show catalytic activity due to their
variable oxidation states. In the variable oxidation states these are capable of forming unstable
intermediate compounds with catalysts. The metal ions while functioning as catalysts change
their oxidation states. They can also provide greater surface area for the reactants to the
absorbed and thus come closer to one another for the reaction to occur readily on their
(catalyst)surfaces.
The catalytic activity of nickel in the hydrogenation of oils, the use of platinum and
vanadium pentoxide, V2O5 in the contact process for manufacturing sulphuric acid and the
use of iron in Haber’s process for manufacturing ammonia are well known.
11. Alloys and interstitial compounds :

Transition metals form intermetallic alloys because they have atoms of nearly the
same size. Their atoms can mutually substitute each other in the metal lattice. They also
form interstitial alloys like stainless steel, chrome steel etc.
Transition metals form interstitial compounds. In interstitial hydrides, the hydrogen
is accommodated in the lattice of the transition element. Interstitial nitrides and carbides of
transition metals are known, which are similar to interstitial hydrides in structure.
11.3 POTASSIUM DICHROMATE K2Cr2O7 :
It is an important oxidant used for preparation of many azo compounds. Besides it finds
its use in leather industry.
Preparation :
Steps involved
(i) Chromite ore (FeCr2O4) is fused with sodium or potasium carbonate in free access
of air producing sodium chromate.
4FeCr2O4 + Na2CO3 + 7O2 ® 8Na2CrO4 + 2Fe2O3 + 8CO2
(ii) The yellow solutions of Sodium dichromate is filtered and acidified with Sulphuric
acid to give a solution from which orange sodium dichromate Na 2Cr2O7.2H2O can
be crystallised.
2Na2CrO4 + 2H+ ® Na2Cr2O7 + 2Na+ + H2O
(iii) The hot saturated solution of Na2Cr2O7 is treated with KCl to produce potasium
dichromate. Sodium dichromate is more soluble than potasium dichromate.
Na2Cr2O7 + 2KCl ® K2Cr2O7 + 2NaCl
Sodium chloride precipitates out from the hot solution and is removed by filtration. On
cooling the mother liquor orange crystals of K2Cr2O7 crystllise out. The oxidation state of chromium
in CrO42– and Cr2O72– is the same. These ions are interconvertible in aqueous solution depending
upon pH of the solution.
2CrO42– + 2H+ ® Cr2O72– + H2O
Cr2O72– + 2OH– ® 2CrO42– + H2O
Structure of CrO42– & Cr2O72–
2– 2–
O
O mO O
9p
17
126°
Cr O Cr Cr
1
O
63
pm
O O O O
O
chromate ion dichromate ion
Potasium dichromate form orange red crystals melting at 671K. It is moderately soluble
in cold water but highly soluble in hot water.
1. On strong heating it decomposes to chromic oxide and oxygen
D
4K2Cr2O7 ¾¾® 4K2CrO4 + 2Cr2O3 + 3O2
2. It reacts with hydrochloric acid evolving chlorine
K2Cr2O7 + 14HCl ® 2KCl + 2CrCl3 + 7H2O + 3Cl2
3. When heated with Conc. H2SO4 and a soluble chloride such as NaCl, gives red vapours
of chromyl chloride.
K2Cr2O7 + 4NaCl + 6H2SO4 ® 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 + 2H2O
4. In volumetric analysis it is used as a primary standard. It is a powerful oxidising agent.
In acidic solution ie the presence of dilute H 2SO4 its oxidising action is represented as
Cr2O72– + 14H+ + 6e ® 2Cr3+ + 7H2O
Some oxidation reactions are given below.
(i) It liberates I2 from KI solution
6I– ® 3I2 + 6e
Cr2O72– + 14H+ + 6e ® 2Cr3+ + 7H2O
Cr2O72– + 6I– + 14H+ ® 2Cr3+ + 7H2O + 3I2
(ii) It oxidises Fe2+ to Fe3+
6Fe2+ ® 6Fe3+ + 6e
Cr2O72– + 14H+ + 6e ® 2Cr3+ + 7H2O
Cr2O72– + 14H+ + 6Fe2+ ® 2Cr3+ + 6Fe3+ + 7H2O
(iii) It oxidises H2S to S & SO2 to sulphuric acid.
3H2S ® 6H+ + 3S + 6e
Cr2O72– + 14H+ + 6e ® 2Cr3+ + 7H2O
Cr2O72– + 8H+ + 3H2S ® 2Cr3+ + 3S + 7H2O
3SO2 + 6H2O ® 3SO42– + 12H+ + 6e

Cr2O72– + 14H+ + 6e ® 2Cr3+ + 7H2O
Cr2O72– + 2H+ + 3SO2 ® 2Cr3+ + H2O + 3SO42–
(iv) It oxidises sulphite ion to SO42– ion.

Cr2O72– + 3SO32– + 8H+ ® 2Cr3+ + 3SO42– + 4H2O
5. In dichromate solution Cr2O72– ions are in equilibrium with CrO42– ions.
Cr2O72– + H2O 2CrO42– + 2H+
Orange red Yellow
(a) On addition of alkali the orange colour changes to yellow
K2Cr2O7 + 2KOH ® 2K2CrO4 + H2O
Orange red Yellow
(b) On addition of acid to the above solution the yellow colour again changes to
orange red.
2K2CrO4 + 2H2SO4 ® K2Cr2O7 + K2SO4 + H2O
Yellow Orange red.
Uses :
(i) In volumetric analysis for estimation of Fe 2+, I– ions.
(ii) In the preparation of several chromium compounds like ZnCrO 4, PbCrO4 etc.
(iii) In photography.
(iv) As a cleansing agent (K2Cr2O7 + Conc H2SO4) for glassware.
(v) In dyeing, chrome tanning etc.
11.4 POTASSIUM PERMANGANATE (KMnO4) :

Method of preparation :
(i) It is prepared from K2MnO4 by the action of dil H2SO4
3K2MnO4 + 2H2SO4 ® 2K2SO4 + 2KMnO4 + MnO2¯ + 2H2O
MnO2 is removed by filtration. Potassium permanganate being less soluble than K 2SO4,
crystallises out first.
(ii) Solid manganese (IV) oxide is fused with KOH and the melt is stirred in contact with air
2MnO2 + 4KOH + O2 ® 2K2MnO4 + 2H2O
Chlorine gas is then passed through green solution of potassium manganate to produce
potassium permanganate.
2K2MnO4 + Cl2 ® 2KCl + 2KMnO4
Since KCl is more soluble than KMnO4, on concentrating the solution KMnO4 separates
out first leaving behind KCl in solution.
(iii) By electrolysis : The manganate solution is taken in the anodic compartment and the
cathodic compartment is filled with dilute alkali solution. Oxidation is carried out
electrolytically using Ni anode and iron cathode.
Reaction at anode :
The manganate ion is oxidised to permanganate ion in the anodic compartment.
Electrolytic
MnO42– MnO4–
oxidation in
manganate ion alkaline solution permanganate ion
Reaction at cathode :
2H+ + 2e ® 2H ® H2
From ionisation
of water
Potasium permanganate forms dark purple (almost black) crystal isostructural with those
of KClO4.
It is not very much soluble in water, about 6.4 gms dissolving in 100 gms of water at
293K.
Both manganate and permanganate ions are tetrahedral. The green manganate is
paramagnetic with one unpaired electron whereas the purple permanganate is diamagnetic.
The p bonding is due to overlap of p-orbital of oxygen with d-orbital of manganese.
O– O
Mn Mn
O O– O O–
O O
Tetrahedral manganate ion (green) Tetrahedral permanganate ion (purple)

1. It decomposes evolving oxygen when heated alone or with alkali.
D
2KMnO4 ¾¾® K2MnO4 + MnO2 + O2
4KMnO4 + 4KOH ® 4K2MnO4 + 2H2O + O2
2. When treated with Conc H2SO4 it produces Mn(VII) oxide which decomposes explosively
when heated.
2KMnO4 + H2SO4 ® Mn2O7 + K2SO4 + H2O
3. It is a powerful oxidising agent. A powdered mixture of sulphur, charcoal and potassium

permanganate is like gunpowder. It burns when heated and explodes when rubbed.
Similarly a powdered mixture of KMnO4 and oxalic acid catches fire spontaneously.
4. KMnO4 is a strong oxidising agent in solution. The course of reaction depends upon the
nature of the solution in which the reaction is carried out i.e. whether it is acidic, neutral
or alkaline.
(a) In alkaline solution : MnO4– ion is first reduced to MnO42– ion and then to
manganese (IV) oxide. The colour of the solution changes from purple to green and
finally becomes colourless.
2MnO4– + 2OH– ® 2MnO42– + H2O + [O]
2MnO24– + 2H2O ® 2MnO2 + 4OH– + 2[O]
alkali
2MnO4– + H2O ¾¾ ¾¾® 2MnO2 + 2OH– +3[O]
In alkaline solution as is evident from the above overall reaction, 2 molecules of
KMnO4 give 3 atoms (or 6 equivalents) of available oxygen. Hence the equivalent
mass of KMnO4 is alkaline solution as an oxidising agent is one third its molar mass.
Example :
(1) Iodides are oxidised to Iodates.
2MnO4– + H2O + I– ® 2MnO2 + 2OH– + IO3–
(2) Ethylene is oxidised to glycol.
CH2 = CH2 + H2O + [O] ® CH2OH
|
CH2OH
(3) Toluene is oxidised to benzoic acid.
C6H5 – CH3 + 3 [O] ® C6H5 – COOH + H2O
(b) In neutral solution : The reaction is almost same as in case with faintly alkaline
solution.
2MnO4– + H2O ® 2OH– + 2MnO2 + 3[O]
Examples :
(1) H2S is oxidised to sulphur.
2MnO4– + 3H2S ® 2MnO2 + 3S + 2H2O + 2OH–
(2) Thiosulphate is oxidised to sulphate and sulphur.
2MnO4– + 3S2O32– + H2O ® 2MnO2 + 3SO42– + 3S + 2OH–
(c) In acidic solution : In acidic solution MnO4– ion is reduced to Mn(II) ion.
2MnO4– + 6H+ ® Mn2+ + 3H2O + 5[O]
The best acid to be used is dilute sulphuric acid, Permanganate titrations with HCl
are not satisfactory since HCl is oxidised to Cl 2 during the titration.
2KMnO4 + 3H2SO4 ® K2SO4 + 2MnSO4 + 3H2O + 5[O]
Most of the volumetric analysis in carried out in acid medium. The end point is
marked by change of colour from purple (MnO4–) to almost colourless [Mn (II) ion]
Examples :
(1) Fe2+ ion is converted to Fe3+ ion.
5Fe2+ + MnO4– + 8H+ ® 2Mn2+ + 4H2O + 5Fe3+
green yellow
(2) I2 is liberated from KI.
10I– + 2 MnO4– + 16H+ ® 2Mn2+ + 8H2O + 5I2
(3) Oxalic acid is oxidised to CO2.
2MnO4– + 16H+ + 5C2O42– ® 2Mn2+ + 8H2O + 10 CO2
(4) Sulphites are oxidised to sulphates
2MnO4– + 6H+ + 5SO32– ® 2Mn2+ + 5SO42– + 3 H2O
(5) H2S is oxidised to sulphur
H2S ® 2H+ + S2–
5S2– + 2MnO4– + 16H+ ® 2Mn2+ + 8H2O + 5S
(6) SO2 is oxidised to H2SO4
2MnO4– + 5SO2 + 2H2O ® 2Mn2+ + 5SO42– + 4H+
(7) Nitrites are oxidised to Nitrates.
5NO2– + 2MnO4– + 6H+ ® 2Mn2+ + 5NO3– + 3H2O
Uses :
(1) In qualitative analysis for detection of halides, sulphites, oxalates etc.
(2) In volumetric estimations.
(3) In the manufacture of saccharine, benzoic acid, acetaldehyde etc.
(4) As a disinfectant.
(5) Alkaline KMnO4 soln. is Bayer’s reagent which finds its use in organic
reactions.

1. A d-block element or transition element may be defined as one that has a partially filled
inner d-orbital. The general configuration for transition element is (n–1) d 1-10 ns1–2.
2. Transition elements are solid metals hard, malleable and ductile. They have high densities,
high melting points and boiling point. They show variable valencies and variable oxidation
states.
3. Transition elements form coloured as well as complex compounds.
4. Transition elements and their compounds are paramagnetic in nature and show catalytic
activity.
5. Transition metals form intermetallic alloys and form interstitial compounds.
6. Potassium dichromate is a very important oxidising agent. It finds application in volumetric
analysis as a primary standard and a powerful oxidising agent in acidic solution. It is used
in photography, dyeing and chrome tanning.
7. Potassium permanganate is another useful compound in qualitative and quantitatve
analysis. It is a strong oxidising agent in solution. The oxidation reactions are carried out
in acidic, alkaline and neutral medium. Potassium permanganate is used as a disinfectant.
It finds its application in the manufacture of saccharine, benzoic acid, acetaldehyde etc.
Alkaline potassium permangnate is known as Bayer’s reagent.
QUESTIONS
A. Very short answer type. (1 mark each)
1. Define a transition element.
2. Mention two characteristic feature of transition elements.
3. What is the oxidation number of Mn in MnO4– ?
4. What is the oxidation number of Cr in Cr2O72– ?
5. What is the reason of paramagnetism in transition metals ?
6. What is the magnetic property of dipositive Zinc ?
7. What is the general electronic configuration of d-block elements ?
8. What is the maximum oxidation state of manganese ?
9. Name a transition element which is not a solid.
10. What happens when acid is added to the yellow coloured potassium chromate solution?
B. Short anwer type. (2 marks each)
1. Transition elements form alloys easily. Give reasons.
2. Why most of the compounds of transitional elements are paramagnetic ?
3. Why Zinc salts are colourless ?

4. Why Cu1+ salts are colourless ?
5. Write the structure of chromate and dichromate ions ?
6. What happens when potassium dichromate is heated ?
7. Mention two uses of potassium dichromate.
8. Write the structure of manganate and permanganate ions.
9. Explain why conversion of chromate ion to dichromate ion is not a redox reaction.
10. Mention two important uses of potassium permanganate.
C. Short answer type. (3 marks each)
1. Explain why CuSO4 is paramagnetic while ZnSO4 is diamagnetic.
2. Why do transition metal ions form complexes ?
3. Transition metals and their compounds act as catalysts- Explain.
4. What happens when KMnO4 is heated alone and with alkali.
5. Why are transition metal compounds coloured ?
6. What happens when H2S gas is passed through acidified K2Cr2O7 solution?
7. What is the equivalent mass of KMnO4 in alkaline solution ? Explain.
8. What are the uses of potassium permanganate ?
D. Long answer type. (7 marks each)
1. What are transition elements ? Describe any four characteristic properties of transition
elements.
2. Describe the preparation of potassium permanganate. How does acidified potassium
permagnate solution react with
(a) KI (b) SO2 (c) iron (II) (d) H2S
3. Discuss the oxidising action of KMnO4 in acidic, alkaline and neutral solutions with
suitable examples.
4. Describe the preparation of potassium dichromate from iron chromite ore. Discuss the
effect of pH on a solution of potassium dichromate.
5. Discuss the oxidising action of K2Cr2O7 and write the ionic equations for its reaction with
(a) KI (b) Fe2+ (c) H2S.
E. Multiple choice type. (Choose correct answers)
1. Which of the following is a transition element ?
(a) Ca (b) Al
(c) Co (d) Na
2. The d-block elements form alloys among themselves, because.
(a) their atomic sizes are nearly same (b) they have unpaired electrons
(c) their ionisation enthalpies are similar (d) they are all metals.
3. Which of the following statements(s) is (are) correct when a mixture of NaCl and K 2Cr2O7
is gently warmed with conc. H2SO4 ?
(a) A deep red vapour is evolved.
(b) The vapour when passed into NaOH solution gives a yellow solution of Na2CrO4.
(c) Chlorine gas is use evolved.
(d) Chromyl chloride is formed.
4. Out of the following indentify the d-block element.
(a) Ca (b) U
(c) Mn (d) Al
5. Which of the following statements about transition metals in wrong ?
(a) They form coloured compounds
(b) All their compounds are diamagnetic
(c) They exhibit variable valency.
(d) They contain partially filled d-orbitals.
6. Acidified potassium permanganate solution is decolourised by
(a) Bleaching powder (b) White vitriol
(c) Mohr’s salt (d) Microcosmic salt.
7. Which one of the metals does not form amalgam ?
(a) Zn (b) Ag
(c) Cu (d) Fe
8. Which ion is not coloured ?
(a) Cu+ (b) Cr2+
(c) Co2+ (d) Cr3+
9. Paramagnetic behaviour in transition metal is due to the presence of
(a) lone pair of electron (b) even number of electrons
(c) unpaired electron (d) odd number of electrons.
10. The general electronic configuration of transition elements is
(a) (n–1)d1–5 (b) (n–1)d1–10ns1
(c) (n–1)d1–10ns1 or 2 (d) none
ANSWER TO MULTIPLE CHOICE QUESTIONS
1. (c) 2. (a) 3. (a) (b) (d) 4. (c) 5. (b) 6. (c) 7. (d) 8. (a)
9. (c) 10. (c) 11. (c)
qqq
CHAPTER - 12
THE f-BLOCK ELEMENTS

THE LANTHANOIDS AND THE ACTINOIDS
12.1 INTRODUCTION :
The elements in which the last electron enters the ante-penultimate energy level, i.e.
(n–2) f-orbitals are called f-block elements. They are also regarded as inner transition metals /
rare earth metals (due to their occurence in traces in nature).
The f-block elements consists of two series :
Lanthanoids : The group of 14 elements following Lanthanum (Z = 58 to 71) are known
as Lanthanoids.. Lanthanum though a d-block element, is included in any discussion of lanthanoids
because it closely resembles them in its properties. The study of lanthanoids is comparatively
easier because they show only one stable oxidation state.
Actinoids : The group of 14 elements following Actinium (Z = 90 to 103) in which the
last electron enters into the ‘5f’ orbital are known as “Actinoids”. Actinium also resembles them
in its properties. The elements of this series are radioactive and exhibit complicated gradation in
properties. They show wide range of oxidation states.
12.2 THE LANTHANOIDS :
12.2.1 Electronic Configuration :

Lanthanoids possess common electronic configuration 6s 2 5d0–1 4f1–14 (Table 12.1) The
exceptional electronic configuration of few elements can be explained on the basis of stability.
(i) The electronic configuration of Cerium (Z = 58) is 4f 2 5d0 6s2.
(ii) Europium (Z = 63) has electronic configuration 4f 7 6s2 and that of Gadolinium is
4f7 5d1 6s2, because of the extrastability due to half-filled orbitals.
(iii) Ytterbium (Z = 70) has electronic configuration 4f 14 6s2 and Lutetium (Z = 71) is
4f145d16s2, which is explained on the basis of extra stability of the completely
filled 4f orbitals.
Table 12.1 : Electronic Configuration and Radii of Lanthanum and Lanthanoids
Atomic Electronic Configuraton Raddi / pm

Name Symbol
Number Ln Ln2+ Ln3+ Ln4+ Ln Ln3+
57 Lanthanum La 5d16s2 5d1 4f° 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f° 183 103
59 Praseodymium Pr 4f 36s2 4f3 4f2 4fl 182 101
60 Neodymium Nd 4f 46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f 56s2 4f5 4f4 181 98
62 Samarium Sm 4f 66s2 4f6 4f5 180 96
63 Europium Eu 4f 76s2 4f7 4f6 199 95
64 Gadolinium Gd 4f75d16s2 4f75dl 4f7 180 94
65 Terbium Tb 4f 96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f 106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f 116s2 4f11 4f10 176 89
68 Erbium Er 4f 126s2 4f12 4f11 175 88
69 Thulium Tm 4f 136s2 4f13 4f12 174 87
70 Ytterbium Yb 4f 146s2 4f14 4f13 173 86
71 Lutetium Lu 4fl45d16s2 4f145d1 4f14 - -
12.2.2 Atomic and Ionic sizes :

In the lanthanoid series there is a regular decrease in atomic and ionic radii from Lanthanum
to Lutetium. (Table 12.1, Fig. 12.1). The cumulative effect of this regular decrease (contraction)
in the atomic and ionic radii of lanthanoids with increasing atomic number is known as
‘Lanthanoid contraction’. Lanthanoid contraction is a unique feature in the chemistry of
Lanthanoids.
Fig. 12.1 : Trends in ionic radii of lanthanoids

THE LANTHANOIDS AND THE ACTINOIDS 363
Cause of Lanthanoid contraction :

Lanthanoid contraction is attributed to the imperfect shielding of one electron by another
in the same sub-shell (i.e. 4f), as the ‘4f’ orbital is more diffused in space. This imperfect shielding
is unable to counter balance the effect of the increased nuclear charge. So the net result is a
contraction in size.
Consequences of Lanthanoid contraction :
(1) Similarity in size of elements of same group of second and third transition series :
The size of an atom of third transition series is nearly same as that of the atom of
the element lying in the same group of the second transition series, due to lanthanoid
contraction.
Ex : 40 Zr – 160 pm 41 Nb – 146 pm
and 72 Hf – 159 pm and 73 Ta – 146 pm
(2) Difficulty in separation Lanthanoids :
The change in sizes of the lanthanoid ions along the series are very small. So their
chemical properties are similar with each other and it is difficult to separate the
lanthanoids in the pure state. However, the slight difference in sizes results in
differences in properties like solubility, hydration, complex ion formation which
enable the separation of lanthanoid elements individually by ion exchange methods.
Lanthanoids possess common oxidation state +3.
The Lanthanoids which acquire a stable configuration of f 0, f7 or f14 by losing 2 or 4
electrons, they show +2 or +4 oxidation state.
Ex. Eu2+ [Xe] 4f 7 ; Yb2+ [Xe] 4f 14
Ce4+ [Xe] 4f 0 ; Tb4+ [Xe] 4f 7
Exceptions :
Pr4+ [Xe] 4f 1 ; Nd2+ [Xe] 4f 4 ; Sm2+ [Xe] 4f 6 ;
Dy4+ [Xe] 4f 8 ; Nd4+ [Xe] 4f 2
The lanthanoids in +2 or +4 oxidation state tend to show +3 oxidation state by loss or
gain of electron.
Sm2+, Eu4+ and Yb2+ ions loose electrons in solutions to show +3 oxidation state and are
good reducing agents.
Ce4+, Tb4+ in their aqueous solution are good oxidising agents as they gain electron and
change to +3 oxidation state.
Though the formation of Ce4+ is favoured by its noble gas configuration, it has a tendency
to show +3 oxidation state and enables it to behave as a strong oxidant.
The E0 value for Ce4+ / Ce3+ is + 1.74 V. So it can oxidise water at a very slow rate and
Ce (IV) is a good analytical reagent. Praseodymium, Neodymium, Terbium and Dysprosium
exhibit +4 oxidation state only in oxides. Their oxides have general formula MO 2. (M = Pr,
Nd, Tb or Dy)
12.2.4 General characteristics of Lanthanoids :
1. Softness : All the lanthanoids are silvery white soft metals. They tarnish rapidly in
air. Their hardness increases with increasing atomic number. Samarium is
exceptionally hard like steel.
2. Melting points : The melting points of lanthanoids range between 1000K to 1200K.
Samarium has melting point 1623K.
3. Thermal and Electrical conductivity : The lanthanoids have metallic structure.
They are good conductors of heat and electricity.
4. Density : They have high densities in the range of 6.77 to 9.77 g.cm–3. Their density
and other properties vary smoothly with increasing atomic number. Europium and
Ytterbium show exceptions.
5. Colour : Lanthanoids are silvery white metals. Most of the trivalent metal ions are
coloured both in the solid state and in aqueous solution. This is due to f-f transitions
of the electrons present in partly filled f–orbitals. The lanthanoid ions with ‘n’
electrons or (14–n) electrons in f-subshells have similar colour.
Ex: (a) La3+ and Lu3+ are colourless, n = 0
(b) Sm3+ and Dy3+ are yellow, n = 5
(c) Eu3+ and Tb3+ are pink, n = 6
6. Magnetic behaviour : The lanthanoid ions are paramagnetic due to presence of
unpaired electrons in the 4f subshell, except La 3+, Ce4+ (f0 configuration) and Lu
(f14 configuration). The paramagnetism is maxium in Neodymium.
(7) Ionisation Enthalpy : The first IE of lanthanoids are 600 kJ mol –1 and second IE
are 1200 kJ mol–1. The second Ionisation Enthalpy of Lanthnoids are comparable
with that of Ca2+. That is why the first few members of the series have reactivity
similar to Calcium.
Lanthanum, Gadolinium and Lutetium possess abnormally low values of 3rd
Ionisation Enthalpy because removal of third electron leads to empty, half-filled
and completely filled f-orbitals respectively.
(8) Chemical behaviour : As discussed previously, the earlier members of lanthanoid

series have reactivity similar to Calcium with increasing atomic number they
resemble Aluminium in their chemical behaviour.
(a) With non-metals : They combine with hydrogen on gentle heating and form
carbides on heating with carbon. With halogens respective halides are formed. Oxides
and hydroxides of the type M2O3 and M(OH)3 are formed due to reaction with
oxygen and water respectively, which are basic in nature.
(b) With dilute acids : They react with dilute acids to liberate hydrogen gas.
SUMMARY
Burn in O 2
SUMMARY Ln2 O3
dilute
H2 gas is liberated
acids
Heated with
LnN
N2
Lanthanoids With
LnX3
(Ln) Halogens
Heated with
Ln2S3
S
H 2O
Ln(OH)3 + H2
C, 2773K
Ln3C, Ln 2C 3 and LnC 2
12.2.5 Uses :
(1) Mischemetal :
Composition : 50% Cerium, 40% Lanthanum and other Lanthanoids, 5% iron, traces
of S, C, Ca and Al.
It is used in making magnesium-based alloy. Because of its pyrophoric nature

(tendency to emit spark when struck), it is employed in production of bullets, shells
and flints.
(2) Their oxides are used for making UV protective lenses.
(3) Ceric sulphate is a well-known oxidising agent.
12.3 THE ACTINOIDS :

As mentioned earlier, Actinoids are radioactive. The earlier members of the series have
relatively long half-lives and the later ones have half-lives ranging from a day to 3 minutes for
Lawrencium.
12.2.1 Electronic Configuration :

The general electronic configuration of Actinoids is 7s 2 6d0–1 5f1–14 (Table 12.2). The
actinoids have their stable configuration for f0, f7 and f14 occupancy. So there is certain irregularity
in their electronic configuration.
Ex : Am – [Rn] 7s25f7
Cm – [Rn] 7s26d15f7
The 5f orbitals are not as buried as 4f orbitals. So they can participate in bonding to a
greater extent.
Table 12.2 : Some properties of Acitinium and Actinoids

Aotmic Electronic congiguration Raddi/pm
Number Name Symbol M M3+ M4+ M3+ M4+
89 Actinium Ac 6d17s2 5f° 111

90 Thorium Th 6d27s2 5f1 5f° 99
91 Protactinium Pa 5f26d17s2 5f2 5f1 96
92 Uranium U 5f36d17s2 5f3 5f2 103 93
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92
94 Plutonium Pu 5f67s2 5f5 5f4 100 90
95 Americium Am 5f77s2 5f6 5f5 99 89
96 Curium Cm 5f76dl7s2 5f7 5f6 99 88
97 Berkelium Bk 5f97s2 5f8 5f7 98 87
98 Californium Cf 5f107s2 5f9 5f8 98 86
99 Einstenium Es 5f117s2 5f10 5f9 - -
100 Fermium Fm 5f127s2 5f11 5f10
101 Mendelevium Md 5f137s2 5f12 5f11 - -
102 Nobelium No 5f147s2 5f13 5f12 - -
103 Lawrencium Lr 5fl46dl7s2 5f14 5f13 - -
12.3.2 Oxidation states :

The 5f, 6d and 7s subshells are of comparable energies. So the actinoids show a greater
range of oxidation states (Table 12.3).
Table 12.3 : Oxidation states of Actinium and Actinoids

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
3 3 3 3 3 3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4 4
5 5 5 5 5
6 6 6 6
7 7
However, like lanthanoids the +3 oxidation state is common to all of them. As evident
from the table the oxidation state of actinoids increases upto the middle of the series and then
decreases for the succeeding elements. This is because the 5f, 6d and 7s subshells are of comparable
energies and all their electrons can take part in bond formation.
12.3.3 Ionic sizes :
The actinoids also show “actinoid contraction” (like lanthanoids) due to the poor
shielding effect of ‘5f’ subshells. As a result, the radii of these atoms or ions decrease across the
series. (Table 12.2)
12.2.4 General characteristics of Actinoids :
1. The actinoid metals are all silvery in appearance.
2. Structure : The actinoids display a variety of structures due to irregularities in
metallic radii.
3. Colour : The actinoid cations are coloured due to f–f transition. Those ions having
no 5f-electron or seven 5f-elecrons (i.e. exactly half-filled f-subshell) are colourless.
Ex : Ac3+ 5f 0 colourless Am3+ 5f 6 pink
U3+ 5f 3 red Cm3+ 5f 7 colourless
Np3+ 5f 4 blue Th3+ 5f 0 colourless
Pu3+ 5f 5 violet etc.
4. Melting and Boiling points : Actinoids have high melting and boiling points. But
they do not show any regular trend.
5. Density : They have high densities.
6. Ionization enthalpies : The actinoids have lower ionization enthalpies than
lanthanoids because ‘5f’ is less penetrating than ‘4f’ and hence is more effectively
shielded from nuclear charge.
7. Electropositive character : Actinoids are highly electropositive like the
Lanthanoids.
8. Magnetic behaviour : The actinoids are strongly paramagnetic. The magnetic

susceptibility of actinoids are higher than the lanthanoids.
9. Chemical behaviour :
(a) Actinoids react with boiling water to give oxides and hydroxides.
(b) They react with most of the non-metals at moderate temperature.
(c) They are rendered passive by action of nitric acid.
12.3.5 Uses of Actinoids :

(1) Thorium : It is used as a nuclear fuel, anti-carcinogen and for manufacture of mantles
of incandescent lamps.
(2) Uranium : It is used as nuclear fuel, textiles, ceramics, medicines and to impart
colour (green) to bulbs.
(3) Plutonium : It is used in nuclear reactors and manufacture of atomic bombs.
12.4 COMPARISON BETWEEN LANTHANOIDS AND ACTINOIDS :
Though Lanthanoids and Actinoids resemble each other in certain properties there are
also some dissimilarities between them.
Similarities :
(1) +3 oxidation state is common for both the series of elements.
(2) Both are electropositive and have low value of Ionisation Enthalpy.
(3) Both exhibit magnetic and spectral properties.
(4) Lanthanoids show ‘Lanthanoid contraction’ and Actinoids show ‘Actinoid
contraction’.
Differences :
(1) They are non-radioactive. (1) They are radioactive.
Exception-Promethium.
(2) Besides +3 oxidation state (2) They show higher oxidation states
they show +2 and +4 oxidation +4, +5, +6, +7 besides +3 oxidation
states only in a few cases. state
(3) Do not form oxocation. (3) UO2+, UO22+, PuO22+ etc.
oxocation are formed by them.
1. The elements in which last electron enters the ante-penultimate energy level, i.e. (n–2) f-
orbitals are called f-block elements.
2. The group of 14 elements following Lanthanum (Z = 58 to 71) are known as Lanthanoids.
3. The group of 14 elements following Actinium (Z = 90 to 103) in which the last electron
enters into the ‘5f’ orbital are known as Actinoids.
4. The general electronic configuration of Lanthanoids is 6s 25d0–14f 1–14 and of Actinoids is
7s26d0–15f 1–14.
5. Due to imperfect shielding of one ‘4f’ electron by another of same sub-shell there is
regular decrease in the atomic and ionic radii of lanthanoids with increasing atomic number.
This phenomenon is known as ‘Lanthanoid contraction’.
6. Both Lanthanoids and Actinoids show common oxidation state +3. The Lanthanoids also
show +2 and +4 oxidation state whereas the higher oxidation states +4, +5, +6 and +7 are
shown by actinoids.
7. Ce (IV) is used as good analytical reagent because Ce 4+/Ce3+ has E0 value + 1.74 V.
8. The trivalent Lanthanoids and Actinoid ions are coloured due to f-f transitions of the
electrons present in partly filled f-orbitals. But those with f 0, f 7 and f 14 configuration are
colourless.
9. Mischmetal is an alloy of cerium. Lanthanides are used in making magnesium-based
alloy with a wide range of applications.
QUESTIONS
A. Short answer type (1 mark each) :

1. What is the general electronic configuration of lanthanoids?
2. Write down the electronic configuration of
(a) Lu2+ (b) Pm3+
3. Indentify the atomic number of the inner transition elements.
24, 35, 59, 65, 73, 87, 91, 102, 105
4. What are the different oxidation states exhibited by lanthanoids?
5. Name an important alloy containing some of the lanthanoid metals.
6. Write the electronic configuration of (a) Yb 2+ (b) Sm2+
7. Which lanthanoid shows maximum paramagnetism.
8. Name the common mineral containing lanthanoids.

9. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation
state.
B. Short answer type (2 marks each) :

1. Define Lanthanoid contraction. Write two consequences of it.
2. ‘Eu’ and ‘Yb’ show +2 oxidation state, whereas +4 oxidation state is shown by Ce and
Tb. Why?
3. Explain with correct reason whether Sm2+ and Eu2+ act as good oxidising or reducing
agent.
4. La3+ and Lu3+ are colourless, whereas Sm3+ and Eu3+ are coloured. Why?
5. Mention important uses of uranium and plutonium.
6. Chemistry of all lanthanoids is quite similar. Why?
7. Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
(Hint : The 5f electrons are more effectively shielded from nuclear charge)
8. Give reason why : Chemistry of all the lanthanoids is quite similar.
C. Short answer type (3 marks each) :

1. Compare the chemistry of actinoids with that of lanthanoids with special reference to :
(a) electronic configuration (b) atomic and ionic radii (c) oxidation states.
2. Name an important alloy containing some of the lanthanoid metals. Mention its uses.
3. Which is the last element in the series of Actinoids? Write its electronic configuration.
Comment on its oxidation states.
4. La (OH)3 is more basic than Lu (OH)3, why ?
(Hint : As the size of Lanthanide ions decrease from La +3 to Lu3+, the covalent character
of the hydroxide increases).
5. Why Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents, but an aqueous
solution of Ce4+ is a good oxidising agent.
D. Long answer type (7 marks each) :

1. (a) Write the general electronic configuration of lanthanoids.
(b) Why Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents ?
(c) Why is the separation of lanthanoid elements difficult ?
2. Compare the chemistry of actinoids with that of lanthanoids with special reference to
(a) electronic configuration (b) oxidation state
(c) atomic and ionic sizes (d) chemical reactivity
E. Multiple choice questions (Choose the correct answer) :

1. Which of the following pairs have same size.
(a) Zn2+, Hf 4+ (b) Fe2+, Ni2+
(c) Zr4+, Ti4+ (d) Zr4+, Hf 4+
2. The main cause of Lanthanide contraction is
(a) Poor shielding of one of the 4f-electrons by another in the subshell.
(b) Greater shielding of 5d electrons by 4f electrons.
(c) Poorer shielding of 5d electrons by 4f electrons.
(d) Effective shielding of one of the 4f electrons by another in the subshell.
3. The maximum oxidation state exhibited by actinide ions is
(a) +4 (b) +5
(c) +7 (d) +8
4. The most common mineral containing lanthanoids is :
(a) pyrites (b) monazite sand
(c) rock salt (d) none
5. Which is the strongest base among the following:
(a) La (OH)3 (b) Lu (OH)3
(c) Yb (OH)3 (d) Ce (OH)3
6. The general electronic configuration of inner transition elements is :
(a) ns2 (n–1) d0–1 (n–2)f 1-14 (b) ns2 (n–1) d1–2 (n–2)f 0-14
(c) ns2 (n–1) d0–1 (n–2)f 0-14 (b) ns2 (n–1) d1 (n–2)f 1-14
7. Which of the following oxidation states is the most common among the lanthanoids?
(a) + 4 (b) +2
(c) +5 (d) +3
8. The lanthanoid ions are coloured due to
(a) p–p transition (b) d–d transition
(c) d–f transition (d) f-f transition
ANSWER
1. (d), 2. (a), 3 (c), 4. (b), 5. (a), 6. (a), 7. (d), 8. (d)
qqq
UNIT - IX
CHAPTER - 13
CO-ORDINATION COMPOUNDS
13.1 NORMAL SALT :
A normal salt is formed by the replacement of all replaceable hydrogen atoms in an

acid by the metal atoms. Thus a normal salt is formed by the complete neutralisation of a
strong acid by a strong base. A normal salt gives almost a neutral solution in water.
Some examples are : NaCl, K 2SO4, NaNO3 etc.
All types of salts are fully ionised when dissolved in water. When NaCl dissolves in
water, it ionises fully while water ionises slightly.
NaCl Na+ + Cl—
H2O H+ + OH—
H+ ion has no tendency to combine with Cl — ions as HCl is fully ionised. Similarly,
OH— ions have no tendency to combine with Na + ions as NaOH is fully ionised.
There are certain exceptions. For example, though Na 2CO3 and CuSO4 are normal
salts their aqueous solutions are basic and acidic respectively. Due to hydrolysis,
2(Na+ + OH ) + H2CO3.
--
Na2CO3 + 2H2O
Due to free OH— the solution is alkaline. Similarly, solutions of copper (II) salts are
acidic due to hydrolysis.
On evaporation of solutions containing two or more salts in simple molar proportions, it is

found that crystals of new compounds separate out. These new compounds are of two types
namely (a) Double salts (b) Co-ordination compounds.
CO-ORDINATION COMPOUNDS 373
13.2 DOUBLE SALTS :

The compounds which when dissolved in water or any other solvent decompose into
their constituent compounds and which exist only in crystal lattices are known as double salts.
The physical and chemical properties of these compounds are almost the same as those of individual
compounds.
Examples include
(i) Al2 (SO4)3.K2SO4.24H2O (Potash Alum)
(ii) FeSO4. (NH4)2SO4.6H2O (Mohr’s salt)
(iii) KCl. MgCl2.6H2O (Carnallite)
So a solution of potash alum shows the same physical and chemical properties as a mixture
of solutions of Aluminium sulphate and Potassium sulphate.
13.3 CO-ORDINATION COMPOUNDS :

The compounds which when dissolved in water or any other solvent retain their identity
are known as co-ordination compounds. The physical and chemical properties of these
compounds are completely different from those of the constituents. Some common examples are
(i) [Co(NH3)6]Cl3 - Hexaamminecobalt (III) chloride
(ii) K4[Fe (CN)6] - Potassium hexacyanoferrate (II)
(iii) [Ni(NH3)6]Cl2 - Hexaamminenickel (II) chloride
Hexaamminenickel (II) chloride ionises in solution as
[Ni(NH3)6] Cl2 [Ni (NH3)6]2+ + 2Cl–
On evaporating the solution, the compound can be recovered. The compound in solution
does not show the properties of Ni2+ ions or ammonia molecules.
13.4 DEFINITIONS OF SOME IMPORTANT TERMS :

(i) Coordination Complex and Complex ions
Two or more stable chemical species combine to form a compound known as Co-
ordination complex. The compound retains its identity both in the solid as well as in dissolved
state.
e.g. CuSO4 and NH3 are two stable chemical species and they combine to form a
coordination complex [Cu(NH3)4]SO4.
A water-soluble co-ordination compound invariably contains a complex ion. For example,
[Cu(NH3)4]SO4 contains [Cu(NH3)4]2+ complex ion and K[Ag(CN)2] contains the complex ion
–
[Ag(CN)2] . A complex ion is thus electrically charged ion which contains a central metal atom
or ion surrounded by a group of ions or neutral molecules. So [Cu(NH 3)4]2+ contains a central ion
Cu2+ surrounded by four ammonia molecules.
(ii) Central ion
The ion to which a fixed number of ions or neutral molecules are bound in a definite
geometrical arrangement around it is known as the central ion. For example, in complex ion
[Ni(NH3)6]2+, Ni2+ is the central ion and in [Fe(CN6]3–, Fe3+ is the central ion. The central ion is a
Lewis acid.
(iii) Ligands
The ions or molecules bound to the central ion in the coordination compounds are called
ligands. For example, in complex ions [Ni(NH3)6]2+ and [Fe(CN)6]3– the ligands are molecules of
ammonia and cyanide ions respectively. The ligands may be simple ions like Cl –, small molecules
like H2O and NH3, larger molecules like H 2NCH2CH2NH2 or N(CH2CH2NH2)3 or even
macromolecules like proteins.
(iv) Coordination Number
The ligands are attached to the central ion through coordinate bonds. The number of
ligands attached to the central ion is known as the coordination number of that ion. For example,
co-ordination number of Ag+ in [Ag(CN)2]– is 2. Co-ordination number of Cu2+ in [Cu(NH3)4]2+ is
4. The most common coordination numbers are 2, 4, and 6.
(v) Coordination sphere
The central ion bonded to the ligands constitute the co-ordination sphere. The co-
ordination sphere is written within the square bracket.
e.g. [Ag (CN)2]–
Types of Ligands
A ligand necessarily contains one or more donor atoms for co-ordination with the central
ion. On the basis of number of donor atoms the ligands may be classified as follows :
(1) Unidentate or monodentate ligands
The ligands which can coordinate to the central ion through only one donor atom are
known as unidentate or monodentate ligands. The common examples are-
H2O, Cl–, NH3, OH–, NO2– etc.
(2) Bidentate or didentate ligands
The ligands which can coordinate to the central ion through two donor atoms are called
bidentate or didentate ligands.
The examples are

O = C – O– ..
CH2 – NH 2
| |
O=C–O – ..
CH2 – NH2
(3) Polydentate ligands

The ligands which can co-ordinate to the central ion through more than two donor atoms
are called polydentate ligands. They may be tridentate, tetrandentate, pentadentate and
hexadentate depending upon the number of donor atoms as 3, 4, 5, and 6 respectively.
e.g. Ethylene diamine tetracetic acid (EDTA) is an important hexadentate ligand. It binds
through two nitrogen and four oxygen atoms of four –COOH groups to the central metal ion.
HOOCH2C N – CH2 – CH2 – N CH2COOH
HOOCH2C CH2COOH
EDTA
(4) Chelating ligands and Chelates
A bidentate or polydentate ligand may link to central metal ion through two or more
donor atoms forming a ring structure. The ligand is called a chelating ligand and the complex is
called a chelate.
For example, ethylene diamine (a bidentate ligand) coordinates through both the Nitrogen
atoms to central Cu2+ ion forming a ring structure.
H 2C CH2 2+
H2C-NH2 H2N-CH2
H2 N
.. NH
.. 2 Cu
H2C-NH2 H2N-CH2
Ethylene diamine
Bidentate ligand Chelate cation
acting as chelating ligand
13.5 WERNER’S CO-ORDINATION THEORY :
To explain the formation and structure of complex compounds Werner in 1823 put forward
the theory of coordination for which he was awarded Nobel prize in chemistry. He is known as
the the father of coordination chemistry.
Postulates
(1) Metal atoms in coordination compounds exhibit two types of valencies (a) Primary valency
(b) Secondary valency. The primary valency is non-directional and ionisable. It corresponds
to oxidation state. The secondary valency is directional and non-ionisable. It corresponds
to coordination number.
(2) Each metal atom exhibits a fixed number of secondary valencies i.e. it has a fixed
coordination number.
(3) The primary valencies are satisfied by negative ions whereas the secondary valencies are
satisfied either by negative ions or by neutral molecules.
(4) The secondary valencies are responsible for imparting a particular geometry to the
coordination compound. For example, if the central metal ion has four secondary valencies,
then they form either a tetrahedral or square planar arrangement around the central metal
ion. If the central metal ion has six secondary valencies, then these are arranged octahedrally
around the metal ion. In otherwords the stereochemistry of the complex is determined by
the secondary valencies.
Explanation of Structure of complexes on the basis of Werner’s theory
The structures of various cobalt ammines may be explained by Werner’s theory. In all such
compounds cobalt exhibits a primary valency of three and secondary valency of six. The primary
valencies are represented by dotted lines whereas the secondary valencies by thick lines in the
following figures.
NH3 Cl NH3
H3N H3N
NH3 NH3
Cl Co Cl Co Cl
H3N H3N
NH3 NH3
NH3 Cl Cl
Fig.13.1 Structure of CoCl3.6NH3 complex Fig.13.2 Structure of CoCl3.5NH3 complex

(a) Total no. of ions = 4 (a) Total number of ions = 3
–
(3 numbers of Cl ion, (2 numbers of Cl– ion,
1 complex ion [Co(NH3)6]3+) 1 complex ion)
(b) The complex = [Co(NH3)6]Cl3 (b) The complex = [CoCl (NH3)5]Cl2
(c) The number of Cl– ions getting (c) The number of Cl– ions getting precipitated
precipitated on addition of AgNO3 = 3 on addition of AgNO3=2
–
(d) One Cl ion exhibits a dual character. It is held
by a secondary as well as a primary valency.
Cl
Cl
H3N
NH3 H3N
NH3
Cl Co
Co
H3N
NH3 Cl Cl
Cl NH3
Fig.13.3 : Structure of CoCl3 .4NH3 complex Fig.13.4 : Structure of CoCl3 . 3NH3 complex
(a) Total no. of ions = 2 (a) Total number of ions = zero.It is a neutral molecule.
(one Cl– ion), one complex ion (b) The complex [CoCl3 (NH3)3]
–
(b) The Compex = [CoCl2 (NH3)4 ] Cl (c) The number of Cl ions getting precipitated on
–
(c) The number of Cl ion addition of AgNO3 = nil.
–
getting precipitated on addition (d) Three numbers of Cl ions are held by primary
of AgNO3 = 1 as well as secondary valencies
–
(d) Two number of Cl ions are held by
primary as well as secondary valencies.
13.6 NOMENCLATURE OF COORDINATION COMPOUNDS: IUPAC SYSTEM :
The International Union of Pure and Applied Chemistry (IUPAC) publication,

Nomenclature of Inorganic Chemistry (1989), Blackwell Scientific Publishers, has given
the rules for systematic naming of coordination compounds. The basic rules are as follows:
I. Order of naming ions: In ionic complexes, the cation is named first and then
the anion. For example:
[ Ni( NH 3 ) 6 ]Cl 2 is named as Hexaamminenickel (II) chloride.
[ Cr ( NH 3 ) 6 ]( NO 3 ) 3 is named as Hexaamminechromium (III) nitrate.
and K 2 [ PtCl 6 ], as Potassium hexachloroplatinate (IV).
II. Non-ionic complexes: They are given one-word name.
For example: [ Pt ( NH 3 ) 2 Cl 4 ] is named as Diamminetetrachloroplatinum (IV)
[ Co( NH 3 ) 3 ( NO 2 ) 3 ] is named as Triamminetrinitrocobalt(III).
III. Naming the complex:
i) When the name of the complex is written, the ligands are written in
alphabetical order regardless of their charge, followed by the metal.
For example: [ Pt. Cl. NO 2 ( NH 3 ) 4 ]SO 4 is named as Tetraammine--

chloronitroplatinum(IV) sulphate.
ii) When the formula of the complex is written, the complex ion should
be enclosed in square brackets. The metal is written first, then the
coordinated groups are listed in the order-- negative ligands, neutral
ligands, positive ligands (and alphabetically according to the first
symbol within each group).
a) The name of the negative ligands end in ‘o’.

Thus,
F- fluoro H- hydrido HS - mercapto NO 2- nitro
Cl - chloro OH - hydroxo S2 - thio CH 3COO - acetato

Br - bromo O2- oxo SO 24 - sulphato S 2 O 23 - thiosulphato
I- iodo O 22 - peroxo CN - cyano NO 3- nitrato
b) Neutral ligands are named as the molecule. Thus, water ( H 2 O) is

named as aqua, ammonia ( NH 3 ) as ammine, CO as carbonyl and NO
as nitrosyl. The ligands N 2 is called dinitrogen and O 2 is called
dioxygen. Organic ligands are given their common names as phenyl,
methyl, ethylenediamine (shortly as ‘en’), pyridine (shortly as ‘py’)
glycine (Gly), dimethyl glyoxime (DMG) etc.
(c) Positive ligands end in ‘ium’ For example, NH 2 - NH 3 is named as

hydrazinium. (But when NO + ligand is used, it is called nitroso).
IV) Prefixes to indicate number of ligands: When there are several simple ligands
of the same kind, their number is indicated by di, tri, tetra, penta and hexa. If
the ligands have complex names, to avoid confusion bis, tris, tetrakis are used
instead of di, tri and tetra and the name of the ligand is kept within brackets.
For example- K 3[Al(C 2 O 4 ) 3 ] is named as Potassium trioxalatoaluminate
(III) and [ CoCl 2 ( NH 2 CH 2 CH 2 NH 2 ) 2 ]2 SO 4 or [ CoCl 2 ( en ) 2 ]2 SO 4 is
named as Dichlorobis (ethylene diammine) cobalt(III) sulphate.
V) Oxidation state of central metal is shown by Roman numerals (I, II, III etc)
in brackets immediately following its name. For zero oxidation state, (0) is
written.
VI) Ending of names : The complex negative ions end in ‘ate’ but complex positive
ions and neutral molecules have no special ending.
For example: K 4 [ Fe(CN ) 6 ] is named as Potassium hexacyanoferrate(II)
and K 3[ Fe(CN ) 6 ] is Potassium hexacyanoferrate (III).
K[ PtCl 5 ( NH 3 )] is named as Potassium amminepenta-

chloroplatinate(IV)
and [ Co( NO 2 ) 3 ( NH 3 ) 3 ] as Triamminetrinitrocobalt(III).

VII) Bridging groups: Ligands which link two centres of coordination are usually
separated from the rest of the complex by a ‘hyphen’( - ) and are denoted by
the prefix m - . If there are two or more bridging groups of the same kind, this
is indicated by di - m - , tri - m - etc. Bridging groups are listed alphabetically
with other groups unless the symmetry of the molecule allows a simpler name.
For Example: [( NH 3 ) 5 Co. NH 2 . Co( NH 3 ) 5 ]( NO 3 ) 5 is named as
m - Amidobis [pentaamminecobalt(III)] nitrate,
CO
[(CO)3Fe CO Fe (CO)3] as Tri - m - carbonyl-bis (tricarbonyliron(0) )
CO
and [(NH3)4 Co Co(NH3)4](NO3)4 as
m - Amido - m - nitrobis [tetraamminecobalt(III)] nitrate.

VIII) Sometimes a ligand may be attached through different atoms. Thus, M-NO 2
is called nitro whereas M-ONO is called nitrito. Similarly, M-SCN in called
thiocyanato and M-NCS is called isothiocyanato. Systematically they are
named as thiocyanato-S or thiocyanato-N to indicate which atom is bonded to
the metal. This convention is extended to other cases where the mode of linkage
is ambiguous. For example, NH 4 [Cr ( NCS) 4 ( NH 3 ) 2 ] is named as Ammonium
diamminethiocyanato-N-chromate(III) and [Cd (SCN) 4 ]SO4 as
Tetrathiocyanato-S-cadmium(II) sulphate. Such ligands are called ambidentate
ligands.
IX) Naming Geometrical isomers:- Geometrical isomers are named by the use
of cis to indicate the adjacent positions of two similar ligands and trans to
indicate the opposite. For a square planar complex such as [ Pt ( NH 3 ) 2 Cl 2 ]
which is isolated in two forms cis and trans can be shown as
2 1 2
1 Cl NH3 H3N Cl
Pt Pt
4Cl 3 4 3
NH3 Cl NH3
cis (1,4 or 2,3 positions are cis) trans (1,3 or 2,4 positions are trans)
X) Naming optical isomers:- Dextro and laevo rotatory optically active complex
compounds are designated as(+) and (--) or as d- and l- respectively.
A few IUPAC names are given below with their formulae.
[Co( NH 3 ) 6 ]Cl 3 Hexaamminecobalt (III) chloride
[CoCl( NH 3 ) 5 ]2 + Pentaamminechlorocobalt (III) ion.
[Co. Cl. CN. NO 2 ( NH 3 ) 3 ] Triamminechlorocyanonitrocobalt(III).
[Co.SO 4 ( NH 3 ) 4 ]NO 3 Tetraamminesulphatocobalt(III) nitrate.
K 3[ Fe(CN) 6 ] Potassium hexacyanoferrate(III). (Pot.ferricyanide).
K 3[ Fe(CN) 5 NO] Potassium pentacyanonitrosylferrate(III)
(Here, NO is neutral)
K 2 [Cr (CN) 2 O 2 (O 2 ) NH 3 ] Potassium amminedicyanodioxoperoxochromate(VI).
Na 3[Ag(S 2 O 3 ) 2 ] Sodium bis(thiosulphato)argentate(I).
Na 2 [ Fe(CN) 5 NO] Sodium pentacyanonitrosoferrate(II) (Here, NO is NO +)
(Sodium nitroprusside)
[ Fe( H 2 O) 5 NO]SO 4 Pentaaquanitrosoiron(I) sulphate (Here, NO is NO +)
(This complex is formed during brown-ring test for

nitrate)
K2HgI4 Potassium tetraiodomercurate (II)
LiAIH4 Lithium tetrahydridoaluminate(III)
[CuCl 2 (CH 3 NH 2 ) 2 ] Dichlorobis(methylamine) copper (II)
[ Pt ( py) 4 ] [PtCl 4 ] Tetrapyridineplatinum(II) tetrachloroplatinate(II).
[Cr (NH3)6][Co(C2O4)3] Hexaamminechromium (III) trioxalatocobaltate (III)
[ Pt ( NO 2 )( NH 3 )(C5H 5 N)(H 2 O) ]Cl Ammineaquanitropyridine platinum(II) chloride.
[Cr ( H 2 O) 4 Cl 2 ]Cl.2 H 2 O Tetraaquadichlorochromium(III) chloride 2-water.
(A hydrated complex)
Ni (DMG)2 Bis(dimethylglyoxamato) nickel (II)
Fe (CO)5 Pentacarbonyliron (O)
13.7 ISOMERISM IN COORDINATION COMPOUNDS :

Compounds which have the same chemical composition but different arrangements
of their atoms are called isomers and this phenomenon is known as isomerism. The isomers
differ in one or more physical or chemical properties.
Metal complexes exhibit different kinds of isomerism. The main types are
(a) Stereoisomerism and (b) Structural asomerism Steroisomerism is further
subdivided into
(I) Geometrical isomerism (II) Optical isomerism.
Stereoisomers have the same chemical formula and chemical bonds, but they have
different spatial arrangements. Structural isomers have different bonds.
(I) Geometrical isomerism — Geometrical isomerism is due to ligands occupying
different positions around central ion. Ligands occupy postions either adjacent
to one another or opposite to one another and are termed as cis-form and
trans-form respectively. Geometrical isomerism of compounds with
coordination numbers 4 and 6 is most important.
Coordination Number 4 — In these complexes two principal geometries are
found i.e. tetrahedral and square planar. Cis-trans isomerism is not possible
in tetrahedral complexes. However, cis-trans isomerism is very common
amongst square planar complexes.
In complexes of type Ma 2b2 such as [Pt(NH3)2Cl2] or [Pd(NH3)2(NO2)2] cis-trans
isomers are found. Similar complexes of Ni(II), Cu (II) and Co(II) are also known
Cl NH3 Cl NH3
Pt Pt
Cl NH3 H3N Cl
cis trans
Fig. 13.1 Cis-trans forms of [Pt(NH 3)2Cl2]
In complexes of type Ma 2bc where M = Pt, a = NH3 and b, c = Cl---, Br---, NO---2 , SCN-
--
etc. cis-trans isomers exist.
Coordination Number 6 — The regular geometric arrangement is octahedral.
Tetraammine dichlorochromium(III) ion exists as cis (violet) and trans (green) forms.
+
Cl + Cl
H3N Cl H3N NH3
Cr Cr
H3N NH3 H3N NH3
NH3 Cl
cis (violet) trans (green)
Fig.13.2 Cis-trans forms of [Cr(NH3)4Cl2]+
Large number of octahedral complexes of the type Ma 4b2 or Ma2b4 or Ma4xy where
M=Co(III), Cr (III), Rh (III) and Pt (IV) exist as isomers.
Complexes of the type Ma 3b3 exist in two isomeric forms.

For example: [Rh(py) 3Cl3], where py = pyridine.
py py
Cl py Cl py
Rh Rh
Cl py py Cl
Cl Cl
(cis) (trans)
Fig. 13.3 Cis-trans forms of [Rh(py)3Cl3]
(II) Optical isomerism — Optical activity is due to lack of symmetry of the

molecule. It is known that d– and 1– isomers are just mirror images of one
another just as the left hand is the mirror image of the right hand. Optical
isomers have identical chemical and physical properties and differ only in
the direction in which they rotate the plane of polarised light. The dextro
form rotates the plane towards the right and laevo form, towards the left.
Only tetrahedral complexes (coordination number-4), containing two
unsymmertrical bidentate ligands of Be (II), B (III) and Zn (II) can be resolved
into optically active forms. Square planar complexes are seldom optically
active.
Coordination Number 6 — Common examples are compounds or ions of
the type [M(aa) 2] whose aa = bidentate ligand (occupies two coordination
positions). For example, trioxalatochromate (III) ion exists in two optically
active forms.
XO
OX
3– 3–
OX
OX
Cr Cr
X
O
O
X
Fig. 13.4 Optical isomers of trioxalatochromate (III) ion

Some other common complexes with coordination number 6, belong to the type
[M(aa)2b2] where ‘aa’ = bidentate ligand. The cis-form of these complexes have been resolved
into d- and l-isomers but the trans-form does not show optical isomerism.
Fig. 13.5. d- and 1-isomers of cis-form of the complex [M(aa)2b2]
An example of this type is the cis-form of dichloro bis (ethylenediamine) rhodium

(III). Also complexes of the type [M(aa) 3] where ‘aa’ = bidentate ligand, for example,
tris(ethylenediamine)cobalt(III) cation gives the d-and 1-isomers.
Fig. 13.6 d– and 1– isomers of tris (ethylenediamine) cobalt(III).

Structural isomerism : This is shown by compounds having different ligands within their
coordination sphere. Various types of such isomerism are discussed below.
1) Ionisation isomerism — This type of isomerism is shown by such compounds
which have same composition but liberate different ions in solution. In such
isomers, the position of groups whithin or outside the coordination sphere
differs.
Examples : [Co(NH3)5SO4]Br (Red) – liberates Br — ions in solution.
and
[Co(NH3)5Br]SO4 (Purple) – liberates SO42— ions in solution.
2) Hydrate isomerism — This type of isomerism results from the replacement

of a coordinated group by water of hydration. These isomers differ widely in
their physical and chemical properties.
Examples : [Cr(H2O)6]Cl3 (Violet) – Does not lose water molecules but

three Cl— ions are precipitated by
AgNO3 solution.
[Cr(H2O)5Cl]Cl2(H2O)(Light green)– Loses one molecule of water but

two Cl— ions are precipitated by
AgNO3 solution.
[Cr(H2O)4Cl2]Cl(2H2O)(Dark green)– Loses two molecules of water on

dehydration, but one Cl — ion is
precipitated by AgNO3 solution.
3) Linkage isomerism — This type of isomerism is shown by such complexes

which contain a monodentate ligand having more than one donor atom. Thus,
cyanide ion : Cº N—: can attach itself to metal M either through the carbon M
- C º N—: or the nitrogen M - N º C:-. Similarly, : N º C--S:- (through N or
: :
S), :C º O: (through C or O).

4) Coordination isomerism— This type of isomerism is shown by such
compounds which contain both cationic and anionic species and it results
from random distribution of ligands.
Example : [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6].
5) Ligand isomerism — When isomeric ligands are associated into complexes,

the complexes are isomers of each other.
Example: [Co(pn)2Cl2]+ and [Co(tn)2Cl2]+
pn=1, 2 - diaminopropane, tn = 1, 3 - diaminopropane

6) Coordination position isomerism— This type of isomerism is shown by
bridged complexes and involve different placement (attachment) of ligands.
It is a special type of coordination isomerism.
H
O
Examples : (NH3)4Co Co(NH3)2Cl2 SO4 and
O
H
H
O
Cl(NH3)3 Co Co(NH3)3Cl SO4
O
H
13.8 BONDING IN COORDINATION COMPOUNDS :

Though the bonding features in coordination compounds were described by Werner, his
theory could not explain the following basic questions.
(a) Why the coordination compounds are formed by only certain elements ?
(b) Why the bonds present in coordination compounds have directional properties ?
(c) Why certain coordination compounds appear coloured and they possess characteristic
magnetic and optical properties ?
Three modern theories have been developed with a view to explaining the nature of
bonding and properties of coordination complexes. These are
(a) The Valence Bond Theory
(b) The Crystal Field Theory
(c) The Molecular Orbital Theory
13.8.1 THE VALENCE BOND THEORY
This theory was develoved by Pauling.
Postulates
1. During the formation of coordination compounds the ligands coordinate with the central
metal ion. For the formation of coordinate bond the central metal ion provides an adequate number
of empty orbitals to accomodate the electron pairs from the ligand. The number of empty orbitals
is equal to the coordination number of the central ion.
2. The atomic orbitals (s, p and d) of the metal hybridise giving hybrid orbitals of equivalent
energies. The number of hybridising orbitals is equal to the number of hybrid orbitals. The hybrid
orbitals are directed to the positions of the ligand depending upon the geometry of the complex.
(see Table -1)
3. Each ligand must have atleast one orbital containing a lone pair of electrons.
4. The inner d-orbitals i.e. (n–1)d or the outer d-orbitals i.e. n d- orbitals participate in
hybridisation. For example, in case of octahedral structure the hybridisation is of (n–1) d 2sp3 type
or n sp3d2 type. The complexes thus formed are known as low spin and high spin complexes
respectively.
5. The ligand -metal coordinate bond is formed by the overlapping of vacant hybrid orbitals
of metal ion with completely filled orbitals of the ligand. The number of such bonds varies with
the number of vacant orbitals made available by the central metal ion.
Table - 1
Coordination Hybrid Molecular Examples
number orbitals geometry
O O –
2 sp Ag(NH3)2+, Ag(CN)2
Linear
O
–
3 sp2 [HgI3]
O O
Trigonal planar
O
4 sp3 O [Ni(CO)4], [Zn(NH3)4]2+

O
O
Tetrahedral
O O
4 dsp2 [Ni(CN)4]2–, [Pt(NH3)4]2+

O O
Square planar
The d-orbital involved
in dx2–y2 of the inner
i.e (n–1)th shell.
O
O
O
3
5 dsp O [Fe(CO)5]
O
T r i g o n a l
The d-orbital involved i.e. dz2 bipyramidal
of the inner i.e. (n–1)th shell.
5 sp3d [SbF5]2 –
The d-orbitals involved

Square pyramidal
i.e. dx2–y2 of the outer i.e. nth shell
6 d 2 sp3 or sp3d 2 [Co(NH3)6]2+
The d orbitals involved are (n-1)d orbitals are involved.
d x2–y2 and dz2 of the inner in (n–1)th [CoF6]3– nd orbitals are
shell in the 1st case and of the outer involved.
i.e. nth shell in the second case
Octahedral
The stereochemical and magnetic properties of co-ordination compounds can be predicted
by Valence bond theory. We know that the substance which contains no unpaired electron is
known as diamagnetic substance and it is repelled by the magnetic field. On the other hand, the
substance which contains unpaired electron is known as paramagnetic substance and it is attracted
by the magnetic field. It is possible to predict the geometry of the complex, the number of unpaired
electrons and the type of hybridisation involved on the basis of Valence bond theory.
Examples of Octahedral complexes
Consider the formation of complexes of Co (III) on the basis of Valence bond theory.
1. Hexaamminecobalt(III) ion, [Co (NH3)6]3+
The outer electronic configuration of Co (III) is 3d 6. The six electrons are to be distributed
among the five numbers of 3d orbitals. The hybridisation scheme is as shown below in the diagram
(Fig.13.5)
orbitals of Co3+ ion

3d 4s 4p
d2sp3 hybridised orbitals of Co3+

d2sp3 hybrid
[Co (NH3)6]3+
(Inner orbital or Six pairs of electrons from six NH3 molecules
low sprin complex)
Fig.13.5 Formation of octahedral complex [Co(NH3)6]3+ involving d2sp3

hybridisation of Co3+ ion orbitals
The six number of hybrid orbitals are occupied by six pairs of electrons one from each NH 3
molecule. The complex has octahedral geometry and because of absence of unpaired electrons it
is diamagnetic in nature . In the formation of this complex the inner orbital 3d is used in
hybridisation. Hence the complex is known as inner orbital or low spin or spin paired complex.
2. Hexafluorocabalt (III) ion, [CoF6]3–
Hexafluorocobalt (III) ion is paramagnetic. In this case the 3d orbitals do not take part in
hybridisation, rather the 4d orbitals are involved. The hybridisation scheme is as shown below in
diagram (Fig.13.6).
Orbitals of Co3+ ion
3d 4s 4p 4d
3 2
sp d hybridised
orbitals of Co3+ 3d sp3d2 hybrid 4d
3–
[CoF6]
(Outer orbital or
high spin complex) 3d Six pairs of electrons from six F– ions 4d
3– 3 2
Fig. 13.6 Formation of octahedral [CoF6] complex involving sp d
hybridisation of Co3+ ion orbitals
The six number of hybrid orbitals are occupied by six pairs of electrons one from each F – ion.
The complex has octahedral geometry and because of the presence of unpaired electrons it
is paramagnetic in nature. In the formation of the complex the outer 4d orbitals are used in
hybridisation. Hence the complex is known as outer orbital or high spin or spin free complex.
Examples of Square planar and Tetrahedral complexes
Consider the complexes of Ni in which the coordination number of the metal ion is 4.
(i) Tetracyanonickelate (II) ion, [Ni (CN)4]2–
The Ni (II) ion has 3d 8 outer electronic configuration. The 8 electrons are to be distributed
in five d orbitals. According to Hund’s rule, there are two unpaired electrons. The hybridisation
scheme is as show below in diagram (Fig. 13.7).
orbitals of Ni2+ ion
3d 4s 4p
dsp2 hybridised
orbital of Ni2+
3d dsp2 hybrid 4p
[Ni(CN)4]2–
(low spin complex) 3d Four pairs of electrons 4p
from 4CN– ions
Fig 13.7 Formation of square planar [Ni(CN)4]2– complex involving dsp2
hybidisation of Ni2+ ion orbitals
The hybridisation involved here in dsp2 and the structure is square planar. In this case one
of the 3d orbitals is made empty and available for hybridisation. This is possible only by the fact
that the two unpaired electrons are paired by the energy available due to the approach of the
ligands. The four hybrid orbitals are occupied by four pairs of electrons, one from each CN – ion.
Since there are no unpaired electrons the complex is considered to be diamagnetic in nature. The
empty hybrid orbitals of the metal overlap with the completely filled orbitals of CN – ions to form
metal- ligand co-ordinate bonds.
(2) Tetrachloronickelate (II) ion, [Ni(Cl)4]2–
The nickel (II) ion has two unpaired electrons as shown below in Fig(10.8). Since the
complex is paramagnetic it would involve unpaired electrons and sp3 hybridisation. The structure
is tetrahedral.
orbitals of Ni2+ ion
3d 4s 4p
3
sp hybridised
orbitals of Ni2+
3d sp3 hybrid
[Ni(Cl)4]2–
(high spin complex) 3d Four pairs of– electrons
from 4Cl ions.
Fig. 13.8 Formation of tetrahedral [NiCl4]2– complex involving sp3 hybridisation of Ni2+ oritals.
–
The four hybrid orbitals are occupied by four pairs of electrons, one from each Cl ion.
Since there are unpaired electrons the complex is considered to be paramagnetic.
Magnetic Properties of Co-ordination Compounds
Magnetic susceptibility experiment measures the magnetic moment of coordination
compounds. The results obtained reveal the structures adopted by the metal complexes.
Let us take the cases of 1st row transition metal series. The magnetic data of co-ordination
compounds of these metals reveal some complications. In case of metal ions Ti 3+ (d1), V3+(d2),
Cr3+ (d3), two vacant d-orbitals are available for d2sp3 hybridisation with 4s and 4p orbitals having
octahedral geometry. The magnetic behaviour of coordination compounds of these ions are similar.
But when there are more than three 3d electrons, the vacant pair of d-orbitals is available
only by pairing. So for d 4 (Cr2+, Mn3+), d 5(Mn2+, Fe3+) and d6(Fe2+, Co3+), as a result of pairing of
d-orbitals two, one and zero unpaired electrons are left respectively. Maximum complications
arise with species having d 4 and d 5 ions, e.g. [Mn(CN)6]3– has a magnetic moment of two unpaired
electrons whereas [MnCl6]3– has a paramagnetic moment of four unpaired electrons. [CoF 6]3– is
paramagnetic with four unpaired electrons whereas [Co (C 2O4)3]3– is diamagnetic. [Fe(CN)6]3–
has a magnetic moment of a single unpaired electron whereas [FeF 6]3– has a paramagnetic moment
of five unpaired electrons.
This anomaly is, however, explained by Valence Bond Theory on the basis of inner orbital
and outer orbital complex formation. The co-ordination complex ion like [Mn(CN) 6]3–, [Fe (CN)6]3–
and [Co (C2O4)3]3– are inner orbital complexes involving d2sp3 hybridisation. But the former two
are paramagnetic whereas the latter one is diamagnetic. Similarly, the complexes like [MnCl 6]3–
, [FeF6]3– and [CoF6]3– are outer orbital complexes involving sp3d2 hybridisation and are
paramagnetic having 4,5 and 4 unpaired electrons respectively.
Limitations of Valence Bond Theory
(1) The colour exhibited by co-ordination compounds can not be explained by the theory.
(2) The quantitative interpretation of magnetic data can not be made by this theory.
(3) The thermodynamic and kinetic stability of co-ordination compounds can not be explained
by the theory.
(4) The theory can not distinguish between weak and strong ligands.
(5) The theory fails to predict the number, position and intensities of the bonds observed in
electronic spectra of coordination compounds.
(6) The theory does not explain satisfactorily why some complexes of a metal ion in a particular
oxidation state are low spin (inner orbital) whereas some other complexes of the same
metal ion in the same oxidation state are high spin (outer orbital) e.g. [Co (NH 3)6]3+ is
diamagnetic and [CoF6]3– is paramagnetic.
(7) Exact predictions regarding the structure of 4-coordinate complexes whether tetrahedral or
square planar can not be made by this theory.
13.8.2 CRYSTAL FIELD THEORY
The theory was developed by H. Bethe and V. Bleck. According to this theory the bonding
between a central metal ion and its ligand arises from purely electrostatic interactions. The ligand
may be an anion or a neutral molecule having unshared or lone pair of electron. In case of anion
the ligands are treated as point charges whereas in case of neutral molecules these are treated as
dipoles. If the ligand is an anion the attraction between the central ion and the ligand is same as
that between two oppositely charged particles. If the ligand is a dipole the negative end of the
dipole is attracted towards the central positive ion.
The five d-orbitals is an isolated gaseous atom or ion are degenate i.e. they have the same
energy. The degeneracy is maintained if the metal ion is surrounded by spherically symmetrical
field of negative charges. But when the metal ion is surrounded by the ligands in a complex, the
negative field becomes asymmetrical and the degeneracy of the d-orbital is destroyed or lifted. It
results in splitting of d-orbitals. The nature of crystal field affects the pattern of splitting.
Orientation of d-orbitals and Crystal field splitting of Energy levels.

Depending upon the nature of orientation in space the d-orbitals are divided into two
groups (Fig.10.9). Three orbitals belonging to one group are oriented in the regions in between
the coordinate axes and are designated as dXY, dYZ, dXZ while the other two orbitals belonging to
another group or oriented along the axes and are designated as dx2–y2 and dz2. In case of a free
metal ion, all the five d-orbitals are degenerate i.e. they are of equal energies.
x x y
- + - + - +
-y y -z z -z z
- + -
+ + -
-y
-x -x
dxy dxz dYZ
dyz
d XY d XZ
y z
+
y
-
-x + + x -x x
- +
-y
-y -z
dx2–y2 dz2
Fig. 13.9 Shape of d-orbitals
Now consider the case when the five d-orbitals of the metal ion are surrounded by the
negative charge of the ligands (anion or dipole). The energy of the orbitals lying along the axes
i.e in the direction of point charges would be raised to a larger extent than that of the orbitals
lying in between the axes. The splitting of five degenerate d-orbitals of the metal ion into set of
orbitals having different energies is called crystal field splitting.
Crystal field splitting in Octahedral complexes

In an octahedral complex there are six ligands surrounding the metal atom or ion. Repulsion
takes place between the electrons in metal d-orbitals and electrons of the ligands. The repulsion
is more pronounced when the metal d-orbital is directed towards the ligand than when directed
away from the ligand. As a result dx2–y2 and dz2 orbitals which point towards the axes along the
direction of the ligand will experience more repulsion than dxy, dyz and dxz orbitals which are
directed between the axes. The energy of dx2 – y2 and dz2 will be raised while that of dxy, dyz
and dxz will be lowered compared to the average energy in spherical Crystal field. Thus due to
metal electron - ligand electron repulsion the degeneracy of the d-orbitals has been lost in octahedral
complex. Two sets of d-orbitals are formed.
(i) t2g set comprising of three orbitals of lower energy
(ii) eg set having two orbitals of higher energy.
The energy separation between the two sets is represented by D0 (The subscript ‘o’ is for
octahedral) (Fig.10.10). The energy of two eg orbitals increases by (3/5) D0 or 0.6D0 or 6Dq and
that of three t2g decreases by (2/5) D0 or 0.4 D0or 4Dq
Energy
z dx2–y2 dz2 eg
y 3/5D0
x D0
2/5D0
Metal dxy dxz dyz t2g
d orbitals
Average energy Splitting of d-orbitals
dx2-y2 , dz2, of the d-orbitals in in octahedral
dxy, dxz, dyz spherical crystal field crystal field
Free metal ion
Fig. 13.10 d-orbital splitting in an octahedral crystal field

The factors that affect the crystal field splitting are (i) charge on the meal ion (ii) field
produced by the ligand. The splitting will be large if the ligands produce strong field whereas the
splitting will be small if the ligands produce weak field. The ligands may be arranged in the
increasing order of the field strength produced by them in a series known as spectrochemical
series as shown below.
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4– < NH3 < en < CN– < CO
The series is based on absorption of light by complexes with different ligands.
Crystal Field Stabilisation Energy (CFSE)

The electron always prefers to occupy orbital of lower energy. In an octahedral complex
containing one d-electron, it is evident that the electron would occupy one of the t 2g orbitals. This
orbital has energy –0.4 D0 compared to energy zero for hypothetical degenerate d–orbitals. Thus
the complex will be 0.4 D0 more stable than predicted by electrostatic theory. The decrease in
energy 0 – (–0.4 D0) = 0.4 D0 is known as the crystal field stabilisation energy of the complex
under consideration.
For a d 2 system, the two d-electrons will prefer to occupy t 2g orbitals. The CFSE is 2×0.4
D0 = 0.8 D0. For a d 3 system the CFSE similarly is 3 × 0.4 = 1.2 D0
But for a d 4 system these are two possibilities.
(i) All the four may occupy the three 2g orbitals. So one electron must be paired.
(ii) Three electrons occupy t2g orbitals and one electron eg orbital
(See Table.2 for CFSE energies for metal ions having different number of d-electrons in
octahedral complexes).
Table - 2
Crystal Field Stabilisation Energies for Metal Ions having Different
Number of d-Electrons in Octachedral Complexes.
No. of Distribution of Electrons Distribution of Electrons
d electrons (High Spin) CFSE* (Low Spin) CFSE
in metal ions t2g eg t2g eg
1 4Dq
2 6Dq**
3 12 Dq
4 6Dq 16 Dq
5 0 20 Dq
6 4Dq 24 Dq
7 6Dq** 18 Dq
8 12 Dq
9 6 Dq
10 0
* Calculated by including the effects of interelectronic repulsions amonst the d electrons and
the effects of d orbital splitting.
** CFSEs of these configurations are 8 Dq if we consider the effects of d orbital splitting
alone and neglect the effects of interelectronic repulsions amongst the d electrons.
Table - 3
Crystal Field Stabilisation Energies for Tetrahedral
Complexes with Metal Ions having different
Electronic Configurations
Electronic Distribution of Electrons CFSE
configuration e t2
d1 6 Dq
d2 12 Dq
3
d 6 Dq*
d4 4 Dq
5
d 0
6
d 6 Dq
d7 12 Dq
8
d 6 Dq*
d9 4 Dq
10
d 0
* CFSEs of these configurations are 8 Dq if we consider the effect of d orbital splitting alone
and neglect the effects of interelectronic repulsions amongst the d electrons
The actual configuration is decided by taking into account D0 and P (Pairing energy i.e the
energy required for pairing the electrons)
(a) If D0 > P, configuration (1) is possible. The complex has less number of unpaired
electrons and it is known as low spin or strong field complex.
(b) If D0 < P, configuration (2) is possible. The complex has maximum number of unpaired
electrons and it is known as high spin or weak field complex.
From detailed calculation it is found that d 4 to d 7 coordination complexes are more stable
for strong field as compared to weak field cases.
Crystal Field splitting in Tetrahedral complexes
In a tetrahedral complex there are four ligands surrounding the metal atom or ion. The d-
orbital splitting in this case is inverted and is smaller as compared to the octahedral splitting. For
the same metal ion and same ligand and metal-ligand distance it is observed that Dt = 4/9 D0 (see
Fig. 13.11)
Pairing of electrons in the orbital does not take place easily since orbital splitting energies
are not sufficiently large for forcing pairing. So low spin configurations are almost not observed.
dxy ,dyz, dxz

t2
2
Dt
5
Dt
3
Dt
5
e
dx2–y2 , dz2
d orbitals Average energy of Splitting of d orbitals in
free ion the d orbitals in tetrahedral crystal field
spherical crystal
field
Fig. 13.11 d orbital splitting in an tetrahedral crystal field.
Colours in Coordination compounds.

A substance which possesses the property of absorbing certain radiations from the visible
region (3800A0 – 7600A0) of the spectrum exhibits colour. So when white light in passed through
the sample of co-ordination compound some of the visible spectrum is removed from the white
light. The colour of the complex is complementary to that which is absorbed. The complementary
colour is the colour produced from the wave length of visible light left over. For example if red
light is absorbed by the complex it appears blue (see Table.10.4) Hydrated copper ions absorb red
light and thus appear blue.
Table. 13.4
Relationship between the Wavelength of Light absorbed and the
Colour obsrved in some Coordination Entities
Coordination Wavelength of light Colour of light Colour of Coordination

entity absorbed (nm) absorbed Entity
[CoCl(NH3)5]2+ 535 Yellow Violet
[Co(NH3)5(H2O)]3+ 500 Blue Green Red
[Co(NH3)6]3+ 475 Blue Yellow Orange
[Co(CN)6]3– 310 Ultraviolet Pale Yellow
[Cu(H2O)4]2+ 600 Red Blue
[Ti(H2O)6]3+ 498 Blue Green Violet
In case of transition metal complexes the energy difference between two sets of d-orbitals
is small. So the excitation of electron from t 2gorbital to eg orbital involves absorption of low
energy radiation and as a result the complex appears coloured. The complex [Ti (H 2O)6]3+ is
having octahedral geometry. It has d 1 configuration. It absorbs radiations in the green and yellow
regions corresponding to wave length around 5000A0. This corresponds to energy 240 kJ (Q E =
hc
hu = , h = Planck’s constant, c = velocity of light) This energy (equals to D0) is required to
l
cause promotion of electron from t2g to eg orbital. The solution of the complex looks purple which
is the complementary colour to the absorbed colour.
Since the value of D0 depends upon the nature of ligands, nature of ions and geometry of
the complex formed, different coordination compounds absorb radiations from different regions
of visible light and exhibit different colours, e.g. octadral [Co (H 2O)6]2+ absorbs in blue region
and appears pink (red). Tetrahedral [CoX4]2– absorb in red region and appears blue. [Co(NH3)6]3+
absorbs in blue region and appears orange in solution.
Transition metal ions having completely filled orbitals or completed empty orbitals are
colourless. So complexes of Cu+(d 10), Zn2+ (d 10), Ag+ (d10), Sc3+(d 0), Ti4+(d 0) etc. are colourless.
Limitations of CFT (Crystal Field Theory)
(1) Anionic ligands are found at the low end of spectrochemical series inspite of the fact
that they produce greatest splitting effect.
(2) It is not concerned with the covalent character of metal-ligand bond.
13.9 BONDING IN METAL CARBONYLS :

In metal carbonyls, a metal atom is directly linked to the carbon atom of a carbonyl group.
Metal carbonyls possess simple structures, in which electrons forming OC ® M bond are furnished
by CO molecules. For this, metal atom in carbonyls is said to be in zero oxidation state. Basing
on the number of metal atoms present, these may be (i) mononuclear carbonyls, M(CO) x and
(ii) polynuclear carbonyls. Mx(CO)y.
According to Valence Bond Theory, the structures of the carbonyls are explained on the
basis of nature of hybridisation of atomic orbitals. For example, Ni(CO) 4 is tetrahedral, Fe(CO)5
is trigonal bipyramidal and Cr(CO)6 is octahedral. O
C
O
O
O
O
O
C
C
C
O O
C C
Ni Cr
Ni
C
C
O
O
C
O C
O
O
Fig.13.12 (a) Ni(CO)4 (b) Fe(CO)5 (c) Cr(CO)6

From the X-ray or electron diffraction method, it is found that the metal-carbon bonds are
intermediate between the M – C º O and M = C = O states, i.e. there is some double bond
character in M – CO. Thus, it can be said that a M – C s bond is formed along with M – C p bond.
While the M – C s bond involves the donation of lone pair of electrons on the carbonyl carbon
atom to an empty metal orbital, the M – C p bond is formed by dative overlapping of a filled d-
orbital of metal with empty antibonding p-orbital of the carbon atom.
dative p bond
Metal carbon monoxide
dative s bond
s
M C O
Fig. 13.13. M ® C p bond and M ¬ C s bond
13.10 STABILITY OF CO-ORDINATION COMPOUNDS :

While studying the stability of a coordination compound formed in solution, following
stepwise addition of ligands to a metal ion is considered. Formation of the complex, ML n is
supposed to take place by the following n consecutive steps.
[ML]
M+L ML : K1 =
[M][L]
[ML 2 ]
ML + L ML2 : K2 =
[ML][L]
[ML 3 ]
ML2 + L ML3 : K3 = [ML ][L]
2
- - - - - - - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - - - - - -
[ML n ]
MLn–1 + L MLn : Kn = [ML ][L]
n -1
Where K1, K2, K3 .............. Kn are referred to as stepwise stability constants and the overall
stability constant, K is expressed as :
ML n
M + nL MLn K = K1K2K3..........Kn =
[M][L]n
Greater the value of the overall stability constant, more will be the stability of the complex.
The reciprocal of stability constant is called dissociation constant or instability constant (1/K).
The value of stability constant depends on the nature of the metal ion and the ligand. It is
observed that, higher the charge density on the central metal ion more is the stability of its
charge
complexes, i.e. for a bigger value of , stability of its complex has a bigger value too.
radius of ion
Again, more basic nature of a ligand also accounts for greater stability of the complex, as the
donation of lone pairs of electrons by the ligands becomes easier.
13.11 IMPORTANCE OF COORDINATION COMPOUNDS :

1. In Qualitative analysis
The coordination compounds are of great importance and have wide range of applications.
Since they are present in the mineral, plant and animal world they find extensive use in analytical
chemistry, metallurgy and biological systems.
In qualitative analysis the detection and estimation of metal ions by chemical and
instrumental methods of analysis are based on colour reactions with a number of chelating ligands
resulting in the formation of coordination entities. Examples of such chelating ligands include
EDTA, DMG etc.
2. Extraction of metals
Extraction processes of metals like silver and gold make use of complex formation. In
presence of oxygen and water gold combines with cyanide to form the complex ion [Au(CN) 2]–
in aqueous solution. By adding zinc to this solution, gold can be separated in the form of metal.
Purification of metal can also be made through complex formation. For example, impure nickel
is converted to [Ni(CO)4] which on decomposition yields pure nickel.
3. In Biological systems
We know that chlorophyll is very much necessary for the process of photosynthesis. It is a
coordination compound of magnesium. The coordination compound of iron is haemoglobin
which acts as an oxygen carrier. Vitamin B12 known as cyanocobalamine is an antipernicious
anaemia factor. It is a coordination compound of cobalt. Similarly many enzymes coordinate
with metal ions forming coordination compounds which are of great importance in biological
systems.
13.12 ORGANOMETALLIC COMPOUNDS :

13.12.1 Introduction :
Compounds containing atleast one carbon-metal bond are called organometallic
compounds. The first organometallic compound was prepared by Zessie in 1830 by the action of
ethylene on a solution of potassium chloroplatinate (II). Quite a good number of such compounds
have been synthesised and investigated during the last few years. Grignard reagent, R Mg X is a
familiar example of organometallic compounds where R is an alkyl group. Other organometallic
compounds include diethyl zinc [Zn(C2H6)], teraethyl lead [Pb (C2H5)4], dibenzene chromium
[Cr(C6H6)2], ferrocene [Fe(C5H5)2] and metal carbonyls.
13.12.2 Classification :
Organometallic compounds may be classified into three classes :
1. Sigma ( s ) bonded complexes.
2. Pi ( p ) bonded complexes.
3. Complexes containing both s - and p -bonding characteristics.
1. Sigma ( s ) bonded complexes :
In these complexes, the metal atom and carbon atom of the ligand are joinedtogether with
a sigma bond. Here, the ligand donates one electron and is therefore, called one electron
donor. Examples are :
(i) Grignard reagent, R-Mg-X where R is an alkyl or aryl group and X is a halogen.
(ii) Dialkyl zinc, R2Zn i.e. (C2H5)2 Zn. Other similar compounds are (CH3)4 Sn, (C2H5)4
Pb, Al2(CH3)6, Al2(C2H5)6, (CH3)4Pb etc.
2. Pi ( p ) bonded organometallics:
Metals form compounds with alkenes, alkynes, benzene and other ring compounds in
this type. In these complexes, the metal and ligand form a bond involving p - electrons of
the ligand. Common examples are Zeise's salt, ferrocene and dibenzene chromium. They
have the formula K[PtCl3( h 2—C2H4)], Fe ( h 5-C5H5)2, and Cr ( h 6-C6H6)2 respectively

where prefixes h 2 (etc), h 5 and h 6 indicate that 2, 5 and 6 carbon atoms are bound to the
metal in the compound.
3. Sigma ( s ) and Pi ( p ) bonded organometallics :
Metal carbonyls which are formed between metal and carbon monoxide belong to this
class. These compounds possess both s -and p -bonding. The oxidation state of the metal
atoms in these compounds is zero. Carbonyls are mainly formed by the tranisitional
metals of VI, VII & VIII groups. Carbonyls may be monomeric, bridged or polynuclear.
Some common examples are tetracarbonyl nickel (0), Ni(CO) 4 ; Pentacarbonyl iron (0),
Fe (CO)5; hexacarbonyl chromium (0), Cr (CO)6 ; and Fe2 (CO)9.
13.12.3 Applications of Organometallic compounds :

Some important applications of organometallic compounds are mentioned below.
i. Tetraethyl lead (TEL) is used as an antiknock compound in gasoline.
ii. Silicones are used as polymers with unique properties.
iii. Grignard reagents and organoalkali are used in many organic synthesis.
iv. The extraction and purification of nickel is based on the formation of Ni(CO) 4.
v. Organometallic compounds are often used as homogeneous and heterogenous
catalysts. Zeigler Natta catalyst [TiCl 4 and triethyl aluminium] acts as a catalyst in
the polymerisation of ethylene to polythene.

1. Double Salt — Double salts are those molecular compounds which exist only in crystal
lattices but breakdown into their constituent compounds when dissoved in water or any
other solvent.
Alum, K2SO4. Al2(SO4)324H2O.
2. Complex Compounds — Complex compounds retain their identities even when dissoved
in water or any other solvent and their properties are completely different from those of
the constituents.
Examples : [Cu(NH3)4]SO4, [Ag(NH3)2]Cl.
3. Ligands - The ions or molecules bound to the central ion in the coordination compounds
are called ligands.
4. Coordination number - The number of ligands attached to the central ion is known as
coordination number of that ion.
5. Coordination sphere - The central ion bonded to the ligands constitutes the coordination
sphere. It is written within square bracket.
6. Unidentate, bidentate & polydentate ligands - The ligands which can coordinate to the
central ion through one, two and more than two donor atoms are known as monodentate,
bidentate and polydentate ligands respectively.
7. Chelates - A bidentate or polydentate ligand may link to the central ion through two or
more donor atoms forming a ring structure. The ligand is called a chelating ligand and
the complex is called a chelate.
8. Inner orbital or low spin or spin paired complex - In the formation of octahedral
complex if the inner 3d orbitals are used in hybridisation (d2sp3) the complex is known as
inner orbital or low spin or spin paired complex.
9. Outer orbital or high spin or spin free complex - In the formation of octahedral complex
if the outer 4d orbitals are used in hybridisation (sp3d2) the complex is known as outer
orbital or high spin or spin free complex.
10. Crystal field splitting - The splitting of five degenerate d-orbitals of the metal ion into
sets of orbitals having different energies is called crystal field splitting.
11. Spectrochemical series - The ligands may be arranged in the increasing order of field
strength produced by them in a series known as spectrochemical series.
12. Geometrical or cis-trans isomerism - Geometrical isomerism is due to ligands occupying
different positions around the central ion. Ligand positions adjacent to one another is
called cis-isomer and positions opposite to one another is called trans-isomer.
13. Optical isomerism - Optical isomers have identical chemical and physical properties
and differ only in the direction in which they rotate the plane of polarised light. Those
which rotate the plane to left are called laevo (1) and those which rotate the plane to right
are called dextro (d). These are mirror image isomers.
14. Structural isomerism - These include ionisation isomerism, hydrate isomerism, linkage
isomerism, coordination isomerism, ligand isomerism, and coordination position
isomerism.
15. Organometallics - Compounds containing atleast one carbon-metal bond are called
organometallics. They are classified into three classes — (i) Sigma bonded complexes
(ii) Pi-bonded complexes and (iii) Complexes containing both sigma and pi-bonding
characteristics. These organometallics have several applications.
QUESTIONS
A. Short answer type question (3 marks each) :
1. What is the difference between molecular compound and complex compound ?
2. Define the terms : central ion, complex ion, ligand, coordination number.
3. Give the IUPAC names of the following compounds :
[Ag(NH3)2]+, [Cu(NH3)4]+, [Cr(H2O)4Cl2], K2[PtCl6], [Fe(CN)6]4--, [Co(en)2Cl2]2SO4,
[Cr(NH3)6] (NO3)3, Na3 [Co(NO2)6], [Co(en)2 Cl(NO2)]+, [Pt(NH3)Cl5]–.
4. Write the formula of the following complexes :-
Hexaamminenickel (II) chloride, hexaamminechromium (III)nitrate, potassium
hexachloroplatinate (IV), trinitritoamminecobalt (III), potassium hexacyanoferrate (II),
potassium hexacyanoferrate (III), potassium trioxalatoaluminate (III), Dichlorobis
(ethylenediamine)-cobalt (III) sulphate, Ammonium tetrathiocyanatodiamminechromate
(III), Potassium pentachloro monoammine platinate (IV).
5. Write notes on Werner’s theory of coordination compounds.
6. Give some examples of molecular (non-ionic)complexes.
7. Give some examples of ionic complexes.
8. What is the symbol used before the bridging ligand while naming a complex ?
9. Give the order of naming the ligands.
10. What type of numeral is used to indicate oxidation state of central ion ? Write the structure
of Fe(CO)5.
11. Give examples of cis-trans isomerism exhibited by complexes of coordination number 4
and 6.
12. Give some examples of optical isomerism exhibited by complexes of coordination
number 6.
13. What are primary and secondary valencies ?
14. How optical isomers are designated ?
15. (a) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br show __________ isomerism.
(Ans: ionisation)
(b) KCl.MgCl2.6H2O is a _____________, but K4 [Fe(CN)6] is a ________.
(Ans: double salt, complex compound )
(c) [Co(NH3)4Cl2]Cl give _______ Cl— ions in solution.
(Ans: one)
(d) Whether cis-trans isomerism is exhibited by [Co(en) 2Cl2]Cl?
(e) Whether [Cr(en)3Cl3] exhibits optical isomerism or not ?
(f) Complexes of type MA4B2 can exist as _________ isomers.

(Ans: cis-trans)
(g) Write the possible isomers of the following compounds.
(i) [Cr(en)3]Cl3 (ii) [Cr(en)2Cl2]Cl.
(h) How many isomers are there for the complex [Co(NH3)3Cl3] ?
(i) Which type of square planar complexes show cis-trans isomerism ?
(j) Which type of octahedral complexes show geometrical isomerism ?
(k) Does [Co(NH3)6]Cl3 show optical isomerism ?
(l) Give an example of two hydrate isomers.
(m) Give as example of two ionisation isomers.
(n) What do you understand by linkage isomerism of CNS— ?
(o) Give an example of two coordination isomers.
(p) Draw all possible isomers of [Cr (NH 3)3Cl3].
(q) Give one example of both ionisation and hydrate isomerism in single
compound.
[Co(NH3)4 (H2O)Cl]Cl2 and [Co(NH3)4Cl2]Cl.H2O
(r) Draw the structure of triammine - 1, 2, 3 trichloroplatinum(IV)chloride.
(s) [Rh(en)3] [IrCl6] and [Rh(en)2Cl2] [Ir(en)Cl 4] are which type isomers ?
(t) How many chloride ions can be precipitated from an aqueous solution of
[Cr(py)2 (H2O)2 Cl2]Cl with AgNO3 ?
(u) How a double salt can be distinguished from a complex salt ?
1. What is the coordination number of each ion in NaCl?
2. (i) Write the name of the compound :
[Co (en) 2 Cl2]SO4
(ii) Write the formula of the compound :
‘Potassium pentachloro monoamine platinate (IV).
3. (i) What is the IUPAC name of the following compound.
K3 [Fe (CN)6]
(ii) Write formula of the following :
Ammonium diamminetetrathiocyanato chromate (III)
4. Write the formula of the following complex :
Tris (ethylene diamine) cobalt (III) sulphate.
5. Write short notes on : Werner’s theory of coordination compounds.

6. Write the name of the compound :
[(C 2 H 5 ) 5 N ]2 [ZnCl 4 ]
C. Very short answer type questions (one mark each) :
1. Fill in the blanks :
(i) Ethylene diamine is an example of ligand.
(ii) The IUPAC name of Fe(CO)5 is .
(iii) Dimethyl glyoxime is used for the gravimetric estimation of ion.
(iv) EDTA is a ligand.
(v) K4[Fe(CN)6] is a complex compound, but potash alum is a
(vi) One molecule of [Pt (NH3)6]Cl4 gives ions in solution and requires of
AgNO3 for complete precipitation of chloride ions.
(vii) Geometrical isomerism is not observed in complexes of coordination number 4 of
geometry..
(viii) The type of magnetism exhibited by [Mn(H 2O)6]2+ ion is
[Answer : (i) bidentate (ii) pentacaronyliron (0) (iii) Ni 2+ (iv) hexadentate (v) double salt
(vi) five, 4 molecules (vii) tetrahedral (viii) paramagnetism]
2. Match the following

1. Double salt (a) [Co (NH3)3Cl3]
2. Neutral molecule (b) Hexadentate
3. EDTA (c) Bidentate
4. Ni (CO)4 (d) Paramagnetic
5. [Cr (NH3)6]3+ (e) FeSO4 (NH4)2SO4.6H2O
6. Low spin complex (f) K4[Fe(CN)6]
7. Glycine (g) Diamagnetic
[Answer : (1-e), (2,-a), (3-b), (4-g), (5-d), (6-f), (7-c)]
3. What type of isomers are the following

(a) [(CO)5MnSCN] and [(CO)5MnNCS]
(b) [Co(en)3] [Cr (CN)6] and [Cr (en)3][Co(CN)6]
(c) [Co(NH3)5NO3]SO4 and [Co (NH3)5 SO4]NO3
(d) [Co(py)2 (H2O)2 Cl2] Cl and [Co (py)2 (H2O)Cl3] H2O
[Answer : (a) Linkage, (b) Coordination, (c) Ionisation, (d) Hydrate
D. Long Answer type (7 marks each) :

1. (a) What are the postulates of Valence Bond Theory ?
(b) Distinguish between inner and outer orbital complex with suitable examples.
2. Account for the following on the basis of Valence bond theory
(a) [Ni(CN)4]2– is diamagnetic and squareplanar.
(b) [NiCl4]2– is paramagnetic and tetrahedral.
3. Discuss in brief the Crystal Field theory. How does it differ from Valence Bond theory ?
Explain the fact that [CoF6]3– is paramagnetic whereas [Co(NH3)6]3+ is diamagnetic
although both are octahedral.
4. (a) Describe the bonding in [Fe(H2O)6]3+ and [Fe (CN)6]3– in terms of Valence Bond
theory and Crystal Field theory.
(b) Tetrahedral complexes do not show low spin configuration - Explain.
5. (a) Discuss briefly how Crystal Field theory explains the magnetic properties of complexes
of transition metals.
(b) Discuss the structure of following complexes on the basis of CFT.
(i) [Co(NH3)6]3+, (ii) [Fe (CN)6]4– .
qqq
HALOALKANES AND HALOARENES 405
UNIT - X
HALOGENATED HYDROCARBONS
(HALOALKANES AND HALOARENES)
CHAPTER - 14
HALOALKANES (ALKYL HALIDES)
14.1 INTRODUCTION :
When hydrogen atoms of an alkane are replaced by same number of halogen atoms the
compound formed is called halogen derivative of alkane. These are synthetic products and not
found in nature. Alkyl halides are the starting materials for the synthesis of a large variety of
aliphatic compounds. The halogen derivatives of alkanes, alkenes and alkynes are known as
alkyl halides (haloalkanes), alkenyl halides (haloalkenes) and alkynyl halides (haloalkynes)
respectively.
14.2 CLASSIFICATION :
Halogenated compounds may be classified in several ways depending on the type of
halogen atoms, number of halogen atoms and position of halogen atoms. Alkyl halides may
be mono, di, tri and so an according to the number of halogen atoms replacing hydrogen atoms
in an alkane. e.g. CH3Cl, CH2Cl2, CHCl3 and CCl4 are mono, di, tri and tetrahalomethane
respectively. Vinyl chloride (CH 2=CH–Cl) and ethynyl bromide (CH º C–Br) are the
monohalogen derivatives of unsaturated hydrocarbons.
14.3 MONOHALOGEN DERIVATIVES OF ALKANES :
When only one hydrogen atom of an alkane is replaced by a halogen atom (X) where
X=F, Cl, Br, I, the compound in called monohalogen derivative of the alkane, It has the general
formula CnH2n+IX and represented as R–X, where R=alkyl group and X = halogen atom.
In general, monohalogen derivatives are usually named as halides of the corresponding
alkane and the homologous series is known as alkyl halides. They can be looked upon as the
derivatives of halogen acids HF, HCl, HBr, HI in which the hydrogen atom of the acid has
been replaced by alkyl group and can be called alkyl halides.
Monohalogen derivatives can be divided into three classes depending upon the attachment
of halogen atom to a primary, secondary or tertiary carbon directly.
Primary halide : R—C—X e.g CH3–CH2–CH2–Br

H (1- Bromopropane)
R CH3
R—C—X CH3—C—Br
Secondary halide :
H H
(2-Bromo propane)
R CH3
R—C—X CH3—C—Br
Tertiary halide : eg.
R CH3
(2-Bromo -2-methylpropane)
14.4 NOMENCLATURE :
Common name to an alkyl halide in assigned by adding halide to the alkyl group .
Examples :
CH3Cl CH3CH2Br. CH3CH2CH2I
(Methyl chloride) (Ethyl bromide) (Propyl iodide)
According to the IUPAC system,, longest chain containing, the halogen atom is selected
and the alkyl halide is named as the substitution product of the corresponding alkane and
named as haloalkanes.
The common and IUPAC name of some alkyl halides are given below.
Formula Common name IUPAC name
CH3Br Methyl bromide Bromomethane
CH3CH2Br Ethyl bromide Bromoethane
CH3CH2CH2F n-Propyl fluoride 1–Fluoropropane
CH3
CH—Cl *Isopropyl chloride 2–Chloropropane
CH3
CH3
CH—CH2 — Br *Isobutyl bromide 1– Bromo - 2 - methylpropane
CH3
CH3
CH3—C—Cl
*tert – Butyl chloride 2– Chloro-2-methylpropane
CH3
* According to the new IUPAC system, trivial or common system like isopropyl, tert. butyl etc. can
also be used in IUPAC nomenclature.
14.5 METHODS OF PREPARATION :

Alkyl halides can be prepared by the following methods.
1. From alkanes :
Alkyl halides can be prepared by the direct halogenation of lower alkanes in the gas
phase, in diffused sunlight or at high temperature (400 0 C) or in the presence of catalyst such
as FeCl3, FeBr3, CuCl2 etc.
R–H + X2 n®
¾h¾ RX + HX
Alkane Alkylhalide
X = Cl or Br.
Cl Cl Cl Cl
CH4 ¾ ¾ ¾2 ® CH3Cl ¾ ¾¾2 ® CH2Cl2 ¾ ¾¾2 ® CHCl3 ¾ ¾ ¾2 ® CCl4
Methane Methyl Methylene Chloroform Carbon
chloride chloride tetrachloride
It is not a suitable method, because a mixture of mono, di, tri and tetra halides are
obtained.
CH3 CH3
Cl
CH3— C — CH3 ¾¾¾2 ® CH3 — C — CH2Cl
3000 C
CH3 CH3
(neopentane) (neopentyl chloride)
Under the influence of heat or light, halogenation takes place through free radical
mechanism
2. From alkenes :
Alkyl halide can be prepared by the addition of hydrogen halide HX(HX = HCl, HBr,
HI) to alkene. The reaction takes place when gaseous halogen halide is passed through a
solution of alkene in an inert solvent, in dark and at low temperature.
H X
C=C + HX ¾
¾® —C— C—
(Alkene) (Alkyl halide)
Addition of halogen acids to unsymmetrical alkenes follows Markownikoff's rule.
X H
R – CH = CH2 + HX ¾
¾® R— CH — CH2
For example :
Br H
CH3 – CH = CH2 + HBr ¾
¾® CH3— CH —CH2
(Prop - 1- ene) (2 - Bromopropane)
In the presence of peroxide, in gas phase and at high temperature the above reaction
follows Anti-Markownikoff's rule.
H Br
Peroxide
CH3 – CH = CH2 + HBr ¾ ¾¾¾® CH3— CH — CH2
(Prop - 1- ene) (2 - Bromopropane)
3. From Alcohols :
(i) By the action of halogen acids :
Alkyl bromides and iodides are prepared by the action of corrosponding halogen halide
(HBr, HI) on the alcohol. Alkyl chlorides can be prepared by the action of concentrated HCl
in the presence of anhydrous zine chloride.
R – OH + HX ZnCl2 R— X + H2O
¾¾ ¾¾®
(Alcohol) (Alkylhalide)
For example :
CH3OH + HBr ZnCl2 CH3Br + H2O

¾¾ ¾¾®
(Methylalcohol) (Methylbromide)
Order of reactivity of different alcohols in this reaction is
Tertiary > Secondary > Primary
Thus tertiary alcohol form tertiary alkyl chloride even in the absence of anhydrous
ZnCl2 in cold.
CH3 CH3
CH3— C — OH + HCl ¾
¾® CH3 — C — Cl + H2O
CH3 CH3
(tert-butyl alcohol) (tert-butyl chloride)
(ii) By the action of phosphorus halides :
Alkyl halides can be prepared by the action of phosphorus halides i.e. PX 5 or PX3 on
alcohols.
R – OH PX5 or PX3 R–X
¾¾¾¾¾¾®
For example :
CH3 – CH2 – OH + PCl5 ¾
¾® CH3 – CH2 – Cl + POCl3 + HCl
3 CH3 – CH2 – OH + PCl3 ¾
¾® 3 CH3 – CH2 – Cl + H3PO3
Methyl iodide and ethyl iodide can be prepared in the laboratory by this method. PI 3
is prepared insitu by the action of Red P and I2 in corresponding alcohol.
P4 + 6I2 ¾RedP
¾¾® 4PI3
3 R – OH + PI3 ¾¾® 3R – I + H3PO3. (R = CH3 or C2H5)
ALCOHOL
IODINE
RED P
SODA LIME
WATER
ETHYL IODIDE
Fig. 14.1 Preparation of ethyl iodide.
(iii) By the action of thionyl chloride :

Alkyl chloride can be prepared by the action of thionyl chloride (SOCl 2) on alcohol in
the presence of pyridine.
Py
R – OH + SOCl2 ¾¾® R – Cl + SO2 + HCl
Py
CH3 – CH2 – OH + SOCl2 ¾¾® CH3 – CH2 – Cl + SO2 + HCl
4. From monocarboxylic acid (Hunsdiecker Reaction)

When silver salt of a carboxylic acid is treated with chlorine or bromine in carbon
tetrachloride solution, alkyl halides are obtained. This reaction is known as Hunsdiecker
reaction.
O
CH3 – C – OAg + Br2 ¾CCl
¾¾4 ® CH3Br + CO2 + AgBr.
(Silver acetate) (Methyl bromide)
14.6 PROPERTIES :
(A) Physical Properties :
(1) State : Lower alkyl halides like methyl chloride, methyl bromide and ethyl chloride
are gases while methyl iodide and rest of the lower members upto C 18 are colourless
liquids. Beyond C18 are odourless crystalline solids.
(2) Colour change : Alkyl iodides decompose even on exposure to light and therefore,
they turn brown on standing due to the liberation of iodine.
2RI ¾
¾® R – R + I2.
(3) Solubility : Alkyl halides are slightly polar, but they are insoluble in water. They
are soluble in organic solvents like alcohol, ether, benzene etc.
This is because, alkyl halides fail to form hydrogen bonds with water and can not
break the hydrogen bonds already existing between water molecules.
(4) Density : Alkyl bromide and iodides are heavier than water, while chlorides are
lighter than water.
(5) Melting Point and Boiling point : Alkyl halides have boiling points higher than
the corresponding hydrocarbons. In general, boiling points rise with the increase
of molecular mass and decrease of branching of alkyl group. Boiling points of
alkyl halides are in the order,
RI > RBr > RCl
Their high boiling points are due to two types of inter molecular forces, i.e. dipole-
dipole attractions and van der Walls forces, which are stronger in them compared
to parent hydrocarbons.
Examples :
(i) Compound : CH3Cl CH3CH2Cl CH3(CH2)2Cl
b.p (K) 249 285.5 320
(ii) Compound : CH3I CH3Br CH3Cl CH3F
b.p (K) 315 277 249 195
(B) Chemical Properties :
Since alkyl halides are polar compounds, the more electronegative halogen atom
withdraws the shared pair of electrons of carbon-halogen covalent bond towards itself, thereby
increasing the electron density around the halogen atoms and acquiring a partial negative
charge. The carbon atom becomes electron deficient and acquires a partial positive charge.
— Cd+ — Xd–
The polarity in carbon-halogen bond produces dipole moment. Some of the important
chemical properties of alkyl halides are given below.
1. Reduction :
Alkyl halides when treated with reducing agents such as Zn – Cu couple and ethanol,
Sn / HCl, LiAlH4, hydrogen in the presence of Pd, sodium in ethanol, sodium amalgam and
water, Zn / HCl etc. are converted into their corrosponding alkanes.
R – X + 2H ¾
¾® R– H + HX
Alkyl iodide may be reduced to alkane with HI and Red P at 1500C.
Red P.
R – I + HI ¾ ¾¾ ¾® R – H + I
1500 C 2
2. Elimination Reaction :
Alkyl halides undergo elimination reaction to form alkenes with the removal of a
molecule of hydrogen halide. During dehydrohalogenation, hydrogen and halogen atoms are
eliminated from two adjacent carbon atoms.
The order of elimination reaction is
Tertiary halides > Secondary halides > Primary halides.
Alkyl halides on boiling with alcoholic KOH produce alkenes.
H X
R – CH – CH2 ¾Alcoholic
¾¾¾¾ KOH
¾¾® R – CH = CH2 + KX + H2O
For example :
CH3 – CH2 – CH2 – Br. ¾Alcoholic
¾¾¾¾ KOH
¾¾® CH3 – CH = CH2 + KBr + H2O
(1 - Bromopropane) (Propene)
When approached by a strong base, haloalkane loses a proton from the b-carbon atom
and halogen atom from µ-carbon atom, which is often called as b-elimination.
B –: H H B....H H H
—
—
—
—
R—C—C—H Slow R—C—C—H Fast R—C = C—H

—
—
—
—
H X H X H
Nucleophilic Substitution Reactions :

Substitution reaction involves replacement of one functional group by another. Here
halogen (X) is replaced by another group (Y)
R–X+Y ¾
¾® R – Y + X
Electron rich reagents are called nucleophilic reagents and the substitution reaction
with those reagents are called nucleophilic substitution reaction.
Here in case of alkyl halide, halide ion (X–) is an extremely weak base. The reagents
which are more basic than the halogen atoms can attack the positively charged carbon and can
easily displace the halogens as halide ions.
Nucleophilic substitution reaction is abbreviated as S N. According to the number of
reacting species, participating in the rate determining step of a particular reaction, the S N
reaction maybe distinguished as SN1, SN2 , where 1 and 2 stands for unimolecular and bimolecular
respectively.
A wide variety of organic compounds can be prepared by the nucleophilic substitution

reaction in alkyl halides. Some of them are given below.
Mechanism : There are two mechanisms, through which this reaction is found to
proceed. (i) SN2 mechanism (ii) SN1 mechanism.
(i) SN2 mechanism : In this case, the reaction involves both the substrate (alkylhalide)
and the nucleophile in the rate determing step and follows a concerted mechanism
where the departure of the leaving group is assisted by the incoming nucleophile.
Rate = k [alkyl halide] [nucleophile]
Example :
HO + CH3 – Br ¾
¾® CH3 – OH + Br:
In SN2 reaction, the nucleophile attacks the substrate from the back side, i.e. the side
opposite to the leaving group.
H H H
d- d-
HO: + C — Br HO C Br HO — C + Br:
H
H H H H
H
Reactants Reactantsstate
Transition Products
As the nucleophile attacks from the backside, the configuration of the product relative
to reactant is inverted, exactly like an umbrella in a gale. This change in configuration
is called as 'inversion of configuration' or Walden inversion.
(ii) SN1 mechanism : This type of reaction involves only the substrate (alkyl halide) in the
rate determining step, where the bond between carbon and the leaving group breaks
forming a carbocation.
Rate = k [alkyl halide]
Example : (CH3)3 C – Br + OH– ® (CH3)3 C – OH + Br
SN1 reaction takes place in two steps. The first step involves the ionization of C–Br
bond to form a 3° carbocation intermediate.
CH3 CH3
—
Slow
CH3 — C — Br CH3 — C Å + : Br
Step-1 :
—
CH3 CH3
(tert-Butyl bromide)
Step-2 : In the 2nd step, the carbocation is attacked by the nucleophile.
CH3 CH3
—
—
( –)
Fast
CH3 — C Å + :OH CH3 — C — OH
—
—
CH3 CH3
tert-Butyl alcohol
Due to the high stability of tertiary carbocation, the order of reactivity for S N1 reaction is :
Tertiary halide > Secondary halide > Primary halide
(a) Substitution by hydroxyl group :
Alkyl halides when treated with aqueous KOH or moist Ag 2O, are hydrolysed
to alcohols
R – X + KOH (aq) ¾
¾® R – OH + KX
i.e. CH3 – CH2 – Br + KOH(aq) ¾

¾® CH3 – CH2 – OH + KBr..
(Ethylbromide) (Ethyl alcohol)
CH3Br + AgOH ¾ ¾® CH3OH + AgBr.

(Methyl moist (Methyl alcohol)
bromide) silver oxide
(b) Substitution by alkoxy group :

Alkyl halides on treatment with metal alkoxides (RO –Na+) produce ethers. This method
of preparation of ethers is known as Williamson synthesis.
R–X + R1O–Na+ ¾ ¾® R – O – R1 + NaX
(Alkyl halide) (Sodium alkoxide) (Ether)
CH3CH2I + CH3CH2ONa ¾
¾® CH3–CH2–O–CH2–CH3+NaI.
(Ethyl iodide) (Sodium ethoxide) (Diethyl ether)
The reaction of alkyl halide with dry silver oxide (Ag 2O) also results in the formation
of an ether.
2RX + Ag2O ¾
¾® R – O – R + 2AgX
2CH3Cl + Ag2O ¾
¾® CH3 – O – CH3 + 2AgCl
(Methyl chloride) (Silver oxide) (Dimethyl ether)
(c) Substitution by cyanide group :
When alkyl halides are heated with aqueous or alcoholic KCN, alkyl cyanides are
formed. This involves the nucleophilic attack of CN – on alkyl halide.
R – X + K+CN– ¾
¾® R – CN + KX
Alkyl halide Alkyl cyanide or acid nitrile
CH3 – CH2 – I + KCN ¾
¾® CH3 – CH2 – CN + KI
(Ethyliodide) (Ethyl cyanide)
O
partial
¾ ¾¾¾¾¾¾ ¾® R—C—NH2
hydrolysis (H 2O)
(alk. H 2 O2 )
(Amide)
O
hydrolysis +
¾ ¾¾¾¾¾¾ ¾® R—C—OH + NH4
2H 2O (dil HCl)
(Acid)
Na / Ethanol or
R—C º N H 2 / Pt
Reduction
¾ ¾¾¾¾¾¾ ¾® R—CH2 —NH2
4H
(Primary amine)
SnCl 2 / HCl
¾ ¾¾¾¾¾¾¾® R—CH = NH.HCl ¾ ¾¾
2 ® H O
R —CHO + NH4Cl
+2H
Since the conversion of an alkyl halide into alkyl cyanide, involves addition of one
carbon atom into the molecule, it affords a means of ascending a homologous series i.e. the
conversion of lower member into a higher member.
Substitution of isocyanide group :
Alkyl halides when treated with aqueous alcoholic silver cyanide, form alkyl isocyanides.
¾® R – N = C
®
R–X + AgCN ¾ + AgX.
(Alkyl halide) (silver cyanide) (Alkyl isocyanide)
CH3 – CH2 – I + AgCN ¾
¾® CH3 – CH2 – NC + AgI.
(Ethyl iodide) (Ethyl isocyanide)
Isocyanides on hydrolysis give primary amines and formic acid and on reduction give
secondary amines.
O
hydrolysis
¾ ¾¾¾¾¾¾ ¾® R—NH2 + H—C—OH
2H 2 O
(Primary amine) (Formic acid)
R—N ®
= C
Reduction
¾ ¾¾¾¾¾¾ ¾® R—NH — CH3
4H (Secondary amine)
(d) Substitution by nitro group :

Alkyl halides when treated with alcoholic solution of silver nitrite, nitroalkanes are
formed. When alkyl halides are treated with alcoholic solution of potassium nitrite (KNO 2),
alkyl nitrites (ester) are formed.
R–X + AgNO2 ¾
¾® R – NO2 + AgX
(Nitroalkane)
C2H5-I + AgNO2 ¾
¾® C2H5 – NO2 + AgI.
(ethyl iodide) (Nitroethane)
R–X+K–O–N=O ¾Heat
¾¾® R – O – N = O + KX
alc.soln
(alkyl nitrite)
Heat
CH3 CH2 Br + K – O – N = O ¾ ¾¾®
alc.soln CH3CH2 – O – N = O + KBr
(Ethyl bromide) (Ethyl nitrite)
[Note : It must be remembered that reaction with alcoholic solution of AgNO 2 gives
+ O
nitroalkane, R—N whereas alcoholic solution of KNO2 gives an ester, nitrite,
O
R–O–N = O. as the major product]
(e) Substitution by amino group :

Alkyl halides when treated with ethanolic ammonia under pressure, give primary
amines.
R – X + H – NH2(alc) ¾
¾® R – NH2 + HX
(Alkyl halide) (Primary amine)
CH2 – CH2 – I + NH3(alc) ¾¾® CH3 – CH2 – NH2 + HI
(Ethylamine)
If excess of alkyl halide is used, the reaction continues to form a mixture of secondary
amine, tertiary amine and finally quatenary ammonium salt.
C2H5I + C2H5NH2 ¾
¾® (C2H5)2 NH + HI
(Diethylamine)
C2H5I + (C2H5)2 NH ¾
¾® (C2H5)3 N + HI
(triethylamine)
¾
¾® (C2H5)4 N I
+ –
C2H5I + (C2H5)3N
(Tetraethyl ammonium iodide)
(Quaternary ammonum salt)
4. Reactions with metals : Alkyl halides react with a number of metals to form
organometallic compounds.
(a) Reaction with magnesium :
Alkyl halides react with magnesium in dry ether solution to form Grignard reagents
(alkyl magnesium halides)
dry Ether
R – X + Mg ¾¾¾¾
¾® R – Mg – X
(Alkyl magnesium halide)
For example :
CH3– CH2 – Br + Mg ¾dry
¾¾¾
Ether
¾® CH3CH2MgBr
(Ethyl bromide) (Ethyl magnesium bromide)
(b) Reaction with sodium :
Alkyl halides when heated with metallic sodium, in dry ether, higher alkanes are
obtained. The above reaction in known as Wurtz reaction.
dry ether
R – X + 2Na + X –R ¾ ¾¾¾ ¾® R – R + 2NaX.
heat
dry ether
CH3 – I + 2Na + I – CH3 ¾ ¾¾¾
heat
¾® CH3 – CH3 + 2NaI.
(Methyl iodide) (Ethane)

(c) Reaction with lead-sodium alloy :
Alkyl halides when treated with lead–sodium alloy, form tetraalkyllead.
For example :
4C2H5Cl + 4Pb(Na) ¾
¾® (C2H5)4 Pb. + 4NaCl + 3 Pb.
Sodium– lead alloy Tetraethyl lead
(TEL)
Tetraethyl lead (TEL) was used as an antiknocking compound in petrol. Due to air
pollution by lead, TEL is no more used in petrol (unleaded petrol)
(5) Alkylation of Aromatic hydrocarbons :
Alkyl halide when treated with benzene in the presence of anhydrous aluminium chloride,
alkyl benzenes are formed. This reaction is known as Friedel Craft's reaction.
R–X + C6H6 ¾Anh.AlCl
¾¾¾¾3 ® C6H5 – R + HX
(Alkyl halide) (Benzene) (Alkyl benzene)
CH3Cl + C6H6 ¾Anh.AlCl

¾¾¾¾3® C6H5 – CH3 + HCl
(Methyl chloride) (Benzene) (Methyl benzene)
or Toluene)
CHAPTER (14) AT A GLANCE - HALOALKANES

General molecular formula : R–X , X = F, Cl, Br or I
A. Preparation of alkyl halide
X
1. R–H ¾ ¾2 ® R – X + HX
hn
(Alkane)
H X
HX
2. C=C ¾¾
¾® C C
(Alkene)
3. R – OH HBr
¾ ¾¾¾¾¾
¾® R – Br + H O
2
(Alcohol)HCl / ZnCl2
¾ ¾¾¾¾¾
¾® R – Cl + H O
2
R – OH ® PX / PX
¾ ¾¾¾¾¾
5 3
¾® R – X
(Alcohol) SOCl2
¾ ¾¾¾¾¾
¾® R – Cl
Red P4 / I2
¾ ¾¾¾¾¾
¾® R – I. + H3PO3
O
Br2
4. R — C – O – Ag ¾ ¾
¾® R – Br + CO2 + AgBr
(Silver salt of acid)
B. Properties of Alkyl halides :
Reduction
¾ ¾¾¾¾¾¾¾¾¾® R – H (Alkane)
Elimination Reaction
(Alc.KOH)
¾ ¾¾¾¾¾¾¾¾¾® Alkene
Aqueous KOH.
¾ ¾¾¾¾¾¾¾¾¾® R – OH (Alcohol)
RONa or Ag2O moist
¾ ¾¾¾¾¾¾¾¾ ¾® R – O – R (Ether)
KCN
¾ ¾¾¾¾¾¾¾¾¾® R – C º N (Alkyl cyanide)
AgCN
¾ ¾¾¾¾¾¾¾¾¾® R – N ® C (Alkyl isocyanide)
R—X¾¾® AgNO2
¾ ¾¾¾¾¾¾¾¾¾® R – NO2 (Nitroalkane)
KNO2
¾ ¾¾¾¾¾¾¾¾¾® R – O – N = O (Alkylnitrite)
NH3
¾ ¾¾¾¾¾¾¾¾ ¾® R – NH2 (Primary amine)
R/COOAg
¾ ¾¾¾¾¾¾¾¾¾® R – COOR /
(Ester)
Mg in dry ether
¾ ¾¾¾¾¾¾¾¾¾® R – Mg – X (Grignard reagent)
Na in dry ether
¾ ¾¾¾¾¾¾¾¾¾® R – R (Higher alkane)
Pb(Na)
¾ ¾¾¾¾¾¾¾¾¾® (R)4Pb (tetraalkyl lead)
C6H6 / Anh. AlCl3
¾ ¾¾¾¾¾¾¾¾¾® C6H5 – R (Alkyl benzene)
QUESTIONS
(A) Short Questions (One mark each)
1. In methyl chloride molecule there are – bonds.
[4 sigma, 3 sigma and one pi, 2 sigma 2 pi; 3 sigma and 2 pi]
2. What happens when chloroform is boiled with aqueous solution of caustic potash ?
3. Write the name of the monomer of teflon.
4. What organic compound is obtained when ethyl bromide reacts with aqueous NaOH
solution ?
5. Write the graphic formula of acid halide.
(B) Short Questions (two marks each)

1. What happens when methyl iodide in treated with metallic zinc ? [CHSE 1987 A]
2. Write with equation, what happens when ethyl iodide is boiled with aqueous alkali ?
3. How will you prepare ethyl amine from ethyl iodide ?
4. Give equation for the reaction of ethyl iodide with equeous and alcoholic potassium
hydroxide.
5. What happens when ethyl bromide is treated with alcoholic KOH ?
6. What happens when methyl iodide reacts with sodium methoxide ?
7. What happens when ethyl iodide is heated with sodium in dry ethereal solution ? Give
equation.
8. How can you get ethyl chloride from ethyl alcohol ? Give equation.
9. How would you distinguish between C6H5Cl and C6H5CH2Cl ?
10. Write all the possible structural formulae and give IUPAC names of the isomers of
C4H9Br, C5H11Br and C3H7Cl.
11. Write the reaction of preparing an alkyl chloride using sulphuryl chloride as halogenating
agent.
12. Write balanced equation for the reaction of methyl iodide with AgOH, C 2H5ONa,
CH3COOAg and AgNO2.
13. Using bromoethane how will you obtain diethyl ether and ethyl amine ?
14. What happens when : (Give equations)
(i) Silver acetate is treated with bromine.
(ii) Ethyl alcohol reacts with iodine in the presence of caustic alkali.
15. (i) Ethyl alcohol is treated with PCl5.
(ii) Ethyl iodide in treated with dry silver oxide.
(C) Short Questions (three marks each)

1. Complete the following equation :
(i) CH3I + AgCN ¾¾®
(ii) CH3I + NH3 ¾¾®
(iii) CH3 CH2CH2Br + KOH (alc) —— + —— + H2O [CHSE, 2002 IR]
(iv) CH3I + KOH(aq) ¾¾®
2. Explain why ?
(i) Although alkyl halides are slightly polar, they are insoluble in water.
(ii) Alkyl halides have higher boiling points than the corresponding hydrocarbons.
3. Explain why?
For a given alkyl group, the order of boiling point is
(i) RI > RBr > RCl > RF.
(ii) For a given alkyl group, the order of reactivity is
RI > RBr > RCl > RF.
4. Explain why?
(i) Alkyl halides undergo nucleophilic substitution reaction.
(ii) Dipole moment of carbon tetrachloride is zero.
(iii) A small amount of alcohol is usually added to chloroform bottle.
5. Explain why?
(i) Alkyl halide of lower alkanes when treated with metallic sodium give higher
alkanes.
(ii) Hydrogen atom of chloroform is definitely acidic but that of methane is not.
(iii) An alkyl halide can be utilised for the synthesis of a desired aliphatic compound.
6. Identify A, B and C in the following reaction sequence.
(i) A ¾PCl
¾¾5® B ¾alc.KOH
¾¾¾¾® C ¾H
¾¾2 /Ni
¾® CH3CH2CH3
(ii) A ¾KCN
¾¾® B ¾4H
¾¾® CH3CH2CH2NH2
(iii) A ¾alc.KOH
¾¾¾¾® B ¾Cl
¾¾2 ® C ¾AgOH
¾ ¾¾® CH2OH – CH2OH
conc. H SO
C2H5OH ¾ ¾¾¾¾ ¾ ®
2 4
(iv) A ¾Br
¾¾2 ® B ¾alc.KOH
¾¾¾¾® C.
D
(v) C2H5I alc.KOH
¾ ¾¾¾¾® A ¾Br
¾¾2 ® B ¾KCN
¾¾® C.
(D) Long Questions : (7 marks each)

1. Describe the general method (only one) of preparation of an alkyl halide. How does it
react with ammonia, metallic sodium and dilute caustic potash.
2. Write notes on
(a) Iodoform reaction
(b) Williamson synthesis.
3. What are halogen derivatives ? How are they classified ?
4. How ethyl bromide is prepared from ethyl alcohol ?
How will you obtain the following compounds from it ?
(i) Ethane (ii) ethene (iii) ethyl methyl ether (iv) ethyl amine.
5. How will you obtain the ethyl bromide from ethylene ?
How does ethyl bromide react with sodium, aqueous KOH, alcoholic KOH and silver
nitrite ?
6. What are the main products formed, when ethyl bromide reacts with KCN, AgCN, KI
in acetone, AgNO2, KNO2, aq.KOH and alcoholic KOH ? Give equations.
7. Explain with equation, how alkyl halide can be prepared from alcohols. What happens
when the following substances react with ethyl chloride ?
(a) CH3ONa (b) Na (c) Alcoholic KOH

1. Ethyl iodide reacts with sodium ethoxide to produce
(a) Butane (b) Acetic acid
(c) Diethyl ether (d) Ethane
2. When alkyl halide is treated with alcoholic KOH, the compound formed is
(a) Alkane (b) Alkene
(c) Alcohol (d) Ether
3. Which of the following is known as freon :
(a) CCl2F2 (b) CHCl3
(c) CH2F2 (d) CF4.
4. Which of the following is optically active ?
(a) CH3CHCl2 (b) CH3CH2CHClCH3
(c) CH3CH2Cl (d) CH2ClCH2Cl
5. Which of the following will not give iodoform reaction
(a) Acetaldehyde (b) Acetone
(c) Ethyl alcohol (d) Methyl alcohol.
6. Which of the following reaction provides an example of nucleophilic substitution of an
alkyl halide (RX).
(a) RX + Mg ¾
¾® RMgX (b) RX + 2H ¾
¾® RH + HX
(c) RX + KOH ¾
¾® ROH + KX (d) 2RX + Na ¾
¾® R – R + 2NaX
7. The reagent required to convert CH3I to CH4 is

(a) Zn – Cu couple and ethanol (b) Magnesium in ether.
(c) Sodium methoxide (d) Sodium in ether.
8. For a given alcohol the order of reactivity with halogen acid is
(a) HI > HCl > HBr. (b) HCl > HI > HBr
(c) HCl > HBr > HI (d) HI > HBr > HCl
9. The compound with zero dipole moment is
(a) CH3Cl (b) CH2Cl2
(c) CCl4 (d) CHCl3
10. IUPAC name of the compound having formula (CH3)3 CCl is
(a) t-butyl chloride (b) Isobutyl chloride
(c) 2-Methyl - 2 - chloropropane (d) n-butyl chloride
11. Alkyl halides react with alcoholic KOH to give
(a) Alkene (b) Alkane
(c) Alcohol (d) ether.
12. CH2Cl2 is the formula of
(a) Methylene chloride (b) Methyl chloride
(c) Ethyl chloride (d) Dichloroethylene.
13. When ethylene dibromide reacts with alcoholic KOH we get,
(a) C2H4 (b) C2H2
(c) C3H6 (d) C2H6
14. Which of the following compound is used as refrigerant ?
(a) Chloroform (b) Carbon tetrachloride
(c) Dichlorodifluoromethane (d) Carbontetrafluoride
15. Which of the following is optically active
(a) CH3CH2OH (b) CH2OH . CHOH .CH2OH
(c) CH3CHOHC2H5 (d) CCl2F2
ANSWERS TO
1. (c), 2. (b), 3. (a), 4. (b), 5. (d), 6. (c),

7. (a) 8. (d), 9. (c), 10. (c), 11. (a), 12 (a),
13. (b), 14. (c) 15. (c).
qqq
HALOARENES (ARYL HALIDES)

Aromatic halogen compounds are obtained by replacement of one or more hydrogen
atoms of an aromatic hydrocarbon by an equal number of halogen atoms. These have been further
classified into the following categories.
(i) Nuclear halogen derivatives : Halogen derivatives of aromatic hydrocarbons in
which the halogen atom
(F, Cl, Br, or I) is directly attached to an aromatic ring are called aryl halides.
Their general formula is Ar-X where Ar (short name for aryl) represents a phenyl, a
substituted phenyl, naphthyl, etc. Some examples of aryl halides are :
F Cl CH3 CH3
I
Br
Fluorobenzene Chlorobenzene 1-Bromo-4-methylbenzene 1-lodo-2methylbenzene
or 4-Bromotoluene or 2-Iodotoluene
(p-Bromotoluene) (o-lodotoluene)
(ii) Side chain halogen derivatives : Halogen derivatives of aromatic hydrocarbons in

which the halogen atom is linked to one of the carbon atoms of the side chain carrying the aryl
group are called arylalkyl (aralkyl) halides. For example,
CH2Cl CHCl2
Benzylchloride Benzal dichloride

(1-Chloro-1-phenylmethane) (1,1-Dichloride- 1-phenylmethane)
2 1
CHCl3 CH2– CH2 – Br
Benzotrichloride p-Phenylethyl bromide

(1,1,1-Trichloro - 1-phenylmethane (1-Bromo-2-phenylethane)
Like alkyl halides, arylalkyl halides are very reactive and thus undergo a number of
substitution reactions. On the other hand, aryl halides are less reactive and thus undergo only a
few substitution reactions that too, under drastic conditions.
14.7 NOMENCLATURE OF HALOGEN COMPOUNDS :

Haloarenes have the common as well as IUPAC names . For dihalogen derivatives, the
prefixes o-, m-, p- are used in the common system but in the IUPAC system, numerical prefixes
1, 2, 1, 3 and 1, 4 are respectively used. In case the parent aromatic hydrocarbon carries a side
chain or substituent, then the numbering of the carbon atoms of the ring begins with the substituent
and in case the parent hydrocarbon is benzene, then the numbering begins with the halogen atom.
However, polyhalogen derivatives do not have common names, but only have IUPAC names in
which the positions of halogens are indicated by arabic numerals. For example,
Cl CH3 CH3
2 Cl 3
2
1 1
Cl
Chlorobenzene o-Chlorotoluene m-Chlorotolune
(Chlorobenzene) (1-Chloro-2-methylbenzene (1-Chloro-3-mehylbenzene
or 2-Chlorotoluene) or 3- Chlorotoluene)
CH3 Br Br
4 1 2 Br
3
2
1
Cl
p-Chlorotoluene Bromobenzene o-Dibromobenzene
(1-chloro-4-methyl-benzene (Bromobenzene) (1,2,Dibromobenzene)
or 4-chlorotoluene)
Br Br
1 1
2 2
3 5 3
4 Br 4
Br
m-Dibromobenzene p-Dibromobenzene
(1,3-Dibromobenzene) (1,4-Dibromobenzene)
Br Br
1 1
2 2
3 5
3
4 Cl Br 4 Br
1-Bromo -3-chlorobenzene 1,3,5 - Tribromobenzene
14.8 METHODS OF PREPARATION OF HALOARENES :

1. From aromatic hydrocarbons by direct halogenation.
(a) Nuclear halogenation : Chloroarenes (aryl chlorides) and bromoarenes (aryl bromides)
can be easily prepared by direct chlorination or bromination of aromatic hydrocarbons. The
reaction is usually carried out at low temperature (310-320K), in the absence of sunlight
and in the presence of a Lewis acid such as anhydrous ferric or aluminium halide as catalyst.
Cl
Anh. FeCl3 or
+ Cl2 Anh. AlCl3 + HCl
310-320 K
Chlorobenzene
Br
Anh. FeBr3
+ Br2 + HBr
310-320 K
Bromobenzene
If excess of halogen is used - a second atom of halogen is introduced in the ring mainly at
o- and p- positions with respect to the first since halogens are o, p- directing.
Cl Cl Cl
Cl
+ Cl2 Anh. FeCl3 +
Cl
Chlorobenzene o-Dichlorobenzene (minor) p- Dichlorobenzene (major)
Similarly, further bromination with excess of bromine in presence of anhyd. FeBr 3 gives a
mixture of o-dibromobenzene (minor) and p-dibromobenzene (major).
If toluene is used instead of benzene, a mixture of o- and p- chlorotoluene is obtained since
CH3 group is o, p - directing.
CH3 CH3 CH3

Cl
+ Cl2 Anh. FeCl 3 +
Cl
Toluene o-chlorotoluene (minor) p-chlorotoluene (major)
Similarly, bromination of toluene with Br 2 in presence of anhydrous FeBr3 gives a mixture

of o-bromotoluene (minor) and p-bromotoluene (major)
The direct iodination of aromatic hydrocarbons is not so useful since HI produced during
the reaction, being a good reducing agent reduces the aryl iodide back to the aromatic hydrocarbon
and iodine.
I
+ I2 + HI
Benzene Iodine Iodobenzene

However, in the presence of oxiding agents such as nitric acid, iodic acid (HIO 3), mercuric
oxide etc. the HI produced is either oxidised to iodine or eliminated as mercuric iodide and thus
the reaction proceeds in the forward direction producing iodobenzene.
2HI + 2HNO3 2NO2 + 2H2O + I2
5HI + HIO3 3I2 + 3H2O
HgO + 2HI HgI2 + H2O
Fluoroarenes (aryl fluorides), however, cannot be prepared by direct fluorination of aromatic
hydrocarbons since the reaction is violent and cannot be easily controlled.
(b) Side chain halogenation : The most convenient method for the preparation of side
chain substituted aryl halides or aralkyl halides is by the direct halogenation of a suitable arene.
For example, when chlorine is passed through boiling toluene in presence of sunlight and absence
of halogen carrier, phenylchloromethane (benzyl chloride) is formed.
CH2Cl
CH3
383 K
+ Cl2 + HCl
Sunlight
(Phenylchloromethane)
If Cl2 is passed for a longer time, the initially formed benzyl chloride reacts further to form
first benzal dichloride and then benzotrichloride.
CH2C1 CHC12 CC13
+ Cl2 383 K, hn Cl2, 383 K, h n

-HCl -HCl
Benzyl chloride Benzal dichloride Benzotrichloride
When the side chain is larger than a methyl group, side chain halogenation preferentially
occurs at the benzylic carbon (i.e. carbon atom next to the benzene ring) and the process is called
benzylic halogenation. For example,
Cl Cl
CH2 – CH3 CH – CH3 Cl – C– CH3
Cl2 , hn Cl2 , h n
273 K 273 K
1-chloro-1-phenylethane 1,1 - Dichloro - 1- phenylethane

Instead of Cl2, sulphuryl chloride (SO2Cl2) at 475 K in presence of light and traces of
peroxide can also be used for benzylic halogenation of arenes. For example,
475 K, h n
C6H5CH3 + SO2Cl2 C6H5 – CH2Cl + SO2 + HCl
traces of peroxide
2. From diazonium salts.
(i) By Sandmeyer reaction - Chloroarenes (aryl chlorides) and bromoarenes (aryl bromides)
are easily prepared when the diazonium salts are treated with CuCl dissolved in HCl or CuBr
dissolved in HBr. This reaction is called Sandmeyer reaction.
+
N NCl Cl
CuCl / HCl
+ N2 + Cl–
(Sandmeyer reaction)
Benzene diazonium chloride
+
N NCl Br
CuBr / HBr
+ N2 + Cl–
(Sandmeyer reaction)
Benzenediazonium chloride Bromobenzene
However, iodoarenes (aryl iodides) are prepared by simply warming the diazomium salt
solution with aqueous KI solution.
+
N NCl I
+ KI (aq) warm + N2 + KCl
Benzenediazonium Iodobenzene
chloride
Benzenediazonium chloride needed for this purpose is obtained by treating aniline
dissolved in dil. HCl with an aqueous solution of sodium nitrite at 273 – 278 K (0 0 - 50C).
NaNO2 + HCl (dil) HONO + NaCl
+
NH2 N NCl
+ HONO + HCl 273-278K + 2H2O
Aniline Benzenediazonium
chloride
Fluoroarenes (aryl fluorides) are prepared by heating the corresponding diazonium
tetrafluoroborate which, in turn are obtained by the diazotisation of suitable aromatic primary
amine with aq NaNO2 in presence of fluoroboric acid (HBF4) at 273 – 278 K.
+
NH2 N NBF4 F
NaNO2 / HBF4
+ N2 + BF3
273-278K
Aniline Fluorobenzene Boron trifluoride

This reaction is called Balz-Schiemann reaction.
(ii) By Gattermann reaction - Haloarenes particularly chloro - and bromoarenes can also
be prepared by Gattermann reaction. It is a modification of Sandmeyer reaction. In this reaction,
a mixture of freshly prepared copper powder in the presence of corresponding halogen acid (HCl
or HBr) is used instead of cuprous halide dissolved in the corresponding halogen acid (CuCl /
HCl or CuBr / HBr) as used in Sandmeyer reaction. The yields are often around 40%.
+
Cl N NCl Br
Cu/HCl Cu/HBr
N2 + + N2
Chlorobenzene Bromobenzene
3. From silver salt of aromatic acids (Hunsdiecker reaction). Like alkyl bromides, aryl
bromides can also be prepared by refluxing the silver salt of aromatic acids with bromine in
boiling carbon tetrachloride.
COOAg Br
+ Br2 CCl 4, Reflux + CO2 + AgBr
Silver benzoate Bromobenzene

4. Commercial preparation Chlorobenzene.
Chlorobenzene is prepared commercially by the Raschig process. In this process, a mixture
of benzene vapours, air and hydrogen chloride is passed over heated cupric chloride.
2C6H6 + 2HCl + O2 CuCl 2 , 2C6H5Cl + 2H2O

14.9 PROPERTIES :
Physical Properties
1. Aryl halides are colourless oily liquids or relatively low melting point solids, having
odour characteristic of aromatic compounds.
2. Because of their low polarity, they are insoluble in water but soluble in all common
organic solvents such as ethanol and diethylether.
3. They have density greater than one.
4. For the same aryl group, the melting points, boiling points and densities rise gradually as
we pass from fluoro to iodocompounds.
F Cl Br I
Haloalkanes
M.P.0C –42 –45 –31 –30

B.P.0C 85 132 156 188
Density 1.031 1.112 1.495 1.838
0
(g/ml at 20 C)
5. The boiling points of o-, m- and p- isomers are so close that these are difficult to separate
by distillation. However, the melting point of a p-isomer is much higher than that of o- or m-
isomer. This is so because the more symmetrical p-isomer fits more easily into a crystal lattice
and the stronger intercrystalline forces result in a higher melting point.
For example, the physical constnts of o-, m- and p- isomers of dichlorobenzene are
Cl Cl Cl
Cl
Cl
ortho meta Cl
para
BPoC 179 172 175
MPoC –17 –26 –53
6. Since the strength of C – X bond decreases in the order C – F > C – Cl > C – Br > C – I,
therefore, stability of the haloarenes having the same aryl group decreases from fluoride to the
corresponding iodide.
7. Many haloarenes show physiological activity and are used as insecticides (DDT)
CHEMICAL PROPERTIES
1. Nucleophilic substitution of aromatic halogen.
Halogens attached to an aromatic ring do not ordinarily undergo displacement (S N1 or
SN2). Thus unlike alkyl halides, aryl halides do not react with nucleophilic reagents under normal
laboratory conditions.
CH3 – Cl + : Nu CH3 – Nu + Cl–
methyl chloride Product
Cl + : N u No Reaction
Chlorobenzene
The following reasons can be attributed to account for the low reactivity of aryl halides.
(i) Resonance effect. In haloarenes (e.g. chlorobenzene), the lone pairs of electrons on the
halogen atom are delocalized on the benzene ring as shown below :
..
.. .
..Cl +Cl .. .. .. .
..Cl d+
. +Cl .. .. . Cl
+Cl..
.. d– d–
..
.. d–
(a) As a result, C – Cl bond acquires some double bond character, i.e. Cl is attached to C by
little more than a single pair of electrons. On the other hand, in case of alkyl halides (say methyl
chloride) carbon is attached to chlorine by a pure single bond. Consequently, C – X bond in aryl
halides is little stronger than in alkyl halides, and hence cannot be easily broken.
(b) As discussed above, aryl halides are stabilised by resonance but alkyl halides are not.
Consequently, the energy of activation for the displacement of halogen from aryl halides is much
greater than that from alkyl halides. Thus aryl halides are much less reactive than alkyl halides
towards nucleophilic substitution reactions.
(ii) Difference in hybridization of carbon atom in C – X bond : In haloalkanes (e.g.

methyl chloride), the halogen is attached to sp 3-hybridized carbon while in haloarenes the halogen
is attached to sp2-hybridized carbon. Since a sp2- hybridized orbital is smaller in size as compared
to sp3 orbital of carbon, the C – Cl bond in chlorobenzene should be shorter and hence stronger
than in methyl chloride. This has been confirmed by the X-ray analysis which shows that the C –
O O
Cl bond in chlorobenzene in 169 pm (1.69 A )whereas in methyl chloride, it is 177pm (1.77 A ).
sp2
Cl Cl
o
1.77A
o C
1.69 A
H
H H
Thus, in chlorobenzene, C – Cl bond is stronger than in methyl chloride and hence difficult
to break.
(iii) Polarity (or Nature) of the carbon-halogen bond. Another reason for the low
reactivity of ary halides over alkyl halides is their lesser polar character.
d–
X d+ d–
d+ C X
Haloalkane or alkyl halide (C – X bond

Haloarene or arylhalide (C – X bond is is more polar than in aryl halides and
less polar and hence X cannot be hence X can be easily displaced by
displaced easily by nucleophiles) nucleophiles)
The sp2-hybrid carbon due to greater s-character is more electronegative than a sp 3 -hybrid
carbon. Therefore, the sp2-hybrid carbon of C – X bond in aryl halides has less tendency to
release electrons to halogen than in sp 3 – hybrid carbon in alkyl halides. As a result, the C – X
bond in aryl halides is less polar than in alkyl halides. This is supported by the observation that
the dipole moment of chlorobenzene is just 1.69 D as compared to the dipole moment of methyl
chloride, i.e. 1.86 D. Consequently, the halogen atom present in aryl halides cannot be easily
displaced by nucleophiles.
(iv) Instability of phenyl cation. In haloarenes the phenyl cation formed as a result of
self-ionization is not stabilized by resonance because the sp 2-hybridized orbital of carbon having
the +ve charge is perpendicular to the p-orbitals of the phenyl ring. Therefore, these cations are
not formed and aryl halide do not undergo nucleophilic substitution reactions easily.
Cl + + Cl
Chlorobenzene Phenyl cation

(v) Electronic repulsions. Since arene halides are electron rich molecules due to the presence
of p-bonds, they repel the electron rich nucleophiles from attacking them.
For the reasons stated above, the substitution of halogen in aryl halides by S N1 mechanism
is considerably more difficult than with alkyl halides. S N2 reactions are not possible because the
usual backside approach of the nucleophile is blocked by the aromatic ring in aryl halides. Hence,
simple aryl halides are ordinarily inert to most of the nucleophiles.
However, at sufficiently high temperature and pressure with nucleophiles e.g. hydroxide,
cyanide ion or ammonia, nucleophilic substitution can be carried out.
aq. NaOH
–
Cl + OH ONa + Cl
300,0pressure
Chlorobenzene Sodium phenoxide
ONa dil HCl

OH
Phenol
(This reaction forms the basis of Dow process for the manufacture of phenol.)
NaCN + CuCN
Cl + C ºN CN + Cl–
200,0 pressure
Phenyl cyanide
aq. NH 3
Cl + 2NH3 + Cu2O 0 NH2 + 2 CuCl + H2O
200, pressure
aniline
These reactions are used for the manufacture of the above derivatives. Because of the high
temperature and pressure required, they are unsuitable as laboratory methods of preparation.
Aryl halides undergo nucleophilic displacement with increasing readiness if a strongly
electron attracting group (– NO2, – C N) is present in the 2-position (ortho) or in 4-position
(para).
Cl OH
+ OH + Cl (55 % yield)
NO2 NO2
4- nitrochlorobenzene 4 - nitrophenol
Cl OH
NO2 NO2
+ OH + Cl (76% yield)
NO2 NO2
2,4 - dinitrochlorobenzene 2,4-dinitrophenol
When three nitro groups are placed in 2,4 and 6- positions to a halogen, the reactivity of the
latter is greatly increased and is comparable to that of alkyl halides.
Cl OH
O2N O2N NO2
NO2
+ H2O + HCl (93% yield)
NO2 NO2
2,4,6-Trinitrochlorobenzene 2,4,6 - Trinitrophenol
(Picryl chloride) (Picric acid)
MECHANISM
The preparation of phenol from chlorobenzene illustrate the reaction mechanisms of the
nucleophilic substitution of aryl halides. The reaction is believed to take place in two steps. In
first step a carbanion is formed by the nucleophilic attack of OH on the carbon carrying the
chlorine. This is a slow and rate determining step. In the second step which is fast, the halogen
leaves the carbanion and phenol is formed.
Cl OH OH
+ OH Slow Fast + Cl–
Chlorobenzene Carbanion Phenol

intermediate
The carbanion is stable as it could be represented as the resonance hybrid of the
following canonical forms.
Cl OH Cl OH Cl Cl
OH OH
Resonance hybrid
It will be noticed that the carbanion has small negative charges in ortho and para positions.
An electron - attracting group such as – NO2 group if present in ortho or para position to chlorine,
spreads the negative charge to the oxygen atom of the –NO 2 group through resonance.
Cl OH
Cl Cl OH
OH
+ OH Slow + Fast + Cl–

N
+ N+
N O NO 2
O O O
O O [A] p- nitrophenol
Thus the carbanion (A) is more stable than in case of hydrolysis of chlorobenzene because
of greater dispersion of the negative charge and the presence of – NO 2 group in para position.
Similar dispersion of the negative charge of the carbanion is also felt when the –NO 2 group is in
ortho position.
Hence the nucleophilic substitution with ortho and para nitrochlorobenzene is facilitated.
2. Electrophilic substitution reactions :
Haloarenes undergo the usual electrophilic substitution reactions of the benzene ring such
as halogenation, nitration, sulphonation and Friedel - Craft reactions. Halogen atom is slightly
deactivating and o, p - directing. Therefore, further substitution occurs at o - and p - positions
with respect to the halogen atom. The o- and p-directing influence of the halogen atom can be
easily understood if we consider the resonance structure of chlorobenzene. Chlorobenzene is to
be regarded as resonance hybrid of the four contributing forms shown below.
... ...
.. +
Cl.. +
Cl. + ..
..
..
Cl Cl
.
.. ..
I II III IV
In structures, II, III or IV , there is negative charge either at o – or p- positions. In other

words, because of resonance, the electron density increases more at o - and p-positions than at m-
positions. Therefore, further electrophilic substitution in haloarenes occurs at o - and p- positions.
However, because of steric hindrance at the o-position, the p-product usually predominates over
the o-product. Further, the halogen atoms because of its –I effect has some tendency to withdraw
electrons from the benzene ring. As a result, the ring gets somewhat deactivated as compared to
benzene and hence the electrophilic substitution reactions in haloarenes occur slowly and under
drastic conditions as compared to those in benzene.
(i) Halogenation
Cl Cl Cl
1 2 Cl 1
2
+ Cl2 Anh.FeCl3 + 3
4
Cl
Chlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene
(o-Dichlorobenzene) (p-Dichlorobenzene
(minor) (major)
(ii) Nitration
Cl Cl Cl
NO2 1
1 2
Conc.H2 SO 4
+ HNO3 +
(Conc.) 4
NO2
Chlorobenzene 1-Chloro-2-nitrobenzene 1-Chloro-4-nitrobenzene
(o-Chloronitrobenzene) (p-Chloronitrobenzene)
(minor) (major)
(iii) Sulphonation
Cl Cl Cl
2 SO3H 4
1
+ H2SO4 +
(Conc.) 1
SO3H
Chlorobenzene 2-Chlorobenzene 4-Chlorobenzene

sulphonic acid sulphonic acid
(minor) (major)
(iv) Friedel-Crafts reaction

Cl Cl Cl
1 CH3
Anh. AlCl3, 2
+ CH3 – Cl +
F.C. alkylation
4
CH3
Chlorobenzene 1-Chloro-2-methylbenzene 1-Chloro-4-methylbenzene
(o-Chlorotoluene) (p-Chlorotoluene)
(minor) (major)
Cl Cl Cl
O 2 COCH3 4
Anh. AlCl3, 1
+ CH3 – C – Cl +
F.C. Acylation
COCH3
Chlorobenzene acetyl chloride 2-Chloroacetophenone 4-Chloroacetophenone
(o-Chloroacetophenone) (p-Chloroacetophenone)
(minor) (major)
3. Miscellaneous reactions
Besides these nucleophilic and electrophilic substitution reactions, haloarenes undergo a
number of other reactions as described below :
(i) Reaction with sodium (a) Wurtz-Fittig reaction. Haloarenes when treated with an
ethereal solution of an alkyl halide in presence of sodium, form alkyl derivatives of benzene.
This reaction is called Wurtz-Fittig reaction
Dry ether
Br + 2Na + Br CH2CH3 CH2CH3 + 2NaBr
Bromobenzene Ethyl bromide Ethylbenzene

(b) Fittig reaction : When only haloarenes are treated with sodium, diaryls are produced.
This reaction is called Fittig reaction.
Dry ether
Cl+2Na+Cl + 2NaCl
Chlorobenzene Chlorobenzene Diphenyl

(ii) Reaction with copper powder - (Ullmann biaryl synthesis.) When an iodoarene is
heated with copper powder in a sealed tube, diaryl is formed. This is called Ullmann biaryl
synthesis.
I + 2Cu + I + 2Cul
Sealed tube
Iodobenzene Iodobenzene Diphenyl
(iii) Reaction with magnesium. Bromo-and iodoarenes form Grignard reagents when their
ethereal solution is treated with magnesium turnings. Chloroarenes form Grignard reagents only
if the reaction is carried out in dry tetrahydrofuran (THF) as solvent.
Dry ether
Br + Mg MgBr
Bromobenzene Phenylmagnesium bromide

Dry THF
Cl + Mg MgCl
Chlorobenzene Phenylmagnesium chloride

(iv) Reaction with lithium. Bromo- and iodoarenes also react with lithium metal in presence
of dry ether to form the corresponding organometallic compounds. For example,
Dry ether
Br + 2Li Li + LiBr
Bromobenzene Phenyllithium
(v) Reduction : Haloarenes can be converted into the corresponding arenes by reduction
with nickel-aluminium alloy in presence of alkali.
Cl
Ni-Al/NaOH
+ 2[H] + HCl
Chlorobenzene Benzene
Cl
14.10 CHLOROBENZENE, Phenyl chloride, C6H5Cl,
Preparation
The preparation and the industrial preparation of chlorobenzene have been discussed in
16.2.
Properties
Chlorobenzene is a colourless, pleasant smelling liquid, b.p. 132 0C. It is insoluble in water,
ethanol and ether. It is heavier than water, density 1.112 g/ml at 20 0C. It is steam-volatile.
Interpretation of its reactivity. The low reactivity of chlorobenzene towards nucleophilic
substitution as compared to alkyl halides is mainly attributed to two factors.
(a) delocalisation of electrons by resonance, and
(b) difference in the nature of C – X bond (sp3C – X and sp2C – X bonds)
(a) Let us look first at the resonance interpretation.
Chlorobenzene is considered to be a hybrid of not only the two Kekule structures I & II, but
also of three structures, III, IV and V, in which the chlorine is joined to carbon by a double bond.
In III, IV and V chlorine bears a positive charge and the ortho or para positions of the ring bear
a negative charge.
.. ..
.. Cl.. ..
.. Cl..
.. . . ..
.
+ Cl. + Cl. + Cl.
H H
.. ..
..
H
I II III IV V
Contribution from III, IV and V stabilizes the chlorobenzene molecule and gives double-
bond character to the carbon chlorine bond. Carbon and chlorine are thus held together by
something more than a single pair of electrons, and the carbon chlorine bond is stronger than if it
were a pure single bond. Moreover the chlorobenzene molecule is stabilised by the contribution
of all the resonating structures I to V and thus slow down the reactivity of the aryl halide.
(b) An alternative interpretation i.e. considering the nature of C – X bond is simple. In alkyl
halides the carbon holding halogen is sp3-hybridised. In aryl halides carbon is sp 2-hybridised, the
bond to halogen is shorter and stronger and the molecule is more stable and accounts for its low
reactivity.
Chlorobenzene gives all the reactions characterstic of aryl halides.
3000C
+ aqNaOH C6H5OH + NaCl
Pressure
Phenol
0
200 C
+ CuCN C6H5 – CN + CuCl
Pressure
Phenyl cyanide
0
Cl 200 C
+ aqNH3 C6H5 – NH2 + HCl
Pressure
Chlorobenzene aniline
+ CH3Cl + 2Na C6H5CH3 + 2NaCl
toluene
+ Mg THF C6H5 – MgCl
Phenylmagnesium chloride
+ Li ether C6H5 – Li
Ni-Al
+ 2H C6H6 + HCl
NaOH
benzene
+ Conc HNO3 (H2 SO4) Cl – C6H4 – NO2 + H2O

o- & p - nitrochlorobenzene
Uses : Chlorobenzene is used in the manufacture of phenol, aniline and DDT.
14.11 POLYHALOGEN COMPOUNDS :
1. DDT, 2, 2-di (p-chlorophenyl)-1, 1, 1 - trichloroethane

DDT was first prepared in 1873, but it was not until 1939 that Paul Muller, at Geigy
pharmaceutical in Switzerland, discovered the effectiveness of DDT as an insecticide. Paul Muller
was awarded the Nobel Prize in medicine and physiology in 1948 for this discovery.
Preparation : It is prepared by heating chlorobenzene with chloral (trichloroacetaldehyde)
in presence of conc. H2SO4.
Cl H Cl
Conc. H2 SO4
+ O = CH - CCl 3 CH - CCl 3+ HO2
Cl H Cl
Chlorobenzene Chloral DDT
Uses : DDT is a cheap but powerful insecticide. It is widely used for sugarcane and fodder
crops and to kill mosquitoes and other insects. It is particularly very effective against Anopheles
mosquitoes which spread malaria and lice that carry typhus. Through its use, malaria has virtually
been eliminated from India and large part of the world.
Tragic side effects : The use of DDT increased enormously on a worldwide basis after
World War II. However, problems related to extensive use of DDT began to appear in the late
1940s. Many species of insects developed resistance to DDT and DDT was also discovered to
have a high toxicity towards fish. The chemical stability of DDT and its fat solubility further
increased the problems. DDT is not completely biodegradable, i.e. it is not very rapidly metabolized
by animals. Instead, it gets deposited and stored in fatty tissues. If this ingestion continues at a
steady rate, DDT builds up within the animal over time. This affects the reproductive system of
animals. Because of these tragic side effects, the use of DDT was banned in USA in 1973. However,
in India and in many other Asian countries, DDT is still being widely used due to the non-
availability of any other cheaper insecticide.
2. Benzene Hexachloride :
In the presence of sunlight or ultraviolet light, chlorine and bromine (but not iodine), add to
benzene to give crystalline hexachlorides and hexabromides, C 6H6Cl6 and C6H6 Br6.
Cl
Cl Cl
hn
+ 3Cl2
300 - 4000C
Cl Cl
Cl
benzene hexachloride
Benzene hexachloride is known by the commercial name BHC or 666, derived from its
formula C 6 H 6 Cl 6 . As we look at its structure, this is also named as 1,2,3,4,5,6 -
hexachlorocyclohexane, and can theoretically exist in nine stereoisomeric forms due to different
arrangement of H and Cl on opposite sides of the plane of the benzene ring. Seven of these have
been isolated from the mixture obtained by the above procedure. The insecticidal properties are
due to one of the isomers i.e. g-isomer which is called Gammaxane or Lindane. It is very stable
and acts more quickly than DDT.
3. Trichloromethane or Chloroform, CHCl3

Chloroform was discovered by Leibig in 1831 and finds its use as a solvent for fats, waxes,
alkaloids, rubber, resins, iodine etc. Previously it was used as anaesthetic but due to its harmful
effects, has been replaced by less toxic, safer anaesthetics such as ether. Now-a-days, chloroform
is used for the production of freon refrigerant R-22.
Chloroform is prepared by distilling ethyl alcohol or acetone with bleaching powder and
water.
(i) Alcohol is first oxidised to acetaldehyde by chlorine, obtained from bleaching powder.
CH3CH2OH + O CH3CHO + H2O
(ii) Acetaldehyde, now reacts with chlorine forming trichloro acetaldehyde, called chloral.
CH3CHO + 3Cl2 CCl3CHO + 3HCl
Chloral
(iii) Chloral, then gets hydrolysed by calcium hydroxide.
Hydrolysis
2 CCl3CHO + Ca (OH)2 2 CHCl3 + (HCOO)2Ca
Chloroform Calcium formate
4. Tetrachloromethane or carbon tetrachloride, CCl4
It is the most useful tetrahalogen derivative of methane. Earlier, carbon tetrachloride was
used in industries as a cleaning agent and in the homes, as a spot remover and fire extinguisher
under the name pyrene. It is now used as a solvent for fats, oils, waxes and greases, resins, iodine
etc. Now. it finds its use in the production of refrigerants and propellants for aerosol cans.
CCl4 is prepared by the process of chlorination of methane which involves heating of methane
with excess of chlorine at 400°C
CH4 + 4 Cl2 400°C CCl4 + 4 HCl

Chloroform can be preapred from carbon tetrachloride by reduction with moist iron fillings.
Fe / H2 O
CCl4 + 2H CHCl3 + HCl
5. Freons :
The chlorofluoro derivatives of methane and ethane are collectively called freons. Freons
are named on the basis of number of fluorine atoms present in these compounds.
e.g. CF4 (Freon-14), CF3Cl (Freon - 13), CF2Cl2 (Freon-12) and CFCl3 (Freon - 11)
The most important and useful freon is Freon-12, which is most widely used refrigerant.
Freon-12 is manufactured from carbon tetrachloride by treating it with antimony trifluoride in
presence of a catalyst, SbCl5 (Swarts Reaction)
SbCl5
3CCl4 + 2 SbF3 3 CCl2F2 + 2 SbCl3
Freon - 12
Freon is an odourless, non-corrosive, non-toxic gas, which is stable at high temperatures
and pressures. Its b.p is – 29.8°C and can be easily liquified by applying pressure at room
temperature for which it is widely used as refrigerant in refrigerators and air conditioners. Most
freons are responsible for destruction of the ozone layer in stratosphere.
14.12 ARALKYL HALIDES :
These compounds, in fact, could be regarded as aryl-substituted alkyl halides. They have
halogen atoms present in the side-chain and are also often referred to as side-chain halogen
derivatives.
The structure of simple aralkyl halides are given below.
CH2Cl CH2Br CH2I
benzyl chloride benzyl bromide benzyl iodide

CHCl2 CCl3 CH2– CH2Cl
benzalchloride benzotrichloride b-chloroethylbenzene

The simple aralkyl halides are mostly derived from toluene.
Cl2 CH2Cl
h (bp) benzyl chloride
CH3
2Cl 2 CHCl2
bp benzal chloride
Toluene
3Cl 2 CCl3
bp benzotrichloride
The aralkyl halides are mostly used as intermediates in organic synthesis.

CHAPTER (14) AT A GLANCE-HALOARENES

1. Haloarenes are halogen derivatives of arenes. They may be nuclear halogen derivatives e.g.
Ar – X or side -chain halogen derivatives, e.g. Ar – (CH2)n – X, where X = halogen and n
= no. of CH2 groups.
2. Methods of Preparation :
(i) Electrophilic substitution reaction
Nuclear halogen derivatives are usually prepared from arenes by direct halogenation at low
temperature in presence of anhydrous AlCl3 or FeCl3 or FeBr3 and in absence of sunlight.
X
Ar – H Ar – X, X = Cl or Br
Anh.AlCl3 or Anh. FeCl3 or Anh.FeBr3
I2
Ar – H Ar – I
HNO3 or HIO3 or HgO
Side-chain halogenation is carried out in presence of sunlight and in the absence of halogen
carriers.
X2
R – CH3 R – CH2 – X or R – CHX2 or R – CX3 depending on the amount of X2.
hn
CuCl/HCl
(ii) Ar - Cl
CuBr/HBr
Ar - Br
} Sandmeyer reaction
+
Ar - N NX aq.KI
Ar - I
Warm
NaNO2/HBF4 D
0 0 Ar - F Balz-Schiemann reaction
0 -5 C
Cu/HX
Ar - X , X = Cl or Br Gattermann reaction
D
CCl4
(iii) Ar – COOAg + Br2 Ar – Br Hunsdiecker reaction
Reflux
(iv) Industrial method for chlorobenzene, Raschig process.
2C6H6 + 2HCl + O2 CuCl2 2C6H5Cl + 2H2O

D
3. Chemical proporties
(i) Nucleophilic substitution under drastic conditions.
aq.NaOH H+
0
C6H5 – ONa C6H5 – OH (Phenol)
300 C/Press.
NaCN/CuCN
0 C6H5CN (Phenyl cyanide)
C6H5 - Cl 200 C/Press.
aq.NH3
C6H5– NH2 (Aniline)
2000C/Press.
Cl Cl Cl
NO2 O2N NO2
readily undergo
, and
NO2 NO2 NO2
nucleophilic displacement reaction with OH giving the corresponding phenols (–Cl is replaced
by – OH)
(ii) Electrophilic substitution reaction under ordinary conditions.

Cl Cl
Anh. AlCl3 Cl
(a) Halogenation : Ar – Cl + (major)
or Anh.FeCl3
(minor) Cl
Cl Cl
NO2
(b) Nitration : Ar – Cl HNDO3/H2SO4 +
(minor) NO2
(major)
Cl Cl
SO3H
(c) Sulphonation : Ar – Cl Conc.
D
H2SO4 + (major)
(minor) SO3H
(d) Friedel Crafts reaction :

Cl Cl
CH3Cl CH3
F.C. Alkylation : Ar – Cl +
Anh. AlCl 3 (major)
(minor)
CH3
Cl Cl
COCH3
CH3COCl
F.C. Acylation Ar – Cl + (major)
Anh. AlCl3
(minor)
COCH3
(iii) Miscellaneous reactions :
2Na, D
2C6H5Cl C6H5 – C6H5 Fittig reaction
Dry ether
(Diphenyl)
C6H5Cl + C2H5Cl 2Na / Dry ether C6H5 – CH2 – CH3 Wurtz - Fittig reaction
D (ethyl benzene)
D
2C6H5–I + 2Cu C6H5 – C6H5 Ullmann biaryl synthesis
C6H5 – X + Mg Dry THF C6H5Mg – X (Phenyl magnesium halide, a Grignard reagent)

D
C6H5 – X + Li dry ether C6H5 – Li (Phenyl lithium)
D
Ni-Al/NaOH
C6H5 – Cl C6H6 (Benzene)
D, Reduction
4. Chlorobenzene can be prepared according to the general methods of preparation [2(i), (ii)
& (iv) ] and is used for the preparation of phenol, aniline and DDT, a powerful insecticide.
5. Aralkyl halides are side chain halogen derivatives and the simple one is prepared from
toluene by direct halogenation in presence of sunlight and a trace of peroxide and in the
absence of halogen carrier.
Cl2, h n
C6H5–CH3 C6H5 – CH2 – Cl + C6H5 CH Cl2 + C6H5CCl3.
BP
6. Benzene hexachloride (BHC) is an insecticide obtained under the trade name Gammaxane
or Lindane. Chlorine adds up to benzene in presence of U.V. light forming BHC. The g-
isomer of this compound is actually active and is called Lindane.
QUESTIONS
I. Multiple Choice Questions
Cl
1. The IUPAC name of the compound is :

Br
(a) 2-bromo-6-chlorocyclohex-1-ene
(b) 6-bromo-2-chlorocyclohexene
(c) 3- bromo - 1- chlorocyclohexene
(d) 1-bromo-3-chlorocyclohexene
2. Flurobenzene (C6H5F) can be prepared in the laboratory
(a) by heating phenol with HF and KF
(b) from aniline by diazotisation followed by heating the diazonium salt with HBF 4
(c) by direct fluorination of benzene with F 2 gas
(d) by reacting bromobenzene with NaF solution
3. Which of the following has highest melting point ?
(a) Chlorobenzene (b) o-Dichlorobenzene
(c) m-Dichlorobenzene (d) p-Dichlorobenzene
4. Chlorobenzene on treatment with sodium in dry ether gives diphenyl. The name of the
reaction is
(a) Fittig reaction (b) Wurtz-Fittig reaction
(c) Sandmeyer reaction (d) Gattermann reaction
5. Order of reactivity towards nucleophilic substitution reaction of the compounds
NMe 2 NO 2 Cl Cl
NO 2 O 2N NO 2
Cl Cl NO 2 NO 2
(i) (ii) (iii) (iv)

(a) i > ii > iii > iv (b) ii > i > iii > iv
(c) iv > iii > ii > i (d) iii > iv > ii > i
6. Which of the following is not an exmaple of Wurtz - Fittig reaction ?
(a) C6H5CH2Cl + CH3Cl Na/ether

(b) C6H5CH2Cl + C6H5Cl Na/ether
(c) C6H5Cl + CH3Cl Na/ether

(d) None of the above
7. The bromination of ethylbenzene in presence of sunlight will preferentially yield,
(a) 1-bromo - 1 - phenylethane
(b) 2-bromo - 1 - phenylethane
(c) p-bromophenylethane
(d) o - bromophenylethane
[ Note : During side chain halogenation, benzylic hydrogen is preferentally substituted]
Answer : 1 (a), 2. (b), 3. (d), 4. (a), 5. (c), 6. (a), 7. (a)
II. Fill in the blnaks (One mark each)

1. Formation of phenol from chlorobenzene is an example of aromatic substi-
tution and occurs through intermediate.
2. The reaction of p-nitrochlorobenzene with sodium methoxide to form p-nitroanisole
occurs by reaction.
3. Preparation of chlorobenzene from benzenediazonium chloride with cuprous chlo-
ride and aq. HCl is known as reaction.
4. Chlorobenzene reacts with in presence of conc. H2SO4 to form D.D.T..
5. Iodobenzene on heating with copper powder forms diphenyl. The reaction is called
Answer : 1. nucleophilic, benzyne

Cl
NaOH
NaOH
, Pressure
Benzyne
ONa
ONa OH
OH
dil. HCl
Phenol
2. bimolecular aromatic nucleophilic substitution
3. Sandmeyer reaction
4. Chloral (CCl3CHO)
5. diphenyl, Ullmann biaryl synthesis
Short Answer questinos (Two marks) :

1. Write the structure of the following aryl halogen compounds
(i) p-Bromochlorobenzene
(ii) Perfluorobenzene
(iii) Benzyl chloride
(iv) Benzal chloride
(v) Benzotrichloride
(vi) D.D.T
F
F F
[Hint. (ii) Perfluorobenzene structure
F
F
F
2. How can the following conversions be carried out ?

(i) Toluene to benzylalcohol
(ii)Benzene to biphenyl
(iii) Benzene to 4-bromonitrobenzene
(iv) Aniline to chlorobenzene
3. Explain the following :
(i) Chlorine present in chlorobenzene is ortho and para directing
(ii)Aryl halides are extremely less reactive towards nucleophilic substitution
(iii) Presence of a nitro group at ortho or para position increases the reactivity of
haloarenes towards nucleophilic substitution.
(iv) Aryl iodides can be prepared by reaction of arenes with iodine in the presence of
an oxidising agent.
Short answer questions (Three marks) :

1. Write the structural formulae of all possible isomers of aromatic compounds having
the molecular formula C7H7 Cl.
2. How will you synthesise phenylacetic acid from toluene ?
[ Hint : Use the following steps :
(i) Cl2/uv, (ii) Mg/ether, (iii) CO2 and (iv) H2O / H+
or, (i) Cl2/ un, (ii) KCN (iii) hydrolysis
3. How will you distinguish between benzyl bromide and p-bromotoluene ?
[Hint : Benzyl bromide forms a preciptitate of AgBr with alcoholic AgNO 3
solution. p-bromotoluene does not react]
Long Questions (7 marks) :

1. Why are aryl halides less reactive towards nucleophilic substitution reactions than alkyl
halides ? How can the reactivity of aryl halides be enhanced ?
2. Discuss the resonating structures of chlorobenzne. How do you account for double bond
character of C-Cl bond ? Describe the industrial method of preparation of
chlorobenzene.
3. Describe the preparation and properties of chlorobenzene.
4. Give the mechanism of nucleophilic substitution in aryl halides.
5. Give a general account for the preparation and chemical properties of aryl halides.
6. Discuss the mechanism of formation of phenol from chlorobenzene by reaction with
aqueous sodium hydroxide at high temperature and pressure. How can you distinguish o-
chlorotoluene from benzyl chloride ?
7. What is the product formed when
(i) Chlorobenzene reacts with chloral in the presence of conc. sulphuric acid.
(ii) Bromobenzne reacts with nitric acid in the presence of sulphuric acid.
8. Write notes on :
(i) Wurtz - Fittig reaction
(ii) Ullmann reaction
(iii) DDT
9. Write notes on :
(i) Freons
(ii) Chloroform
qqq
ALCOHOLS 447
UNIT - XI
ALCOHOLS, PHENOLS AND ETHERS
INTRODUCTION :
Alcohols and phenols are formed when a hydrogen atom in aliphatic hydrocarbon and
aromatic hydrocarbon is replaced by –OH group respectively.
–H –H
R–H R – OH ; C6H5H C6H5 – OH
+OH +OH
Alkane Alcohol Benzene Phenol
In alcohols the – OH group is directly attached to the carbon atom of an aliphatic system.
Thus, alcohols are the hydroxyl derivatives of aliphatic hydrocarbons.
In phenols the –OH group is directly attached to carbon atom of an aromatic system.
Phenols are the hydroxy derivatives of aromatic hydrocarbons in which the hydroxyl group
is directly attached to the carbon atom of the aromatic ring.
Hydroxy derivatives in which the hydroxyl group is present in the side chain of an aromatic
hydrocarbon is called aromatic alcohols. For example,
CH2 – OH CH2 – CH2 – OH
Phenylmethanol 2 - Phenylethanol
(or benzyl alcohol)
In benzylic alcohols, the – OH group is attached to carbon next to an aromatic ring, e.g.
benzyl alcohol.
In aliphatic or benzylic alcohols the hydroxyl group is attached to a sp3–hybridised carbon
atom. In aromatic system the hydroxyl group is attached to a sp2–hybridised carbon atom and
phenols thus obtained are quite stable, whereas, in aliphatic alcohols when the hydroxyl group is
attached to sp2–hybridised carbon atom, the resultant alcohol is unstable. For example vinyl
alcohol, CH2 = CH – OH is unstable.
The substitution of a hydrogen atom in a hydrocarbon by an alkoxy (OR) or aryloxy

(OAr) group yields a class of compounds known as ethers. Ethers are also regarded as alkyl or
aryl derivatives of alcohols i.e. H of OH is replaced by alkyl or aryl group.
–H –H
R–H R – O – R¢ ; Ar – H Ar – O – R¢
+OH +OH
Ether Ether
–H –H
Ar – H Ar – O – Ar ; R – OH R – O – R¢
+OAr +R¢
Ether Alcohol Ether
R or R¢ may be alkyl or aryl (Ar) group, same or different.
Ethers may also be regarded as dialkyl or diaryl derivative of water, both H of water is
replaced by alkyl or aryl group.
H–O–H R–O–H R–O–R

Water Alcohol Ether
or
Phenol
Functional group of ether is OR, where R is alkyl or aryl group.
In this unit chemistry of three classes of compounds, namely alcohols, phenols, and ethers
are discussed in different chapters.
ALCOHOLS 449
CHAPTER - 15
ALCOHOLS
15.1 INTRODUCTION :
Alcohols may be defined as the hydroxyl derivatives of hydrocarbon.
-H ®
R–H ¾+¾¾¾
( -OH)
R – OH
Hydrocarbon Alcohol
The hydroxyl group is the functional group of all alcohols. When the functional group is directly
attached to aliphatic hydrocarbon chain, it is called an alcohol. But, if the functional group is
directly attached to aromatic ring, it is called a phenol. The alcoholic –OH group is neutral
towards litmus, whereas phenolic –OH group is acidic in character.
15.2 CLASSIFICATION OF ALCOHOLS :
All alcohols can be broadly classified into two categories, i.e, aliphatic alcohols and
aromatic alcohols.
(i) Aliphatic alcohols : In aliphatic alcohols, the hydroxyl group is directly attached to aliphatic
hydrocarbon chain.
For example,
OH
|
CH3OH C2H5OH CH3 — CH — CH3
Methanol Ethanol Propan-2-ol
(Methyl alcohol) (Ethyl alcohol) (Isopropyl alcohol)
(ii) Aromatic alcohols : In aromatic alcohols, the hydroxyl group is directly attached to the
side chain of an aromatic hydrocarbon.
For example,
CH 2OH
(Benzyl alcohol)
Alcohols can further be classified as monohydric, dihydric, trihydric and polyhydric

alcohols, depending upon the number of the hydroxyl groups present in the molecules. If the
molecules contain one, two or three hydroxyl group, they are termed as monohydric, dihydric or
trihydric alcohols respectively. If their molecules contain four or more hydroxyl groups, they are
called polyhydric alcohols.
Monohydric alcohols Dihydric alcohols Trihydric alcohols Polyhydric
(Alkanol ) (Alkane diols) (Alkane triols ) alcohols
CH3OH CH2— OH
Methyl alcohol | vcc CH2— OH CH2— OH
(Methanol) CH2— OH | mmmmmm | m
Ethylene glycol CH— OH (CH— OH)4
(Ethane - 1,2 - diol) | , | ,
CH2— OH CH2— OH
C2H5OH Glycerol or
Ethyl alcohol Glycerine Sorbitol
(Ethanol) (Propane-1,2,3- triol)
Note : If two or more hydroxy groups are attached to the same carbon atom, the molecule
will be unstable. It will immediately lose water to form an aldyhyde or ketone or a
carboxylic acid.
—C—O H ¾-¾¾
H 2¾
O® —C = O + H2O
OH Aldehyde or Ketone
OH OH
—C—O H ¾-¾¾
H 2¾
O®
—C = O + H2O
OH Carboxylic acid
15.3 MONOHYDRIC ALCOHOLS :

The general formula of monohydric alcohols is C nH2n+1OH or Cn H2n+2 O or R — OH.
Monohydric alcohols are further classified as primary, secondary, and tertiary alcohols according
as the hydroxyl (–OH) group is attached to a primary, a secondary or a tertiary carbon atom
respectively.
(i) Primary alcohol : R — CH2 — OH or R — OH
R
(ii) Secondary alcohol : CH—OH
R/
ALCOHOLS 451
R/
|
(iii) Tertiary alcohol : R — C — OH
|
R//
Here, R/ and R// represent the same or different alkyl groups.
(i) Primary alcohol : In a primary alcohol, one alkyl group is attached to the saturated carbon
atom containing the hydroxyl group. It is represented by the general formula,
H
|
R — C — OH
|
H
Here, 'R' is any alkyl group or a hydrogen atom. Thus, a primary alcohol should contain a
–CH2 OH group.
Examples :
H H H
| | |
H — C — OH CH3 — C — OH CH3 — CH2 — C — OH
| | |
H H H
Methyl alcohol Ethyl alcohol n-Propyl alcohol
or Methanol or Ethanol or Propanol
(ii) Secondary alcohol : In a secondary alcohol, two alkyl groups are attached to the saturated
carbon atom containing the hydroxyl group. It is represented by the general formula,
R
CH—OH
R/
Here, R and R' may be same or different alkyl groups.
Thus, secondary alcohol should contain CH—OH group.
Examples :
CH3 CH3 CH2
CH—OH CH—OH
CH3 CH3
Isopropyl alcohol sec-butyl alcohol
or Propan-2-ol or Butan-2-ol
(iii) Tertiary alcohol : In a tertiary alcohol, three alkyl groups are attached to the saturated
carbon atom containing the hydroxyl group. It is represented by the general formula,
R/
|
R — C — OH
|
R//
Here, R, R/ and R// may represent the same or different alkyl groups.
Example :
CH3
|
H3C — C — OH
|
CH3
tertiary butyl alcohol
or
2- Methylpropan -2- ol
Thus, tertiary alcohol should contain – C– OH group.
15.4 NOMENCLATURE OF MONOHYDRIC ALCOHOLS :

In the common system, alcohols are named as alkyl alcohols. In IUPAC system, the names of
saturated alcohols are derived from the corresponding alkanes by replacing 'e' of an alkane by 'ol' . In
IUPAC system, alcohols are named as alkanols.
-e
Alkane ¾ ¾¾ ¾® Alkanol
+ ol
Structural formula Common name IUPAC name
CnH2n +2O Alkyl alcohol Alkanol
CH3OH Methyl alcohol Methanol

CH3—CH2—OH Ethyl alcohol Ethanol
CH3—CH2— CH2 — OH n-propyl alcohol Propan - 1 - ol
OH
|
CH3— CH — CH3 Isopropyl alcohol Propan - 2 - ol
CH3—CH2—CH2—CH2—OH n-Butyl alcohol Butan - 1 - ol
1 - Butanol
OH
|
CH3— CH2—CH — CH3 sec-butyl alcohol Butan - 2 - ol
CH3
|
CH3—C — OH tert-butyl alcohol 2- Methylpropan -2- ol
|
CH3
CH3
|
CH3— CH — CH2 — OH Isobutyl alcohol 2- Methylpropan -1- ol
Besides these systems, there is another system of naming of alcohols in which CH 3OH is called
carbinol and other alcohols are considered as alkyl derivatives of carbinol. However, this carbinol
system of nomenclature is not preferred now.
ALCOHOLS 453
CH3
|
CH3OH CH3— CH2— OH CH3 — C — OH
|
CH3
Carbinol Methylcarbinol Trimethylcarbinol
15.5 ISOMERISM IN ALCOHOLS :

Higher aliphatic alcohols exhibit three types of structural isomerism along with
stereoisomerism.
(a) Chain Isomerism : All alcohols are the derivatives of alkanes. Therefore, they exhibit
chain isomerism due to the presence of different types of carbon chains.
For example, C4H9OH has the follwing chain isomers.
(i) CH3 — CH2 — CH2 — CH2 — OH

n – Butyl alcohol
CH3 CH3
| |
(ii) CH3— CH — CH2 — OH (iii) CH3— CH2 — CH — OH
Isobutyl alcohol see-butyl alcohol
CH3
|
(iv) CH3— C — OH
|
CH3
tert-butyl alcohol
(b) Position Isomerism : This isomerism is due to the different positions of –OH group in the
same carbon chain. For example, C3H7OH has two position isomers.
OH
|
(i) CH3— CH2— CH2 — OH CH3 — CH — CH3
Propan - 1 - ol Propan - 2 - ol
(c) Functional Isomerism : This isomerism is due to the difference in the functional group.
For example, C2H6O represents dimethyl ether and ethyl alcohol, which have different
functional groups.
CH3 — CH2 — OH CH3 — O — CH3
Ethyl alcohol Dimethyl ether
Thus, ethyl alcohol and dimethyl ether are functional isomers.
(d) Stereoisomerism : Higher alcohols exhibit optical isomerism, due to the presence of
asymmetric carbon atom. For example, butan-2-ol can give two optical isomers.
CH H5C2
| 2 5 |
H3C — C — OH HO — C — CH3
| |
H H
(d-Butan - 2 - ol) (l - Butan - 2 - ol)
mirror
15.6 GENERAL METHODS OF PREPARATION :
Monohydric alcohols can be prepared by the following general methods.
1. By the hydrolysis of alkyl halides :
When alkyl halides are boiled with aqueous solution of sodium or potassium hydroxide,
alcohols result.
heat
R–X + KOH(aq) ¾¾
¾® R–OH + KX
(Alkyl halide) (Alcohol)
heat
C2H5–Br + KOH(aq) ¾¾
¾® C2H5– OH + KBr
(Ethyl bromide) (Ethyl alcohol)
In this reaction, small amount of ether is also formed along with alcohol. But, when KOH
is replaced by mild alkali, such as moist Ag 2O (Ag2O + H2O ) , alcohol is obtained in better yield.
heat
C2H5Br + AgOH ¾¾
¾® C2H5 – OH + AgBr
(Ethyl bromide) (Ethyl alcohol)
The order of reactivity of alkyl halides towards hydrolysis is RI > R –Br > RCl.
2. By hydrolysis of esters :
When esters are boiled with aqueous solution of sodium or potassium hydroxide, alcohols
result along with the salt of the carboxylic acid. This process is called saponification.
O O
|| ||
R—C—O—R/ + NaOH(aq) ¾heat
¾¾® R— C—ONa + R/—OH
Ester Alcohol
heat
CH3COOC2H5 + NaOH(aq) ¾¾ ¾® CH3COONa + C2H5OH
Hydrolysis of esters can also be carried out in the presence of a dilute mineral acid as a
catalyst. In this case, alcohol and carboxylic acid are produced.
dil. HCl
CH3COOC2H5 + H2O CH3COOH + C2H5OH
3. By reduction of aldyhydes and ketones :
Carbonyl compounds, such as aldehydes and ketones can easily be reduced to alcohols.
The commonly used reducing agents are (i) hydrogen in the presence of a catalyst, such as finely
divided Ni, Pt or Pd. (ii) nascent hydrogen obtained by the action of sodium in ethanol and (iii)
complex metal hydrides, such as sodium borohydride (NaBH 4) or lithium aluminium hydride
(LiAIH4).
ALCOHOLS 455
Aldehydes and ketones can be reduced by sodium in ethanol to give primary and secondary
alcohols respectively. This process is otherwise known as Bouveault - Blanc reduction. A tertiary
alcohol can not be obtained by this method.
O
||
R—C—H + 2H Na/C H OH
¾ ¾¾¾¾¾¾
2 5 ® R—CH2—OH
(Aldehyde) (10– Alcohol)
CH3—CHO + 2H ¾Na/C 2 H5 OH ® CH —CH —OH
¾¾¾¾¾¾ 3 2
(Acetaldehyde) (Ethanol)
R R
C=O + 2H ¾Na/C
¾¾¾¾¾¾
H
2 5 OH ® CH—OH
R/ /
R
(Ketone) (20Alcohol)
CH3 CH3
C=O + 2H ¾Na/C 2 H5 OH ®
¾¾¾¾¾¾ CH—OH
CH3 CH3
(Isopropyl alcohol)
4. By the action of Grignard reagents on aldehydes and ketones :
Grignard reagents (R - Mg - X) can be prepared by the addition of alkyl halides to
magnesium, suspended in dry ether (R - X + Mg ® R - Mg - X). Grignard reagents react with
aldehydes and ketones in the presence of dry ether to give addition products. These addition
products on hydrolysis with dilute mineral acids (dil. HCl or dil H 2SO4) produce alcohols. All the
three types of alcohols can be prepared by this method.
(a) Primary alcohols are obtained by the action of Grignard reagent with formaldehyde.
H
H OMgBr
H—C
CH3 – Mg – Br + H—C=O ¾ ¾® CH3
(Methyl magnesium bromide)
H2O dil HCl
.
CH3– CH2– OH+Mg(OH)Br
(Ethanol)
(b) Secondary alcohols are obtained by treating the Grignard reagent with aldehyde other than formal-
dehyde.
H
H
CH3 —C = O ¾¾® OMgBr
CH3 – Mg – Br + CH3 —C
CH 3
(Methyl magnesium bromide)
H2 O dil HCl
CH3
CH3– CH –OH +Mg(OH)Br
(Propan-2-ol)
(c) Tertiary alcohols are obtained by the action of Grignard reagent with ketones.
CH3 CH3 OMgI

CH3 – Mg – I + C=O ¾ ¾® C
(Methyl magnesium iodide) CH3 CH3
CH3
H2O dil. HCl
CH3
CH3– C –OH + Mg(OH) I
CH3
(2-Methylpropan -2- ol )
5. From aliphatic primary amines :
When aliphatic primary amines (except CH3NH2) are treated with a cold solution of sodium
nitrite and dilute hydrochloric acid, primary alcohols are produced. The nitrous acid, prepared by
the reaction of sodium nitrite and dilute HCl reacts with the 1 0-amine.
NaNO2 + dil. HCl ¾¾
¾® HNO2 + NaCl
R — NH2 + HNO2 ¾¾
¾® R — OH + N2 - + H2O
(10-amine) (10 - alcohol)
¾® CH3 — CH2 — OH + N2 - + H2O

CH3 — CH2 — NH2 + HNO2 ¾ ¾
(Ethyl amine) (ethyl alcohol)
6. Addition of water (Hydration)
Alkenes undergo acid-catalysed addition of water to form alcohols. The method is used to
prepare ethanol industrially. The commonly used acids are sulphuric acid and phoshoric acid.
The reaction follows Markownikoff’s rule
H3PO4
CH2 = CH2 + H2O 0 CH3CH2OH (ethanol)
300 C
(Ethene)
CH3
CH3 H2PO4
C = CH2 + H2O 0
CH3 C OH
CH3 25 C
CH3
2-Methylpropene (tert. Butyl alcohol)
Acid transfers the proton to alkene is usually the solvated hydronium ion. Water itself
is too weak to transfer the proton to the alkene. So acid - catalyst is essential
..+ +
CH3 – CH = CH2 + H – O – H CH3 – CH – CH3 + H2O
Propene H
(Hydronium ion)
ALCOHOLS 457
+ .. +
CH3 CH CH3 + H2O CH3 CH CH3 H 3C – CH – CH 3 + H3O
H2O
..
O OH
H + H (2-Propanol)
7. Hydroboration - Oxidation
Alkenes undergo hydroboration with the reagent diborane (BH3)2 to produce trialkyl boron
R3B which on subsequent oxidation with H2O2 in presence of alkali NaOH yields alcohol (10)
CH = CH CH = CH CH = CH
(BH3)2¾¾¾ 2 ¾ ¾¾ 2 ® CH CH BH¾¾ ¾
3 2 2
2 ¾ ¾¾ 2 ® (CH CH ) BH¾¾ ¾
3 2 2
2 ¾ ¾¾
2 ® (CH CH ) B
3 2 3
Diborane Triethylboron
(CH3CH2)3 B + 3H2O2 OH 3CH3 CH2OH + B (OH)3
Triethylboron hydrogen peroxide Ethyl alcohol Boric acid
Diborane is a toxic gas prepared by the reaction of sodium borohydride and boron trifluoride.
3NaBH4 + 4BF3 ® 2B2 H6 + 3NaBF4
Diborane is the dimer of hypothetical BH3 (Borane)
Tetrahydrofuran is used as the solvent in the hydroboration reaction in which diborane
exists as monomer forming a complex.
H H H
H H
H B O
H B B B
H H H H
H
Borane Diborane Borane - tetrahydrofuran complex
Borane undergoes rapid and quantitative reaction with alkene to form organoboranes
(R3B). The overall reaction is the result of three separate steps.
H BH2
| |
Step (i) CH2 = CH2 + B – H ¾® CH3 – CH2
|
H
BH2
|
Step (ii) CH2 = CH2 + CH3 – CH2 ® (CH3 CH2)2 BH
Step (iii) CH2 = CH2 + (CH3CH2)2 BH ® (CH3 CH2)3 B.

Triethyl borane
(An organo borane)
Other examples
(BH3)2 H2O2,OH
CH3 – CH = CH2 CH3 – CH2 – CH2 – OH
THF
Propene n - propylalcohol
(BH3)2 H2O2,OH
CH3 – CH2 – CH = CH2 CH3 – CH2 – CH2 – CH2 – OH
THF
1- Butene n-Butylalcohol
CH3 CH3
| (BH3)2 H2O2,OH |
CH3 – C = CH2 CH3 – CH – CH2 OH
THF
Isobutylene Isobutyl alcohol
Mechanism
A four centred transition state is formed prior to the formation of organoborane.
Hydroboration is thus a cis-addition.
+d
Step I d-
CH3 – CH = CH2 + H – BH2 ¾® CH3 – CH – CH2 ® CH3CH2CH2BH2
|+ H .......
H .......B
H
TS
CH3 – CH = CH2 + CH3 CH2 CH2 BH2 ® CH3 – CH – CH2

......
| + CH2CH2CH3
H ........B
TS H
¯
(CH3 CH2 CH2)2 BH
CH3 – CH = CH2 + (CH3 CH2 CH2)2 BH ® (CH3 CH2 CH2)3 B

Tripropyl borane
(R3B) say
Step II
Trialkyl borane is oxidised with H2O2 in presence of NaOH to form alcohol.
–
H – O – O – H + OH– ® H2O + O – O – H
R
– –
R–B–R+O–O–H® R–B–O–R
| |
R R R
1,2-shift of R
OR
2 OOH 3 OH 3ROH + B (OH)3
RO B OR
-2 OH Hydrolysis alcohol Boric acid
Hence, in case of propene, the product is CH3 CH2 CH2 OH (n-propylalcohol).
ALCOHOLS 459
The hydroboration – oxidation process gives products corresponding to anti -

Markownikoff addition of water to C = C bond.
(8) Oxymercuration - demercuration
Alkenes react with mercuric acetate in presence of water to form hydroxy mercurial com-
pounds which on subsequent reduction yield alcohols.
OCOCH3 Demercuration
oxymercuration NaBH4
C = C + H2O + Hg C C C C H
OCOCH3 OH HgOCOCH3 OH H
The first stage in oxymercuration which involves the addition of –OH and – HgO COCH3
to C=C bond. The second stage is demercuration is which – HgOCOCH3 is replaced by – H. The
over all result amounts to hydration of alkene. The process is very fast and the yield is over 90%.
At room temperature alkene is added to an aqueous solution of mercuric acetate diluted with
solvent tetrahydrofuran.
Oxymercuration - demercuration is highly regioselective and produces alcohols corre-
sponding to Markownikoff’s addition of H2O to C = C bond.
For example,
(i) (CH3COO)2 Hg OH
CH3 – CH = CH2 CH3 – CH – CH3

(ii) NaBH4 isopropylalcohol
Mechanism
Step (I) Alkene when treated with mercuric acetate in presence of H 2O and THF forms
hydroxy alkyl mercurial compound. A three centred transition state is formed as intermediate.
Dissociation of mercuric acetate :-
Hg (O2CCH3)2 ® +Hg O2C.CH3 + O2 CCH3
¬
Electrophilic attack O
+
CH3 – CH = CH2 + Hg – O – C – CH3 ® CH3 – CH – CH2
HgOCOCH3
3 centred TS
H2O
OH
CH3 - CH - CH2
HgOCOCH 3
Step II
(Organomercuric compound)
The hydroxy alkyl mercurial compound on reduction with NaBH4 produces 20 alcohol.
OH
OH |
CH3 – CH – CH2 CH3 – CH – CH3
| Isopropyl alcohol
HgOCOCH3
Other examples
CH3 CH3
Hg(OAc)2 OH
1.
H2O
1- methyl cyclopentene 1- methyl cyclopentanol

CH3 CH3
Hg(OAc)2 NaBH4
2. CH = CH2 CH3 – CH – CH – CH3
H2O
CH3 CH3 OH
3, 3- dimethylbutan-2-ol
15.7 PROPERTIES :
(A) Physical Properties :
1. Physical state : At ordinary temperature, the lower members of alcohols are colourless
volatile liquids having distinct odour and burning taste.
2. Solubility : The first three members are completely miscible in water. The solubility
decreases rapidly with increase in the molecular mass. The higher members are completely
insoluble in water but are soluble in organic solvents like benzene, ether etc.
The solubility of lower members of alcohols in water is only due to the formation of hydrogen
bonding between alcohol and water molecules.
H
H
O
O
H
H H
H
O H
O O
Hydrogen
bonds
R
R R
The increase in the molecular mass of the alcohol increases the size of the non-polar part
of the hydrocarbon. As a result of which, it resists the formation of hydrogen bonding with water
molecules and hence the solubility in water decreases.
Amongst isomeric alcohols, the solubility in water increases with branching of the chain.
It is because, the surface area of the non-polar part in the molecule decreases. As for example, n-
butyl alcohol is least soluble in water while tert -butyl alcohol is highly soluble.
3. Boiling points : The boiling points of alcohols are much higher that those of hydrocarbons,
ethers and haloalkanes of comparable molecular masses. This arises due to the intermolecular
ALCOHOLS 461
hydrogen bonding in alcohols. Due to the intermolecular hydrogen bonding, alcohols exist
as associated molecules rather that discrete molecules. Thus, large amount of energy is
required to break these bonds.
R
R
O
O
H
H H
H
O H
O O
Hydrogen
bonds
R R R
Compounds : CH3– CH2–OH CH3 – O – CH3 CH3Cl CH3 - CH2 - CH3

Ethanol Methoxymethane Chloromethane Propane
Mol. mass : 46 46 50.5 44
Boiling point : 351K 297K 249K 231K
Amongst the isomeric alcohols, the boiling points follow the order;
Primary > Secondary > Tertiary
For example, among n-butyl alcohol, sec-butyl alcohol and tert - butyl alcohol, the boiling point
of n-butyl alcohol is more.
Alcohol : n-Butyl alcohol sec-butyl alcohol tert-butyl alcohol
Boiling point : 391K 372.5K 356 K
This can be explained on the fact that branching decreases the surface area which in turn
decreases intermolecular forces of attraction. Hence, boiling point becomes low. However, with
the increase in molecular mass boiling points of alcohols increase regularly.
4. Physiological effect : Alcohols are toxic in nature when taken internally. Amongst all
alcohols, ethyl alcohol is least toxic. Methyl alcohol, in turn, is quite toxic. Drinking methyl
alcohol may cause blindness or death.
(B) Chemical properties :
The chemical properties of alcohols are mainly due to their functional group, i.e. hydroxyl
(– OH) group. The chemical reactivity of alcohols can be calssified as follows.
1. Reactions involving replacement of hydrogen atom of the hydroxyl group (cleavage
of oxygen- hydrogen bond)
2. Reactions invloving replacement of the hydroxyl group (cleavage of carbon-oxygen
bond)
3. Reactions involving both alkyl group and hydroxyl group.
1. Reaction involving the cleavage of oxygen- hydrogen bond :

(i) Reaction with alkali metals : Alcohols react with alkali metals like Li, Na, K to form
metal alkoxides with the liberation of hydrogen gas.
2R — OH + 2Na ¾¾
¾® 2 RONa + H2 -
Alcohol Sodium alkoxide
2CH3OH + 2Na ¾¾
¾® 2 CH3ONa + H2 -
Methanol Sodium methoxide
2 C2H5OH + 2Na ¾¾
¾® 2 C2H5ONa + H2 -
Ethanol Sodium ethoxide
CH3 CH3
| |
2 H3C — C — OH + 2K ¾¾
¾® 2 H3C — C — OK + H2 -
| |
CH3 CH3
tert-butyl alcohol Potassium t-butoxide
In this reaction, the order of reactivity is

primary alcohol > sec - alcohol > tert. - alcohol.
(ii) Reaction with carboxylic acids :

Alcohols react with carboxylic acids in presence of conc. H 2SO4, which acts as catalyst to
form esters. This reaction is known as esterification reaction.
O O
|| ||
R—C— OH + H —O—R/ ¾conc. H2 SO¾
¾¾¾¾¾ 4 ® R—C—O—R/ + H O
2
(carboxylic acid) (alcohol) (ester)
O O
|| ||
CH3—C— OH + H —O—C2H5 ¾conc.
¾¾¾¾¾
H2 SO¾
4 ® CH — C — O — C H
3 2 5
+ H2O
(acetic acid) (ethyl alcohol) (ethyl acetate)
(iii) Reaction with inorganic acids :
Alcohols react with inorganic acids like, HCl, H2SO4 etc. forming the corresponding
alkyl halide, alkyl hydrogen sulphate respectively.
R — OH + HCl ¾Anh.ZnCl
¾ ¾¾2 ® R — Cl + H2O
C2H5OH + HCl ¾Anh.ZnCl

¾ ¾¾2 ® C2H5 — Cl + H2O
(Ethyl alcohol) (ethyl chloride)
The order of reactivity of alcohols is as follows; 3 0 > 20 > 10
ALCOHOLS 463
Ethyl alcohol when treated with equimolar amount of conc H 2SO4 at 1000C, forms the
corresponding inorganic ester (C2H5HSO4)
C2H5 — OH + H2SO4 ¾ ¾
¾® C2H5 — HSO4 + H2O
When ethyl alcohol is taken in excess at 140 0C, diethyl ether is formed.
C2H5 — HSO4 + HO C2H5
C2H5 — O — C2H5 + H2SO4

On the other hand, when conc. H2SO4 is taken in excess at 1600C, ethylene is formed.
D
C2H5 — HSO4 ¾¾0 ® C2H4 + H2SO4
160 C
(ethylene)
2. Reaction involving the cleavage of carbon-oxygen bond :
(i) Reaction with phosphorus halides :
With PCl5 : Alcohols react with PCl5 to form the corresponding alkyl chlorides, phosphoryl
chloride and HCl.
R — OH + PCl5 ¾¾ ¾® R — Cl + POCl3 + HCl -
Alcohol alkyl chloride phosphoryl
chloride
C2H5OH + PCl5 ¾ ¾ ¾® C2H5 — Cl + POCl3 + HCl -
Ethyl alcohol ethyl chloride
With PCl3 : Alcohols react with PCl3 to form the corresponding alkyl chlorides, and
phosphorus acid.
3 R — OH + PCl3 ¾¾ ¾® 3R — Cl + H3PO3
Alcohol alkyl chloride phosphorous acid
3 C2H3OH + PCl3 ¾ ¾ ¾® 3 C2H5 — Cl + H3PO3
Ethyl alcohol ethyl chloride
(ii) Action of thionyl chloride (SOCl2) :
Alcohols react with thionyl chloride in the presence of pyridine (a base) to form the
corresponding alkyl chloride, SO2 gas and HCl gas.
R — OH + SOCl2 ¾Pyridine
¾¾¾¾® R — Cl + SO2 - + HCl -
Alcohol Thionyl Alkyl
chloride chloride
Pyridine C2H5Cl + SO2 - + HCl -
C2H5 OH + SOCl2 ¾ ¾¾¾¾®
Ethyl alcohol Thionyl Ethyl
chloride) chloride
3. Reactions involving both alkyl and hydroxyl groups :

(i) Oxidation of alcohols :
The process of oxidation involves the removal of hydrogen. In the oxidation of alcohols,
hydrogen is removed from the carbon atom to which the functional group is directly linked (a-
hydrogen atom) and also from the functional group. As a result of which a carbonyl group is
produced.
H
—C—O—H ¾¾
¾® — C =O
—O = –O+ H+)
+ (H
X (H++ H–) + [O] ¾ ¾

¾® H2O
Thus, the process of oxidation involves the breaking of a carbon -hydrogen and oxygen -
hydrogen bond. Here, a carbonyl compound is formed along with hydrogen gas. But in the presence
of solution of oxidising agents, it produces water in place of hydrogen gas.
The reagents commonly used for the oxidation of alcohols are,
(a) sodium or potassium dichromate solution and conc. sulphuric acid,
(b) alkaline solutions of potassium permanganate.
(c) conc. nitric acid and
(d) heated metal catalyst, such as silver and copper.
The products of oxidation depend on the type of alcohol used and also on the nature of
oxidising agent.
(a) Oxidation of primary alcohols :
A primary alcohol is first oxidised to an aldehyde, having the same number of carbon
atoms as the parent alcohol when treated with acidified potassium dichromate solution. Since the
aldehyde formed also contains an a - hydrogen atom, it can readily be oxidised to carboxylic
acid, having same number of carbon atoms as the parent alcohol.
H H
| K2Cr2O7 |
R — C — OH + [O] ¾ ¾¾¾¾ ¾® R — C = O + H 2O
| dil.H 2SO4
(aldehyde)
H
(10-alcohol)
H O
| ||
K Cr O
2 2 ¾
7®
R — C = OH + [O] ¾ ¾¾¾¾ R — C — OH
dil.H 2SO4
(Aldehyde) (carboxylic acid)
Thus, ethyl alcohol when treated with acidified potassium dichromate solution, is first
oxidised to acetaldehyde and then to acetic acid.
ALCOHOLS 465
H H O
| [O]
| [O]
||
¾¾¾¾¾¾¾ ¾® ¾ ¾¾¾¾¾¾ ¾®
CH3 — C — OH K Cr O / dil.H SO CH3 — C = O K Cr O / dil.H SO CH3— C —OH
| 2 2 7 2 4 (Acetaldehyde) 2 2 7 2 4 (acetic acid)
H
(Ethyl alcohol)
However, oxidation of 10-alcohol with potassium permanganate converts it directly to carboxylic
acid.
[O]
R—CH2—OH ¾ ¾¾¾® R—COOH
KMnO4
[O]
CH3—CH2—OH ¾ ¾¾¾® CH3 COOH
KMnO4
(Ethyl alcohol) (acetic acid)
(b) Oxidation of secondary alcohols :
A secondary alcohol when treated with acidfied potassium dichromate solution, is oxidised
to a ketone, having same number of carbon atoms as the parent alcohol.
R
|
R — C — OHH + [O] K2Cr2O7
¾ ¾¾¾ ¾® R — C = O + H2O
| dil. H 2SO 4 |
H R
(sec-alcohol) (ketone)
Since the ketone formed has no oxidisable a — hydrogen atom, ordinarily it does not
undergo further oxidation. However, on vigorous oxidation, the ketone formed is further oxidised
and gives a mixture of lower carboxylic acids.
H
| K2Cr2O7
CH3 — C — OH + [O] ¾ ¾¾¾¾ ¾® CH3 — C = O
| dil.H 2SO4 |
CH3 CH3
(isopropyl alcohol) (acetone)
vigorous [O]
oxidation
CH3COOH + HCOOH
(acetic acid) (formic acid)
CO2 + H2O
OH O
| ||
CH3 — CH — CH2 — CH3 [O]
¾ ¾¾¾® CH — C —CH2—CH3
3
(2-butanol) (2-butanone)
vigorous [O]
oxidation
2CH3COOH
(Acetic acid)
(c) Oxidation of tertiary alcohols :

Tertiary alcohols do not contain a — hydrogen atoms. Hence, it is resistant to oxidation
in alkaline solution.
R
|
[O]
R — C — OHH ¾ ¾¾¾¾ ¾® No oxidation.
| alk.KMnO4
R
However, on drastic oxidation, tertiary alcohol is oxidised to give a ketone and lower
carboxylic acid, when treated with hot acid oxidising agents. Thus, tert-butyl alcohol when treated
with dil HNO3, is oxidised to acetone and formic acid. The initial step of oxidation involves the
dehydration of alcohol to alkene, which is then oxidised.
CH3 CH2
| ||
dil.HNO
¾ ¾ ¾ ¾ ¾3 ®
CH3 — C — OH CH3 — C
| (- H 2O) |
CH3 CH3
HNO3 [O]
CH3 — C = O + HCOOH
|
CH3
[O]
[O]
CH3 COOH + HCOOH CO2 + H2O
Here acetone formed is further oxidised to acetic acid and formic acid. Similarly, formic
acid formed is further oxidised to CO2 and H2O.
(ii) Catalytic dehydrogenation :
Alcohols are oxidised in presence of heated metal catalyst such as Cu or Ag. In this case,
oxidation of alcohols involves the removal of a hydrogen molecule or dehydrogenation. Thus,
when vapours of three types of alcohols are passed over heated copper at 300 0C, primary, secondary
and tertiary alcohols are oxidised to give different products. Depending on the products formed,
the three types of alcohols can be easily distinguished.
(a) When vapours of primary alcohol is passed over heated reduced copper catalyst at 300 0C,
the alcohol is dehydrogenated to give an aldehyde.
R — CH2— OH ¾¾0®
Cu
R — CHO + H2 -
300 C
(10- alcohol) (aldehyde)
CH3 — CH2— OH ¾¾0®
Cu
CH3 CHO + H2 -
300 C
(Ethyl alcohol) (acetaldehyde)
ALCOHOLS 467
(b) When vapours of secondary alcohol is passed over heated reduced copper catalyst at 300 0C,
the alcohol is dehydrogenated to give a ketone.
R— CH — OH ¾¾0®
Cu
R — C = O + H2 -
300 C
| |
R R
(20- alcohol) (ketone)
CH3 — CH — OH ¾¾0®
Cu
CH3 — C = O + H2 -
| 300 C |
CH3 CH3
(Isopropyl alcohol) (acetone)

(c) But the tertiary alcohol is not dehydrogenated. Rather it is dehydrated to form an alkene,
when passed over heated reduced copper catalyst at 300 0C.
CH3 CH2
| ||
CH3— C — OH ¾¾0®
Cu
CH3— C + H2O
| 300 C |
CH3 CH3
(t-butyl alcohol) (2- methylpropene)
15.8 DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY ALCOHOLS :
The following methods are used to distinguish primary, secondary and tertiary alcohols.
1. Oxidation method :
Primary, secondary and tertiary alcohols on oxidation produce different types of products.
Basing on the products formed, three types of alcohols can be distinguished.
(i) A primary alcohol on oxidation first gives an aldehyde, which on further oxidation gives a
carboxylic acid. Here, both the oxidation products contain the same number of carbon
atoms as the parent alcohol.
For example, ethyl alcohol on oxidation first gives acetaldehyde, which on further oxidation
gives acetic acid.
H H OH
| | |
[O] [O]
CH3— C — OH ¾¾¾® CH3— C = O ¾¾¾® CH3 — C = O
|
H (Acetaldehyde) (Acetic acid)
(Ethyl alcohol)
(ii) A secondary alcohol on oxidation first gives a ketone, having same number of carbon
atoms as the parent alcohol. Since ketone does not contain a - hydrogen atom, it can not
undergo further oxidation. But on vigorous oxidation, that is, on prolonged action of hot
oxidising agents, ketone can be oxidised to give a mixture of carboxylic acids, each
containing less number of carbon atoms than the parent alcohol.
For example, isopropyl alcohol on oxidation first gives acetone, which on vigorous oxidation
gives a mixture of acetic acid and formic acid.
CH3
CH3
CH—OH [O]
¾¾
¾® C= O ¾[O]
¾
¾® CH3COOH + HCOOH
CH3
CH3
(Isopropyl alcohol) (Acetone) (Acetic acid) (Formic acid)
(iii) A tertiary alcohol can not be oxidised in presence of neutral or alkaline solution. But it is
readily oxidised by an acid oxidising agent to give a mixture of ketone and carboxylic acid,
each containing less number of carbon atoms than the parent alcohol.
CH3
CH3
[O]
¾¾¾® C=O ¾¾
[O]
¾® CH3COOH + HCOOH
CH3 — C — OH
CH3 (Acetic acid) (Formic acid)
CH3
(tert. butyl alcohol) (acetone)
2. Catalytic dehydrogenation method :
In this method, the vapours of the given alcohol is passed over reduced copper at 300 0C
and the products obtained are identified. Here a primary alcohol on dehydrogenation produces an
aldehyde, whereas a secondary alcohol produces a ketone. But under the same condition, a tertiary
alcohol is not dehydrogenated, rather it is dehydrated to produce an alkene. The method is
summarised as follows :
10 - alcohol ¾¾0 ® Aldehyde + H2

Cu
300 C
20 - alcohol ¾¾0 ® Ketone + H2

Cu
300 C
30 - alcohol ¾¾0 ® Alkene + H2

Cu
300 C
3. Lucas Test :
This test consists of reactions of the different types of alcohols with Lucas reagent, which
is an equimolar mixture of conc.HCl and anhydrous ZnCl2 at room temperature. On reaction,
coresponding alkyl chlorides are formed, which being insoluble appears as turbidity in the solution.
R — OH + Conc. HCl ¾Anh.ZnCl

¾ ¾ ¾¾ 2® R — Cl + H2 O
(Alcohol) Alkyl chloride
(turbidity)
The alcohols are differentiated from each other on the basis of time required for the
appearance of turbidity.
conc.HCl
(i) 30 - alcohol ¾ ¾¾¾ ¾® Turbidity appears immediately..
anh. ZnCl 2
conc.HCl
(ii) 20 - alcohol ¾ ¾¾¾ ¾® Turbidity appears after five minutes.
anh. ZnCl 2
conc.HCl
(iii) 10 - alcohol ¾ ¾¾¾ ¾® No turbidity appears even after several hours.However,,
anh. ZnCl 2
turbidity appears on heating.
ALCOHOLS 469
4. Victor Meyer's Test :

This test is performed as follows :
(i) The given alcohol is converted to the corresponding alkyl iodide by treating with red
phosphorus and iodine.
(ii) Then the alkyl iodide obtained is treated with silver nitrite (AgNO 2) in order to get
the corresponding nitroalkane.
(iii) The nitroalkane obtained is then treated with nitrous acid (NaNO 2 + dil H2SO4).
(iv) Finally, the resultant solution is made alkaline with aqueous KOH or NaOH.
If the resultant solution becomes blood red colour by performing the above tests, then the
alcohol is primary. If the solution become blue in colour, the alcohol is secondary and if a colourless
solution is obtained it is tertiary alcohol.
H H CH3
CH 3 — C — OH CH3 — C — OH CH3 — C — OH
H CH 3 CH3
P/I 2 P/I2 P /I 2
H H CH3
CH 3 — C — I CH3 — C — I CH3 — C — I
H CH 3 CH3
AgNO 2 AgNO2 A gN O 2
H H CH3
CH 3 — C — NO 2 CH3 — C — NO 2 CH3 — C — NO2
H CH 3 CH3
HO-N=O HO-N=O H O -N = O
NO 2 CH3 NO 2
CH 3 — C C
CH3 N=O (N o reaction)
N OH
(nitrolic acid) (Pseudonitrol)
dil KOH dil KOH dil K O H
Blood red colour Blue colour Colourless
15.9 TESTS FOR ALCOHOLIC –OH GROUP :

In order to detect the presence of alcoholic group in an unknown organic compound, the
following tests may be performed.
(i) When a piece of sodium metal is added into a flask containing dry alcohol, hydrogen
gas is evolved.
¾® 2RONa + H2 -
2ROH + 2Na ¾ ¾
(ii) Similary, if PCl5 or acetyl chloride is added HCl gas is obtained with liberation of heat.
R OH + PCl5 ¾¾® R — Cl + POCl3 + HCl - + heat

(iii) Treatment of of the dry compound with acetyl chloride (CH3COCl). CH3COCl
reacts with a compound containing a hydroxyl group with the evolution of HCl gas
and the production of an ester.
CH3O H + Cl OCCH3 ¾¾® CH3COOCH3 + HCl

Methyl acetate
(iv) Ceric Ammonium Nitrate Test. This is the most delicate and sensitive test. When a
few drops of an organic compound containing OH group is added to the aqueous
solution of ceric ammonium nitrate which is orange, the colour changes to red.
(NH4)2Ce(NO3)6 + 2ROH ¾¾® Ce(NO3)4 (ROH)2 + 2NH4NO3

(Orange) (Red)
15.10 MANUFACTURE OF METHYL ALCOHOL FROM DESTRUCTIVE

DISTILLATION OF WOOD :
Methyl alcohol can be commercially manufactured by the destructive distillation of wood.
Principle : The principle involved in this process is heating of wood at about 400 0C in the
absence of air. The heating of wood at high temperature in iron retorts in absence of
air is known as destructive distillation of wood.
Main products of distillation :
The main products of destructive distillation of wood are illustrated below.
WOOD
Destructive
distillation
Wood Gas Pyroligneous acid Wood Tar Wood Charcoal
(i) Wood Gas : It consists of CH4, C2H6, H2, CO, CO2 and N2 . It is used as a fuel for
heating the iron retorts in wood distillation.
(ii) Pyroligneous acid : The aqueous distillate which is collected over wood tar (as shown
in figure 21.1) is called pyroligneous acid. In addition to water, it contains,
ALCOHOLS 471
Methyl alcohol = 2.0 to 4.0 %

Acetone = 0.5 %
Acetic acid = 10.0 %
(iii) Wood Tar : It is the thick black liquid, settled at the bottom of the settling tank.
(iv) Wood charcoal : It is the solid residue left in the iron retort after the distillation is
over. It consists mainly of carbon and is used as a very good domestic fuel.
Recovery of methyl alcohol from Pyroligneous acid :
Pyroligneous acid is a homogeneous mixture of methyl alcohol, acetone and acetic acid. Hence,
methyl alcohol can be recovered from the pyroligneous acid by removing acetone and acetic acid. The
process of removal involves the following steps.
(i) Removal of acetic acid : First pyroligneous acid is treated with milk of lime [Ca(OH) 2].
Acetic acid when reacts with milk of lime produces calcium salt of acetic acid.
2CH3COOH + Ca(OH)2 ¾ ¾
¾® (CH3COO)2 Ca + H2O
Fig. 21.1 Destructive distillation of wood.
Now the mixture contain, CH3OH, CH3COCH3 and (CH3COO)2 Ca . When the mixture is subjected
to distillation, methyl alcohol and acetone distil over, leaving calcium acetate in the retort.
When calcium acetate is treated with conc. H 2SO4, again acetic acid is obtained.
(CH3COO)2 Ca + H2SO4 ¾¾
¾® 2CH3COOH + CaSO4 .
(ii) Removal of acetone : The mixture of methyl alcohol and acetone, obtained is then subjected
to fractional distillation. At 329K acetone is collected and at 338 K methyl alcohol is
collected.
(ii) Purification of methyl alcohol :
The fraction collected at 338K contains mostly methyl alcohol along with small amount
of acetone and water. First, it is treated with anhydrous CaCl 2. Methyl alcohol forms a crystalline
compound, CaCl2 4CH3OH. Then it is filtered. The crystalline compound is then decomposed by
boiling with water to give free alcohol. Finally, it is dried over quick lime and redistilled to obtain
pure methyl alcohol.
15.10.1 Uses :
Methyl alcohol is used :
1. As a solvent for fats, oils, paints and varnishes.
2. To denature (to make it unfit for drinking) rectified spirit.
3. As antifreeze for automobile radiators.
4. In the manufacture of formaldehyde, methyl chloride, dimethyl sulphate etc.
5. In the preparation of artificial perfumes like methyl salicylate and methyl
anthranilate.
6. In the preparation of dyes, perspex, plastics etc.
15.10.2Tests :
1. When heated with salicylic acid and concentrated sulphuric acid, methyl alcohol
forms methyl salicylate, which has characteristic smell of oil of winter-green or
Amritanjan like smell (distinction from ethyl alcohol.)
2. Does not form iodoform when warmed with iodine and alkali (distinction from
ethyl alcohol).
15.11 MANUFACTURE OF ETHYL ALCOHOL FROM STARCHY MATERIALS :

Ethyl alcohol is commercially prepared from starchy grains, such as potatoes, barley,
rice, wheat etc. by fermentation process. The process of fermentation is defined as the slow
decomposition of complex organic compounds into simpler compounds by the catalytic action of
enzyme.
The different steps involved in this process are,
1. Saccharification
2. Alcoholic fermentation
and 3. Distillation
ALCOHOLS 473
1. Saccharification : Starch can not be directly fermented by yeast. First starch is converted
to maltose, which on fermentation produces alcohol. The process of conversion of starch
into maltose is called saccharification and it involves the following steps.
(i) Preparation of malt extract : First the moist barley seeds are allowed to germinate in dark
at the 150C for a few days. After germination is complete, the temperature is raised to 60 0C
in order to check the growth. After that, the seeds are crushed and extracted with water.
This extract is called malt extract, which contain the enzyme diastase.
(ii) Mashing : The starchy materials like potato, rice etc. are heated in steam under pressure.
Then a paste like starchy material is obtained, which is called mash.
(iii) Hydrolysis : When malt extract is added to mash at 50 0C, hydrolysis takes place and
maltose results.
2 (C6H10O5)n + nH2O ¾ d¾
iastase
¾¾ ¾® n C12 H22 O11
Starch (mash) (Maltose)
2. Alcoholic Fermentation : The solution of maltose obtained after saccharification is cooled
to 300C. Then to it yeast is added. Yeast contains enzymes like, maltase and zymase. Here,
the maltase, converts maltose into glucose and zymase converts glucose into ethyl alcohol.
C12 H22O11 + H2O ¾Maltase

¾ ¾¾® 2 C6 H12 O6
present in
yeast
(Maltose) (glucose)
zymase
C6 H12O6 + H2O ¾ ¾ ¾ ¾® 2 C2 H5OH + 2 CO2-
present in
yeast
(Glucose) (ethyl alcohol)
3. Distillation : The fermented liquor obtained above contains 4.8% of ethyl alcohol along
with water and impurities. Then pure ethyl alcohol can be prepared by fractional distillation.
15.11.1 Uses of Ethyl alcohol :

1. Ethyl alcohol is used in the preparation of various alcoholic beverages for drinking
purpose.
2. In the manufacture of pharmaceutical preparation and medicines.
3. In the manufacture of varnishes, polishes, dyes, perfumes, transparent soaps, fruit
essences etc.
4. In the manufacture of chloroform, ether, chloral, iodoform etc.
5. As a solvent in the laboratory.
6. As a fuel in the form of alcohol.
7. For preservation of dead animals in biological laboratories.
15.11.2 Tests :
(i) Iodoform test : When a few drops of alcohol are warmed with iodine and potassium
hydroxide, yellow precipitate of iodoform with characteristic smell is obtained.
(ii) Fruity odour test : When alcohol is heated gently with sodium acetate and sulphuric
acid, a characteristic fruity odour of ethyl acetate is obtained.
(iii) Heat the alcohol with potassium dichromate and dilute sulphuric acid in test tube, a
characteristic smell of acetaldehyde is obtained.
15.11.3 Distinction of Ethanol form Methanol :

Ethanol can be distinguished from methanol by the following:
(i) Ethanol give iodoform test, whereas methanol does not.
(ii) Ethanol give acetic acid on oxidation while methanol gives formic acid. Formic acid
being a powerful reducing agent is readily distinguished from acetic acid.
[Formic acid reduces ammoniacal AgNO3 solution to metallic silver.]
15.11.4 Iodoform reaction :

Principle : A compund containing CH3CO group or a compound which on oxidation
produces another compound containing CH3CO group responds to iodoform reaction.
Example : CH3CHO, CH3COCH3 etc., respond to iodoform reaction. C2H5OH on oxidation
produces CH3CHO and therefore responds to iodoform reaction. But CH3OH on oxidation produces
HCHO which does not contain CH3CO group. Hence CH3OH does not respond to iodoform
reaction.
Statement : When warmed with iodine and alkali C2H5OH produces yellow solid iodoform
with a characteristic odour.
Reaction :
CH3CH2OH + I2 CH3CHO + 2HI
Ethyl alcohol Acetaldehyde
H H
| |
CH3 – C = O + 3I2 Cl3 – C = O + 3Hl
(Triiodoacetaldehyde)
H
|
Cl3 – C = O + NaO H CHI3 + HCOONa
(Iodoform) (Sodium formate)
(b) Ethyl alcohol similarly reacts with Cl 2 and alkali or with bleaching powder to give
chloroform.
ALCOHOLS 475
15.12 SOME IMPORTANT CONVERSIONS :

1. Primary to secondary alcohol :
conc. H2SO4 HX
R—CH2—CH2—OH ¾ ¾¾¾¾ ¾® R—CH=CH2 ¾ ¾
¾® R — CH — CH3
0
(1 alcohol) X
aq.KOH
¾¾¾¾ ¾® R — CH — CH3
OH
(20 alcohol)
2. Secondary to tertiary alcohol :
R oxdn. R R"MgX R OMgX
CH — OH ¾ ¾¾¾¾ ¾® C =O C
R' K2Cr2O7 /H 2SO4 R' R' R"
(20 alcohol)
R
Hydrolysis
R' C — OH
R"
(30 alcohol)
3. Primary to tertiary alcohol :
R PCl5 R alc.KOH R
CH — CH2OH CH — CH2 — Cl C = CH 2
R' R' R'
(10 alcohol) HX
R aq .KOH
C — CH3 ¬¾¾¾¾
R'
R
C — CH3 OH R
R' C CH3
X
0
(3 alcohol) R'
X
4. Methyl alcohol to ethyl alcohol :
PCl5
Redn.
CH3OH CH3Cl ¾KCN CH3CH2NH2
¾¾® CH3CN Na / C2H5OH HNO2
(Methanol)
CH3CH2OH
(Ethanol)
5. Ethyl alcohol to methyl alcohol :
conc.H SO Ozonolysis Pt / H2
CH3CH2OH ¾ ¾¾¾¾
2
¾4 ® CH2 = CH2 HCHO CH3OH
Redn.
(Methanol)
(Ethanol)
K2Cr2O7 /
aq. KOH
Conc
. H2SO4
Na-Salt Cl 2
CH3COOH CH4 CH3Cl
Sodalime , heat hn
Monohydric alcohols
General Formula : R — OH, CnH2n+2O
Methods of Preparation :
1. From alkyl halides
R — X + KOHaq R — OH + KX
R — X + AgOH R — OH + AgX
2. From esters : Hydrolysis
RCOOR' + KOHaq RCOOK + R'OH
3. From aldehydes and Ketones :
Reduction by Na/C2H5OH or H2/Pt,Pd or Ni, or
NaBH4 or LiAlH4
Redn.
R — CHO R CH2OH
R Redn. R
C=O CH — OH
R' R'
4. From Grignard reagent :
H 2O
HCHO + RMgX ® RCH2OMgX RCH2OH (10)
R H 2O R
R'CHO + RMgX ® CH — OMgX CH — OH (20)
R' R'
R R
H 2O
R' CO R" + RMgX ® R' C — OMgX R' C — OH (30)
R" R"
5. From aliphatic primary amines :
R — NH2 + HNO2 ® R — OH + N2 + H2O (except CH3NH2)
Reactions :
(a) Reactions involving H— atom of — OH group
Reactivity : 10 > 20 > 30
(i) With alkali metals like Na or K or Li
2R — OH + 2Na ® R — ONa + H2 (Exothermic)
(ii) With carboxylic acids, acid chlorides
ALCOHOLS 477
conc.H 2SO 4
R — OH + HOOCR' R'COOR + H2O
R — OH + ClOCR' ® R'COOR + HCl
(b) Reactions involving —OH group
Reactivity : 30 > 20 > 10
(i) With mineral acids : HI > HBr > HCl in reactivity
anh. ZnCl2
R — OH + HCl (dry) R — Cl + H2O
heat
R — OH + HBr R — Br + H2O
heat
R — OH + HI R — I + H2O
(ii) With PCl5, PCl3, PBr3, PI3, or SOCl2
R — OH + PCl5 ® R — Cl + POCl3 + HCl
3R — OH + PBr3(P4+Br2) ® 3R — Br + H3PO3
3R — OH + PI3(P4+ I2) ® 3R — I + H3PO3
R — OH + SOCI2 ® R — Cl + SO2 +HCl
(c) Reactions involving the entire molecule
(i) Oxidation : Acidified K2Cr2O7, or alkaline KMnO4 or acidified KMnO4
R — CH2 — OH ® RCHO ® RCOOH
R R drastic
CH — OH ® C=O Mixture of acids with
R' R' oxdn.
less no. of C — atoms.
R
R' drastic
C — OH Mixture of ketone and acid with less no.of C– atoms.
oxdn.
R"
(ii) Catalytic dehydrogenation.

Alcohol vapour passed over reduced Cu at 3000C
Cu
RCH2OH RCHO + H2
3000C
Cu R
R — CH — OH C = O + H2
3000C R'
R'
R Cu R
R' C — OH 3000C C = CH2 + H2O
R'
CH3
Distinction between 10 , 20 and 30 alcohols
K 2C r2O 7
1. Oxidation : 10 alcohol Aldehyde and acid (with same no. of C - atoms)
H 2S O 4
20 alcohol ® ketones oxdn Acids (with less no. of C - atoms)

30 alcohol ® ketones and acids (with less no. of C - atoms)
2. Catalytic dehydrogenation : Reduced Cu at 3000C
10 alcohol ® Aldehyde
0
2 alcohol ® Ketone
30 alcohol ® Olefin
3. Lucas Test : Conc. HCl in presence of anhydrous ZnCl2
30 alcohol ® Immediate turbidity
0
2 alcohol ® Turbidity after 5 minutes
10 alcohol ® Turbidity on heating only.
(No turbidity in cold)
4. Victor Meyer's Test :
AgNO 2
R — CH2— OH P I 3 R — CH2 — I R — CH2 — NO2
(10 alcohol )
HNO2 alkali
R — C — NO 2 Blood red colour
N — OH
(Nitrolic acid)
R P I3 R AgNO 2 R
CH — OH CH — I CH — NO2
R' R' R'
(20 alcohol )
HNO2 R alkali
C — NO 2 Blue colour
R'
N=O
(Pseudonitrol)
R R R
R' P I3 R' AgNO 2 R'
C — OH C— I C — NO2
R" R" R"
HNO2 alkali
No reaction No colour
ALCOHOLS 479
QUESTIONS
Very short Anser Questions ( 1 mark each)
1. What class of compounds have a molecular formula C nH2n + 2O
2. How does metallic sodium react with methyl alcohol ?
3. Methyl alcohol does not give iodoform test, why ?
4. Complete the following equation.
CH3CH2OH + SOCl2 ® —— + —— + HCl -
5. What is the name of the functional group in CH3CH2OH
6. Give the IUPAC name of a compound which is isomeric with diethyl ether.
7. How ethyl alcohol can be converted to acetic acid ?
8. Ethanol is obtained by —— reaction of acetaldehyde. (oxidation, reduction, polymerisation)
9. What is the IUPAC name of the following compound ?
Cl
|
Cl – CH – CH2 – OH
10. What alcohol is present in pyroligneous acid ?
11. Write the structural formula of Butan - 2 - ol.
12. What organic compound is obtained when ethyl bromide reacts with aqueous NaOH solution.
13. What happens when ethanol is treated with conc. H2SO4 at 443 K ?
14. Complet the following equation- C2H5OH + CH3COCl ® —— + ——
Short answer Questions (2 marks each) :
1. Give equation for the reaction of ethyl bromide with aqueous and alcoholic KOH. Name
the products giving equation for the reaction.
2. A primary alcohol is treated with PCl5. Name the products giving equation for the reaction.
3. Isopropyl alcohol is oxidised with K2Cr2O7 and H2SO4. Write the products giving equation.
4. Give one chemical test to distinguish between CH3CH2OH and CH3OH.
5. Write with equation, what happens when ethyl alocohol vapour is passed over reduced
copper at 3000C.
6. In the preparation of aldehydes from primary alcohol on oxidation, aldehyde is distilled
out. Why is it so ?
7. Complete the following reactions assigning structures of A, B, and C
+
¾PCl
¾5 ® ¾KCN
¾¾®
H
CH3CH2OH A B ¾H¾¾® C.
2O
8. (a) How do you distinguish between a primary and secondary alcohol ?

(b) How different classes of alcohols can be tested by Lucas test ?
9. What happens when acetic acid reacts with ethyl alcohol in presence of conc.H 2SO4 ?
10. How do you distinguish between primary and secondary alcohol by catalytic
dehydrogenation ?
11. How is maltose converted to ethyl alcohol by fermentation process.
12. Write the equations for the oxidation of aliphatic primary, secondary and tertiary alcohols.
13. How many structural isomers of alcohol with molecular formula C 4H9OH are possible ?
Give their IUPAC name. Which one of the isomers is optically active ?
14. Alcohols are freely soluble in water but alkyl halides are not, explain why ?
15. Boiling points of alcohols are higher than the corresponding alkane. Give reasons.
16. Arrange the following in order of their increasing reactivity towards Lucas reagent.
Butan-2-ol, 2-methylpropan - 2-ol, Butan-1-ol.
17. (a) Write a method of conversion of methyl alcohol to ethyl alcohol. Give equation.
(b) How will you convert ethyl alcohol to methyl alcohol?
18. How can you get ethyl chloride from ethyl alcohol ? Give equation.
19. What happens when acetyl chloride is treated with ethyl alcohol ? Give equation.
20. How will you convert ethanol to 2-hydroxy -3-butenoic acid.
21. Molecular mass of ethanol and dimethyl ether is the same. Explain why ethanol is a liquid
at room temperature and dimethyl ether is a gas.
22. Explain why sodium can not be preserved in alcohol.
23. A neutral liquid A on treatment with Lucas reagent produces a compound B, which upon
treatment with alc.KOH yields a compound C. The compound C decolourises bromine
water and upon ozonolysis forms only methanal. Deduce the structures of A,B and C and
explain the reactions.
24. (a) Identify A, B, C and D in the following sequence of reactions :
C2H5OH ¾K 2Cr2O7 ® A
¾¾¾¾ [O]
¾¾
NH 3 ® C
¾® B ¾ ¾¾
H SO 2 4
heat
D
(b) Identify A & B in the following reaction :
O3
¾® B ¾¾® CH2O + CH3COCH3
A ¾Cu
¾
573 K H 2O/Zn
ALCOHOLS 481
25. An organic compound A (C4H10O) reacts with HI giving a compound B (C4H9I), which on
reduction gives n-butane. On oxidation 'A' gives a compound C (C4H8O) and then an acid
D (C4H8O2).
Deduce the structures of A, B, C and D and mention their IUPAC names.
26. Describe a method to distinguish a primary alcohol from a secondary alcohol.
Short Answer type Question (3 marks each) :

1. How are the alkanols classified ? Give an example of each class with their IUPAC names.
2. These are three unlabelled bottles containing methyl alcohol, ethyl alcohol and diethyl
ether. How will you identify each of them?
3. How will you convert methanol to ethanol and vice versa?
4. How many different isomeric alcohols having molecular formula C 4H10O are possible?
Name them. How will you diffentiate them?
5. Ethyl alcohol (A) reacts with conc. H2SO4 at differnt temperatures to give different products
B, C and D.
167 – 170°C
®B
100°C
A + conc H2SO4 ® ®C
(Excess of A)
®D
140°C
Name the compounds B, C and D.
6. An organic compound gives hydrogen on reacting with sodium metal. It also gives iodoform
test and forms an aldehyde of molecular formula C 2H4O on oxidation with acidified
dichromate. Name the compound and give the equation of these reactions.
7. How will you convert ethanol to iodoform and chloroform?
8. Exaplain why :
(i) Ethanol is less acidic than phenol.
(ii) Though dimethyl ether and ethanol are isomers, still the dimethyl ether is a gas and
ethonol is a liquid at room temperature.
Long Answer type Question (7 marks each) :

1. Describe two methods of preparation of alcohol. Write its reaction with (a) PCl 5 (b)
CH3COOH. How would you prepare methyl alcohol from it.
2. How ethyl alcohol can be converted to methyl alcohol and vice-versa ? Write any two
reactions by which ethyl alcohol is distinguished from methyl alcohol.
3. Write notes on any two of the following :

(a) Victor Meyer's method for distinction of different classes of alcohols ?
(b) How methyl alcohol can be converted into ethyl alcohol and vice versa ?
4. What are primary, secondary and tertiary alcohol ? How can you obtain each one of these
by using a Grignard reagent ? What happens when these classes of alcohols are (i) oxidised
with K2Cr2O7 and H2SO4 (ii) passed over heated copper.
5. What is fermentation ? How is ethanol obtained commercially by fermentation of starch ?
What happens when ethanol reacts with (i) sodium metal (ii) copper at 300 0C (iii) ethanoic
acid and (iv) Red phosphorus and I2.
6. How can you distinglish between primary, secondary and tertiary alcohols by oxidation
method ?
Write the principle of manufacture of ethyl alcohol from starchy materials.
How can you prepare (a) ethyl alcohol from methyl alcohol (b) methyl alcohol from ethyl
alcohol.
7. Describe the principle of manufacture of methyl alcohol from wood. Give the conversion
of methyl alcohol to ethyl alcohol and vice versa.
8. How would you distinguish between 10, 20 & 30 alcohols by
(a) Oxidation method (b) Catalytic dehydrogenation method ?
9. How do you classify different types of monohydric alcohols? Distinguish the different
classes of alcohols by Victor Meyer's method. How can methyl alcohol be converted to
ethyl alcohol.
MULTIPLE CHOICE QUESTIONS WITH ANSWERS
1. Which of the following compound is optically active ?

(a) CH3CH2OH (b) CH2OH . CHOH . CH2OH
(c) CH3CHOH C2H5 (d) CCl2F2
2. An isomer of ethanol is
(a) methanol (b) dimethyl ether
(c) acetone (d) diethyl ether
3. How many optically active stereoisomers are possible for Butane - 2, 3-diol ?
(a) 1 (b) 3
(c) 4 (d) 2
ALCOHOLS 483
4. Butan - 1 - ol and Butan - 2 - ol are

(a) Chain isomers (b) Functional isomers
(c) Position isomers (d) Optical isomers
5. Which of the following compound is called carbinol ?
(a) CH3OH (b) C2H5OH
CH 3
(c) C3H7OH (d) CH — OH
CH 3
6. How many structural isomers of alcohol with molecular formula C 4H9OH are possible ?
(a) 5 (b) 7
(c) 3 (d) 6
7. Which one is primary alcohol ?
(a) Butan – 2 – ol (b) Propan – 2 – ol
(c) Butan – 1 – ol (d) 2,3 dimethylhexan – 4 – ol
8. Action of nitrous acid on ethyl amine gives
(a) C2H6 (b) C2H5OH
(c) C2H5OH and C2H4 (d) C2H5OH and NH3
9. Ethyl alcohol is heated with conc. H2SO4 . The product formed is,
(a) CH3CO . OC2H5 (b) C2H6
(c) C2H4 (d) C2H2
10. The compound 'B' formed in the following sequence of reaction .
CH3CH2CH2OH ¾PCl
¾5 ® A ¾alc.KOH
¾¾¾¾® B, is
(a) Propyne (b) Propanal

(c) Propane (d) Propene
11. The compound which reacts fastest with Lucas reagent at room temperature is,
(a) Butan – 1 – ol (b) Butan – 2 – ol
(c) 2–methylpropan –2–ol (d) 2 – methylpropan – 1 – ol
12. Primary and Secondary alcohols on action of reduced copper gives
(a) aldehydes and ketones respectively (b) ketones and aldehydes respectively
(c) only ketones (d) only aldehydes.
13. When vapours of an alcohol are passed over hot reduced copper, alcohol is converted into
alkene, the alcohol is
(a) Primary (b) Secondary
(c) Tertiary (d) None of these
14. Dehydrogenation of 2 – butanol gives

(a) 2 – butene (b) butanone
(c) Butanal (d) None of these
15. Which of the following compounds is oxidised to prepare methyl ethyl ketone ?
(a) Propan – 2 – ol (b) Butan – 1 – ol
(c) Butan – 2 – ol (d) t – butyl alcohol
16. Which of the following gives secondary alcohol
(a) CH3CO CH3 (b) CH3CHO
(c) CH3COOH (d) CH3—O—CH3
17. Fermentation of starch solution to ethyl alcohol does not require
(a) diastase (b) invertase
(c) maltase (d) zymase
18. The boiling point of ethyl alcohol should be less than
(a) Propane (b) dimethyl ether
(c) Formic acid (d) None of the above
19. A low boiling alcohol failed to give the Lucas test, but gives a positive iodoform test. The
alcohol is :
(a) Methanol (b) Propan – 1 – ol
(c) Butan – 1 – ol (d) Ethanol
20. A compound 'X' having molecular formula C4H10O when oxidised produces an acid having
formula C4H8O2. The compound 'X' is
(a) secondary alcohol (b) primary alcohol
(c) tertiary alcohol (d) an ether
21. The enzyme which can catalyse the conversion of glucose to ethanol is
(a) Zymase (b) Invertase
(c) Maltase (d) Diastase
22. An organic compound 'X' on treatment with acidified K2Cr2O7 gives a compound 'Y'
which reacts with I2 and sodium carbonate to form tri-iodomethane. The compound 'X' is,
(a) CH3OH (b) CH3COCH3
(c) CH3CHO (d) CH3CH(OH) CH3
23. The compound which does not respond to iodoform test is,
(a) CH3OH (b) CH3CHO
(c) CH3COCH3 (d) C2H5OH
ALCOHOLS 485
24. The reaction between alcohol and carboxylic acid is called.

(a) Hydrolysis (b) Saponification
(c) Esterification (d) Hydrogenation
25. In CH3CH2OH, the bond that undergoes heterolytic cleavage most readily is,
(a) C–C (b) C – O
(c) C–H (d) O – H
26. Which one of the following is an isomer of diethyl ether ?
(a) (CH3)3 C – OH (b) (CH3)2 CH OH
(c) C3H7 OH (d) (C2H5)2 CH OH
27. 1 – Chlorobutane on reaction with alcoholic potash gives,
(a) But – 1 – ene (b) Bnt – 2 – ene
(c) Butan – 1 – ol (d) Butan – 2 – ol
28. Ethyl alcohol is miscible with water in all proportions. It is because,
(a) It is acidic in nature (b) It dissociates in water
(c) It is basic in nature (d) It forms hydrogen bonding with water
29. Which of the following compounds has the highest boiling point ?
(a) CH3CH2CH3 (b) CH3CH2OH
(c) CH3Cl (d) CH3—O — CH3
30. Which of the following compounds has the lowest boiling point ?
(a) n – butyl alcohol (b) sec – butyl alcohol
(c) tert – butyl alcohol (d) 2 – methyl propan – 1 – ol
31. Hydrogen bonding is maximum in,
(a) Ethyl chloride (b) Ethanol
(c) Diethyl ether (d) Triethylamine
32. Which one of the following is soluble in water ?
(a) CCl4 (b) C6H6
(c) CH3OH (d) CH4
33. Hydrochloric acid reacts fastest with,
(a) Propan – 1 – ol (b) Propan – 2 – ol
(c) 2 – methyl propan – 1 – ol (d) 2 – methylpropan – 2 – ol
34. A mixture of water and alcohol can be separated by
(a) evaporation (b) decantation
(c) distillation (d) filtration
35. Secondary alcohol on oxidation gives,

(a) Ketone (b) Aldehyde
(c) Ether (d) Hydrocarbon
ANSWERS
1. c 2. b 3. d 4. c 5. a 6. b 7. c
8. b 9. c 10. d 11. c 12. a 13. c 14. b
15. c 16. a 17. b 18. c 19. d 20. b 21. a
22. d 23. a 24. c 25. d 26. a 27. a 28. d
29. b 30. c 31. b 32. c 33. d 34. c 35. a
qqq
PHENOLS 487
CHAPTER - 16
PHENOLS
Phenols are compounds with the general formula Ar – OH, where Ar is phenyl, substituted
phenyl or other aryl groups. Phenols differ from alcohol in having –OH group directly attached to
an aromatic ring. Phenols are often considered as derivatives of benzene, the simplest member of
the family being phenol. Methyl phenols are called cresols. Phenols are classified as mono–, di
– or trihydric phenols according as they contain one, two or three –OH groups attached directly to
aromatic nucleus. Monohydroxy benzene is called phenol.
OH OH OH OH OH
Cl CH3
CH3
Phenol o-Chlorophenol o- cresol m-cresol CH3
p-cresol
The functional group in phenol is phenolic –OH group. Phenol is also known as carbolic
acid.
16.1 METHODS OF PREPARATION :
The following general methods of synthesis of phenols are used for their preparation.
(i) Hydrolysis of Aryl halides : Aryl halides yield phenol when hydrolysed with aque-
ous sodium hydroxide. For example chlorobenzene is hydrolysed to phenol at high temperture
and pressure by NaOH. The is known as Dow’s Process.
+
Cl 370,o 4000 psi ONa
+2 NaOH NaCl,
H2O
Chlorobenzene
OH
HCl + NaCl
The above hydrolysis can also be effected by water in presence of copper as catalyst at
4000C temperature and 4000 psi pressure.
Cl Cu-catalyst OH
o
+ H2O + HCl
4000 Psi
(ii) Alkali fusion of sodium arenesulphonates
Simple phenols are prepared conveniently by fusing sodium arenesulphonates with so-
dium hydroxide at about 300OC. A mixture of sodium phenoxide and sodium sulphite is pro-
duced from which phenol is liberated by acidification.
Ar – SO3– Na+ + 2 NaOH ArO– Na+ + Na2SO3 + H2O
Sodium arenesulphonate Sodium phenoxide
– +
Ar O Na + HCl ArOH + NaCl
For example, phenol is synthesised from benzene as follows.
Benzene sulphonic acid can be obtained from benzene upon sulphonation with fuming
sulphuric acid. Benzene sulphonic acid is fused with NaOH at 300 0 C. A mixture of sodium
phenoxide and sodium sulphite is produced which upon acidification yields phenol.
SO3H ONa OH
NaOH
H2SO4, SO3 HCl
3000C
Benzene sulphonic acid Sod. phenoxide Phenol
(iii) From diazonium salts : When an aqueous solution of aryldiazonium chloride is

heated, the diazonium group is replaced by –OH group and phenol is formed.
+
Cl 2 OH + HCl
benzene diazonium chloride Phenol

This reaction is usually conducted in an acid medium to prevent the coupling of phenol
with unreacted diazonium salt.
Application : The method is useful for the preparation of m-chlorophenol which cannot
be prepared by electrophilic chlorination of phenol.
Cl Cl
+
Cl+ H2O OH + HCl
m-chlorophenol
PHENOLS 489
Mechanism :
In this process, water H2O is the nucleophile.
+
..
HO2
N2 N2 + +
+
OH2 + OH
-H
Phenol
(iv) From Cumene : The most recent commercial synthesis of phenol is from cumene,
isopropyl benzene. The process involves two steps.
(a) Preparation of cumene (isopropylbenzne)

Cumene is synthsised from benzene and propylene, both derived from petroleum by Friedel-
Crafts Reaction.
CH3
C H
Anhyd.AlCl3
CH3
Cumene
(b) Cumene is then oxidised by aerial oxygen at 130 0C in the presence of metal catalyst
(or initiator) to cumene hydroperoxide, which is converted by aqueous acid (dilute sulphuric
acid) into phenol and acetone. This process is of great importance as it provides the principal
source for the commercial preparation of phenol and acetone.
CH3 CH3
C H O2 C O
0
130 C, Cat
CH3 CH3 OH
Cumene hydroperoxide
CH3
+ OH
H2O, H
+ C=O
CH3
Acetone
16.2 PROPERTIES :
(A) Physical properties :
The simplest phenols are either liquids or low melting solids having quite high boiling
points. Phenol is a colourless crystalline solid with low melting point (43 0C), fairly soluble in
water (9g/100gH2O). The solubility is due to the hydrogen bonding with water molecules. Most
of the other phenols are insoluble in water, but soluble in organic solvents. Phenol has a
characteristic odour and is very poisonous.
While comparing the physical properties of nitrophenols, it has been observed that o-
nitrophenol has low m.p. and is volatile. It has low solubility (0.2g/100g H 2O at 250C). This is
because of the proximity of –OH and – NO2 group in the benzene ring for which they form
intramolecular hydrogen bonding.
O
H + +
+O O N O H O N O H
N
O O
O
Intramolecular hydrogen bonding Intermolecular hydrogenbonding
in o-nitrophenol in p-nitrophenol.
This gives rise to a stable six membered ring (chelation) and can not form associated
molecules. Therefore, it exists as a single unit and it has low m.p, low b,p, low solubility and high
volatility compared to its other isomers. On the other hand, due to the greater distance between –
OH and –NO2 group in m-nitrophenol and p-nitrophenol, such intramolecular hydrogen bonding
is not possible. They form associated molecules by intermolecular hydrogen bonding and have
higher m.p., b.p than o-isomer. They are much less volatile than o-isomer. Their solubility is
more in water because they form hydrogen bonding with water. This is the reason why o-nitrophenol
is steamvolatile and it can be separated from m-and p-isomers by steam distillation.
(B) Chemical properties

ACIDITY OF PHENOLS
The acidity of a compound is defined as its ability to release a proton in presence of water.
Phenols when dissolves in water form phenoxide ions, hence acidic in nature.
.. – +
—O
.. — H —O + H
Phenol Phenoxide ion
Phenols are weaker acids than carboxylic acid. This is evident from their K values. (K
-10 -5
for phenol is 10 and that of CH COOH is 10 )
3
PHENOLS 491
Both phenol and phenoxide ion exhibit resonance. A number of resonating structures
can be written for both phenol and phenoxide ion.
.. .. + .. + .. + +d
OH OH
..
..
OH OH OH OH
| | || – || – || ||
d-
|||
–
Phenol
I II III IV V Resonance
hybrid
O– O– O O O O
| | || || || – || –
–
|||
–
Phenoxide ion
I II III IV V Resonance
hybrid
In case of phenol forms I and II are the two Kekule resonating structures. In forms III, IV
and V, there is charge separation. Since separation of charge costs energy, these forms are known
as high energy forms and they do not contribute to the resonance hybrid.
One the otherhand, in case of phenoxide ion structures I to V contribute to the resonance
hybrid. In this case there is no charge separation, rather there is charge delocalisation. Thus
resonance hybrid of phenoxide ion is more stable than that of phenol. The equilibrium between
the two is represented as
....
— .... –
— + H+
O— O
H
Phenol Phenoxide ion
(resonance hybrid structure) (resonance hybrid structure)
Since the phenoxide ion is more resonance stablised thean phenol itself, the equilibrium
+
is shifted towards right releasing H ions. This explains why phenol behaves as a weak acid.
Effect of substituents on acidity of phenol
Presence of electron releasing group decreases the acidity of phenol whereas presence
of electron withdrawing group enhances the acidity. When an electron releasing group (say CH
3
– , C H – etc) present the –ve charge on the phenoxide ion gets intensified. As a result the anion
2 5
becomes less sable and acidity of phenol decreases.
–
O H + H2O O + H3O+
R R
R = Electron releasing Destabilised
On the other hand, when an electron withdrawing group ( -X, -CHO, - NO , - COOH
2
etc.) is present, electrons from the ring system are withdrawn and that results in greater dispersal
of the –ve charge of the phenoxide anion. The phenoxide ion thus gets stabilised and acidity of
phenol is enhanced.
–
O H + H2O O + H3O+
R R
R = Electron withdrawing Stabilised
Thus, methyl phenols are less acidic than phenol whereas chlorophenols are more acidic than
phenol.
Again, since inductive effect of a substituent operates only through the covalent bonds,
its intensity gets reduced with increase in distance from the reaction centre.
In case of isomeric chlorophenols, the K ortho > K meta >K para.
a a a
However in all the cases the acidity of phenol can not be explained by taking only
inductive effect into account. For example, among nitrophenols meta isomer is the weakest acid
whereas among alky1 phenols, meta isomer is the strongest. This can be explained by taking
resonance effect into account along wit inductive effect. The phenoxide anion gets stabilized by
the dispersal of –ve charge.
–
O O O O
| || || ||
– –
| | || |
+ N – +N
– N – N –
–O
|
||
||
||
|
O O O O + O O + O
The lower acidity of metanitro isomer is due to the fact that m-nitro phenoxide anion is
stabilised by inductive effect only and no resonance effect is operating due to absence of conjugate
system. –
O O
| || –
+ O + O
||
||
N N
|
| |
O– O–
(no further resonance with NO2 group)
PHENOLS 493
The values of K for three nitrophenols are metioned below.

a
OH OH OH
| NO2 | |
|
NO2 |
NO2
o-nitrophenol m-nitrophenol p-nitrophenol
Ka = 600 x 10–10 Ka = 50 x 10–10 Ka = 690 x 10–10
It is important to mention here that presence of electron withdrawing group at the ortho
position in some cases makes the phenol weaker than the para isomer. For example, o –fluorophenol
and o-nitrophenol are weaker than their corresponding p-isomers.
The reason behind this is that the acidic hydrogen is involved in intramolecular hydrogen
bonding with fluorine and oxygen.
–
+ O
O—H O N—
||
| | H
|
—F —O
o - Fluorophenol o - Nitrophenol
(a) Esterification Reaction : Phenol reacts with acid chlorides or acid anhydrides in
presence of aqueous alkali solution to give phenyl esters. The alkali first forms the phenoxide
ion which then reacts with the acid chloride to form the ester.
OH + Na2CO3 O Na+ + H2O
(Phenol) (Sodium phenoxide)

O O
+
O Na + CH3 - C - Cl O - C- CH3 +NaCl
(Sodium phenoxide) (Phenyl acetate)

O O
+
O Na + C - Cl O-C + NaCl
(Sodium phenoxide) (Phenyl benzoate)

Introduction of acetyl group (CH3CO–) in phenol forming an ester is called acetylation.

Acetylation of salicylic acid gives acetyl salicylic acid (aspirin).
COOH COOH
OH OCOCH3
+ (CH3CO)2O H+ + CH3COOH
Salicylic acid Acetylsalicylic acid

(aspirin)
When a mixture of phenol and benzoylchloride is shaken with excess of aqueous NaOH,
the ester phenyl benzoate is formed and this is called benzoylation and the reaction is known as
Schotten Baumann reaction.
(b) Electrophilic Substitution reactions

As already discussed the –OH group activates the benzene ring to electrophlic attack
and is ortho paradirecting.
(i) HALOGENATION :
When treated with excess of aqueous bromine solution phenol produces 2, 4, 6–
+
tribromophenol. Br is the electrophile.
Br2 + Br2 Br+ + Br3–
OH OH
|
Br Br
+ 3Br+
|
Br
2, 4, 6 tribromophenol
But when phenol is treated with limited amount (1 mole) of Br 2 dissolved in less polar
solvents like CHCl3, CS2 etc monobromophenols are produced
OH OH OH
| | |
Br2 Br
+
+ HBr
CS2 |
Br
o-bromo phenol p- bromophenol
PHENOLS 495
(ii) SULPHONATION
When treated with conc H2SO4 phenol is readily sulphonated to produce o-phenol
(+)
sulphonic acid and p–phenol sulphonic acid. SO3H is the electrophile.
+ –
2H2SO4 SO3H + HSO4 + H2O
OH OH OH
| | |
ConcH2SO4 SO3H
+
|
SO3H
o- phenol
p- phenol
sulphonicacid
sulphonicacid
At room temperature, ortho isomer is the main product while at 100 0c, para isomer is the
main product.
(iii) NITRATION
Phenols undergo nitration when treated with dilute HNO3. The products are o-nitro
phenol and p-nitro phenol. NO +2 is the electrophile.
+ –
2HNO3 NO2 + NO3+ H2O
OH OH OH
| | |
dil HNO3 NO2
+
|
NO2
o-nitro phenol p- nitrophenol
(iv) Reimer – Tiemann Reaction

When phenol is treated with chloroform (CHCl ) is presence of aq. NaOH at 330 K,
3
to –CHO group is introduced mainly in the ortho position to –OH group. The process is known
formylation. Though ortho isomer is the major product, yet para isomer is obtained to a smaller
extent. Bot the isomers can be separated by steam distillation after acidification. This reaction is
known as Reimer - Tiemann Reaction.
Reimer Tiemann reaction :

– –
OH O O
| | CHO |
aq. NaOH
|
+ CHCl3
330K
H3O+ |
CHO
OH H3O+
| CHO OH
|
|
o - Hydroxy benzaldehyde |
or Salicylaldehyde CHO
(Major product)
p - Hydroxy benzaldehyde
Mechanism: (Minor product)
Formation of very reactive intermediate dichlorocarbene by the action of base on

chloroform.
– – H2O – Cl
–
OH + H – CCl3 : CCl3 :CCl2
Dichlorocarbene.
(electrophile)
The carbon atom in :CCl2 contains only six valence electrons, thus acts as an electrophile in
aromatic substitution.
Electrophilic substitution in benzene ring

– –
O O O
| || H | CHCl2
–H+
|
–
|
: CCl2 CCl2
o - (dichloromethyl)
phenoxide ion.
PHENOLS 497
Hydrolysis and acidification :
– –
OH Cl OH Cl
| C | C –
Cl – O — H + OH
+ OH
–
O
| CHO –
|
+ Cl + H2O
–
O OH
| CHO | CHO
H3O+
|
|
Salicylaldehyde
(Major product)
Ortho-isomer predominates due to its greater stability resulting from intramolecular hydrogen
bonding which is shown below.
H
— O
O ||
|
C
H
|
Intramolecular hydrogen bonding in salicylaldehyde
If CCl4 is taken in place of CHCl3, salicylic acid is obtained instead of salicylaldehyde
OH OH OH
| | |
NaOH(aq) — COOH
+ CCl4 — +
OH
|
COOH
o - Hydroxy benzoic acid p - Hydroxy benzoic acid

or Salicylic acid (Minor product)
(Major product)
(c) Oxidation : Phenol is easily oxidised without disruption of its carbon skeleton to form
p-benzoquinone.
CrO2Cl2
OH + 2[O] O O + H2O
Phenol p-Benzoquinone
Similarly, hydroquinone on oxidation with silver salts yield p-benzoquinone
HO OH + 2Ag+ OH– O O + 2Ag + 2H2O
Hydroquinone p- benzoquinone
The oxidation of phenols is explained by the fact that the presence of – OH group in the
ring furnishes electrons to the ring which thus renders susceptible to oxidation especially in
alkaline medium.
(d) Reaction with zinc dust : When a phenol is distilled with zinc dust, the –OH group is
replaced by a hydrogen atom. Zinc removes the oxygen of the phenolic group as zinc oxide, to
yield the parent hydrocarbon.
OH + Zn + ZnO
Phenol Benzene
1. Dow’s Process : Chlorobenzene reacts with aqueous sodium hydroxide under high
temperature and pressure to form phenol.
2. Acidity of phenol is due to resonance stabilisation of phenoxide ion.
3. Presence of electron releasing group decreases the acidity of phenol whereas presence of
electron withdrawing group increases its acidity.
4. Reimer-Tiemann reaction : Phenol is treated with chloroform in presence of aq.NaOH at
330 K forming salicylaldehyde upon acidification.
5. Phenolic –OH group can be acetylated or benzoylated forming esters. Benzoylation process
is known as Schotten Baumann reaction.
PHENOLS 499
QUESTIONS
A. Very Short Answer Type (1 Mark)
(i) Phenol is acidic because is more stable than .
(ii) Formylation of phenol is reaction
(iii) Benzene can be obtained by heating phenol with
(iv) Phenol reacts with to give o-and p- Nitrophenols.
(v) Phenol gives with CrO2Cl2
B. Short Answer Type (2 Marks)
1. Complete the following reaction giving the names of the products :
(i) C6H5OH + Zn dust
(ii) C6H5OH + Br2 water
conc H2SO4
(iii) C6H5OH + HNO3
(iv) C6H5OH + HNO2
(v) C6H5OH + CHCl3 + KOH
(vi) C6H5OH + CCl4 + KOH
(vii) C6H5OH + CO2
2. Give the resonating structures for phenol and phenolate ion.
3. How will you distinguish between ethyl alcohol and phenol.
4. Give the reaction of phenol with benzene diazonium chloride.
5. How will you obtain the following form phenol.
(i) Salicyladehyde (ii) Benzene
(iii) Picric acid (iv) Nitrophenol
(v) Salicylic acid (vi) p-cresol
C. Short answer type (3 Marks)
(i) What is Dow’s process ?
(ii) What is Reimer-Tiemann reaction ?
(iii) Why phenol is acidic, but alcohol is neutral. Explain.
(iv) How can you carry nitration is phenol ? Explain.
(v) What is the directive influence of phenolic group ? Explain with reasons.
D. Long answer type (7 marks each)
(i) How is phenol prepared from benzene ? How can phenol be converted to
(i) benzene (ii) salicylaldehyde.
(ii) How can phenol be prepared from cumene ? Convert phenol to aspirin and p-
benzoquinone.
(iii) Starting from benzene diazonium chloride, how can phenol be prepared ? How can
phenol be sulphonated ? What is the electrophile for this reaction ?
E. Multiple choice type questions

(i) When phenol is distilled with zinc dust, the product is
(a) toluene (b) benzene (c) xylene (d) none of these
(ii) Phenol is less acidic than
(a) acetic acid (b) p-methoxy phenol (c) o-nitrophenol (d) ethanol
(iii) Electrophilic substitution in phenol takes place at
(a) o-position only (b) p-position only (c) o- and p-position (d) m-position only.
(iv) Sodium salt of benzene sulphonic acid on fusion with caustic soda gives
(a) C6H5OH (b) C6H6 (c) C6H5COOH (d) none of these
(v) Phenol gives salicylaldehyde on heating with CHCl3 & NaOH. The reaction is called
(a) Cannizzaro’s reaction (b) Claisen condensation
(c) Reimer-Tiemann reaction (d) Perkin reaction
(vi) Chlorobenzene on heating with NaOH at high temperature and pressure gives
(a) Phenol (b) Benzaldehyde (c) Benzene (d) Chlorophenol
(vii) Phenol reacts with Br2 in CCl4 at low temperature to give
(a) m-bromophenol (b) o- and p-bromophenol (c) p-bromophenol (d) 2,4,6-
tribromophenol
(viii) Intramolecular hydrogen bonding is found in
(a) phenol (b) o-nitrophenol (c) p-nitrophenol (d) m-nitrophenol
(ix) p-nitrophenol is stronger acid than phenol because nitrogroup is
(a) Electron donating (b) Electron withdrawing (c) Acidic (d) Basic
(x) The most convenient method of removing a phenolic group from a compound is by
(a) reduction with Sn + HCl
(b) heating strongly
(c) heating strongly with copper
(d) distilling with zinc dust.
ANSWER
A. (i) phenoxide, phenol (ii) Riemer-Tiemann (iii) Zinc (iv) dil HNO 3 (v) p-benzoquinone
D. (i) b (ii) a (iii) c (iv) a (v) c (vi) a (vii) b (viii) b (ix) b (x) d.
qqq
ETHERS 501
CHAPTER - 17
ETHERS
The general formula of ethers is R–O–R'. Both the alkyl or aryl groups (R/Ar or R'/Ar')
may be same or different. The functional group of ether is 'OR / OAr' (alkoxy/aryloxy).
17.1 CLASSIFICATION OF ETHERS :

Ethers are classified as simple or symmetrical ethers if the two alkyl or aryl groups
attached to the oxygen atom are the same, and mixed or unsymmetrical ethers if the two groups
are different.
(a) Simple or Symmetrical ethers :
CH3—O—CH3 CH3CH2—O—CH2CH3 C6H5—O—C6H5
Dimethyl ether Diethyl ether Diphenyl ether
(b) Mixed or Unsymmetrical ethers :
CH3—O—CH2CH3 C6H5—O—CH3 C6H5—O—CH2C6H5
Ethyl methyl ether Methyl phenyl ether Benzyl phenyl ether
1. Aliphatic ethers in which R and R' are both alkyl groups. For example,
CH3—O—CH3 CH3—O—CH2CH3 CH3CH2—O—CH2CH3
Demethyl ether Ethyl methyl ether Diethyl ether
2. Aromatic ethers in which either one or both R and R' are aryl groups.
Aromatic ethers are further subdivided into phenolic ethers and diaryl ethers.
Ethers in which one of the groups is aryl while the other is alkyl are called phenolic
ethers or alky aryl ethers. On the other hand, ethers in which both the groups are aryl are called
diaryl ethers. For example,
C6H5—O—CH3 C6H5—O—C6H5
Methyl phenyl ether Diphenyl ether
(Phenolic ether) (Diaryl ether)
17.2 NOMENCLATURE OF ETHERS :

1. Common system : The common names of ethers are derived by naming the two akyl
or aryl groups linked to the oxygen atom as separate words in alphabetical orders and adding the
word ether. In case of symmentrical ethers, the prefix di is used before the name of the alkyl or
aryl group.
2. IUPAC system : The IUPAC system, ethers are named as alkoxyalkanes. The ethereal
oxygen is taken with the smaller group and forms a part of the alkoxy group while the larger
group is considered to be a part of the alkane or arene.
The common and IUPAC names of some ithers are given below:
Structural formula Common name IUPAC name
CH3—O—CH3 Dimethyl ether Methoxymethane
CH3—O—CH2CH3 Ethyl methyl ether Methoxyethane
CH3CH2—O—CH2CH3 Diethyl ether Ethoxyethane
CH3—O—CH2CH3CH Methl n-proply ether 1-Methoxypropane
CH3
—
2 3
CH3—O—CH—CH3 Isopropyl methyl ether 2-Methoxypropane
1 1
CH3 CH3
—
3 2 2 Di-isopropyl ether 2-(2-Propoxy) propane

CH3—CH—O—CH—CH3
1
CH3
— —
2
CH3—O—C—CH3 tert-Butyl methyl ether 2-Methoxy-2-methylpropane
3
CH3
1
CH3 CH3
— —
— —
2
CH3—C—O—C— CH3
Di-tert-Butyl ether 2-(2-Methyl-2 propoxy)
3
CH3 3
CH3 methylphropane
C6H5—O—CH3 Methyl phenyl ether (Anisole) Methoxy benzene

C6H5—O—CH2CH3 Ethyl phenyl ether (Phenetole) Ethoxybenzene
C6H5—O—C6H5 Diphenyl ether or phenyl ether Phenoxy benzene
C6H5—O—(CH2)6CH3 n-Heptyl phenyl ether 1-Phenoxyheptane
1 2 3 4
C6 H5 —O—CH2CH2—CH—CH3
—
Isopentyl phenyl ether (3-Methyl-1-butoxy) benzene

CH3
CH3O—CH2—CH2—OCH3 1, 2 Dimethoxyethane
ETHERS 503
17.3 STRUCTURE OF ETHERS :

Since ether is regarded as dialkyl or diaryl dervatives of water, its structure is similar to
that of water. The structure is V-shaped with bond angle »110°. Bond angle in ether is greater
than water (105°) due to the repulsion between two bulky alkyl groups. As size of R increases,
bond angle also increases.
141 pm
..
H O
.. H
H C C H
111.7°
H H
Methoxymethane
17.4 PREPARATION OF ETHERS :
Ethers are prepared by the following general methods.
1. From alcohols : (a) Simple or symmetrical ethers are prepared by heating a primary
alcohol with concentrated sulphuric acid at lower temperature (413K). Two molecules of the
alcohol eliminate a molecule of water (dehydration) to form ether.
H2SO4
R— O—H + H —O—R R—O—R + H2O
413k
H 2SO4
2CH3CH2OH CH3CH2—O—CH2CH3
413K
Ethyl alcohol Diethyl ether
Diethyle ether boils at 35°C (308K) and is removed from the reaction mixture as it is
produced.
Note : (a) The success of this method depends upon the careful control of experimental
conditions. The temperature is kept at 413K and alcohol is used in excess. If the temperature
is increased to 443K, the product from ethyl alcohol is mainly ethylene which is produced by
intramolecular dehydration of alcohol.
H 2SO4
CH3CH2OH CH2 = CH2 + H2O
413K
Ethyl alcohol Ethylene
Remember, lower temperature favours the formation of ether whereas higher temperature
favours the formation of alkene.
H2SO4
Excess alcohol CH3 CH2 —O—CH2 CH3
413K Diethyl ether
CH3CH2OH
H2SO4
443K CH2= CH2
Ethylene
Mechanism : The formation of ether is a bimolecular reaction (S N2) involving the attack
of the alcohol on a protonated alcohol molecule. It consists of the following three steps:
.. + + H
(i) CH3 – CH2 – O
.. – H + H CH3 – CH2 – O
H
.. + H +
(ii) CH3 – CH2 – O + CH3 – CH2 – O CH3 – CH2 – O – CH2 – CH3 + H2O
..
| H |
H H
+ +
(iii) CH3 – CH2 – O + CH2 – CH3 CH3 – CH2 – O – CH2 – CH3 + H
|
H
(b) Mostly primary alcohols and to some extent secondary alcohols, react with sulphuric
acid at 413K to form ethers, tertiary alcohols almost exclusively yield alkenes.
CH3 CH3 CH3
—
Conc.H 2SO4 —
CH3—CH—OH CH3—CH—CH = 2 + CH3—CH—O—CH—CH3
413K
Isopropyl alcohol Propylene Diissopropylether
(2° Alcohol) (Major product) (Minor product)
CH3 CH3
— —
Conc.H 2SO4
CH3 —C—OH CH3—C = CH2 + H2O
413K
CH3 Isobutylene
tert-Butyl alcohol
(3° Alcohol)
The order of dehydration of alcohols leading to the formation of ethers follows the
sequence: primary > secondary > tertiary.
Limitations : (i)This methods is generally not suitable for the preparation of
unsymmetrical ethers since complex mixtures are obtained. For example.
Conc.H2SO4
ROH + R'OH ROR + ROR' + R'OR'
ETHERS 505
(ii) This method of preparation of ethers is suitable only for industries since reaction
conditions must be carefully controlled.
In place of H2SO4 other protonic acid like H3PO4 can also be used for preparation of
ethers.
(c) Catalytic dehydration of alcohols to ether can also be achieved by passing the vapours
of an alcohol over heated alumina at 513–523K. For example,
Al2 O3
CH3CH2— OH + H —OCH2CH3 CH3CH2—O—CH2CH3 + H2O
513–523K
Ethyl alcohol (two molecules) Diethyl ether
(d) By the action of diazomethane on alcohols. Methyl ethers can also be prepared by
the action of diazomethane (CH2N2) on alcohols in presence of tetrafluoroboric acid (HBF 4) as
catalyst.
HBF4
CH3CH2OH + CH2N2 CH3CH2—O—CH3 + N2
Ethyl alcohol Diazomethane Ethyl methyl ether
2. From Sodium Alkoxide, Williamson Synthesis : It is an important laboratory method
for the preparation symmetrical and unsymmetrical ethers. In this method, an alkyl halide is
allowed to react with sodium alkoxide. The sodium alkoxide is prepared by the action of sodium
on a suitable alcohol.
– +
2R' – OH + 2Na 2R' – ONa + H2O
Alcohol Sod. alkoxide
R – X + R' – ONa R – O – R' + NaX
Alkyl halide Ether
Ethers containing substituted alkyl group (secondary or tertiary) may also be prepared by
this method.
Mechanism : The reaction involves SN2 attack of an alkoxide ion on primary alkyl
halide.
– d+ d-
R¢ – ONa+ + R – X R¢ – O – R + NaX
Sod. Alkoxide Alkyl halide Ether
Limitations : Williamson synthesis is very sucessful with primary alkyl halides.

The alkoxide ions are both powerful nucleophiles and bases and bring about
dehydrohalogenation of the tertiary and secondary halides to form alkenes preferentially.
Phenols are also converted to ethers by this method. In this, phenol is used as the phenoxide
moiety.
–+
OH ONa O–R
+ NaOH R–X + NaX
Phenol Sod. Phenoxide Ether
This method can also be used for the preparation of both symmetrical and unsymmentrical
ethers. For example,
d+ d-
CH3CH2 —O Na + CH3CH2—Br 330K
– + + –
CH 3CH 2—O—CH 2CH 3 + Na Br
Sod. ethoxide Ethyl bromide Diethyl ether
CH3 CH3
— —
— —
d+ d-
– + + –
CH3 —C—O Na + CH3—Br CH3—C—OCH3 + Na Br
Methyl bromide
CH3 CH3
Sod. tert-butoxide tert-Butyl methyl ether
Similarly, alkyl aryl ethers (phenolic ethers) can be easily prepared by treating sodium
phenoxide with suitable alkyl halides. For example,
– + – +
O Na OCH3 O Na OCH2CH3
D D
+ CH3—Br ; + CH3CH2 — I
Methyl (–NaBr) Ethyl (–Nal)
Sod. phenoxide bromide Anisole Sod. phenoxide iodide Phenetole
– +
O Na O–CH2–CH=CH2
+ CH2 = CH – CH2 – Br D + NaBr

Allyl bromide
Sod. phenoxide o-Allyphenol
or o-Allyl phenyl ether
However, these ethers cannot be prepared by treating bromobenzene or iodobenzene

with sodium salts of the corresponding alcohols, i.e. sodium methoxide, sodium ethoxide or
sodium allyl alkoxide
ETHERS 507
Br
CH3O–Na+ or CH3CH2O–Na+ or CH2 = CHCH2O–Na+ Bromobenzene No reaction

Sod. methoxide Sod. ethoxide Sod. allyl alkoxide
This is due to the reason that the halogen is attached to the sp 2 carbon atom of the
aromatic ring and the halides are much less reactive than alkyl halides towards nucleophilic
substitution reaction.
Further, this method cannot be used for preparing diaryl ethers since aryl halides do
not undergo nucleophilic substitutions easily.
Br Heat
– +
O Na + O + NaBr
Sod. phenoxide Bromobenzene Diphenyl ether
3. From alkyl halides : Simple ethers can be prepared by boiling alkyl halides with dry
silver oxide.
R–I
+ Ag2 O R – O – R + 2AgI
R–I Ether
4. From Grigrand reagent : This is a good method for preparing higher ethers from
lower members. Thus, the action of a lower halogenated ether react with Grignard reagent to
give a higher member. Thus,
Br
CH3O CH2Cl + BrMgC2H5 CH3O CH2CH2CH3 + Mg
Monocloro- Ethyl magnesium- Methyl propyl Cl
dimethyl ether bromide ether
5. From alkenes : Alkenes can be converted into ethers by the following reaction.
OR¢
(i) Hg (OAc)2 / R ¢OH
R – CH = CH2 –
R – CH – CH3
Alkene
(ii) NaBH 4 / OH Ether
17.5 PHYSICAL PROPERTIES OF ETHERS :

1. Colour, state and odour : Lower members like dimethyl ether and ethylmethyl ether
are gases at ordinary temperature while the other lower homologues are colourless liquids with
characteristic pleasant odour 'ether smell'.
2. Dipolar nature : Ether molecules are slightly polar and thus have dipole moment.
The dipole moment of ethers is due to the polar character of the C–O bonds. The dipole moment
of dimethyl ether is 1.3D and that of diethyl ether is 1.18D.
3. Boiling point : The weak polarity of ethers do not appreciably affect their boiling
points which are comparable to those of the alkanes of comparable molecular masses but are
much lower than the boiling points of isomeric alcohols. The large difference in boiling points of
alcohols and ethers of same molecular masses (isomeric) is due to the presence of hydrogen
bonding in alcohols.
4. Solubility : The solubility of lower ethers in water is due to the formation of hydrogen
bonds between water and ether molecules.
R H H
..
.. O
..
O
.. ..
O
..
R H H
Diethyl ether is 7.5 percent soluble in water. As the molecular mass increases, the solubility
of ethers in water decreases due to the corresponding increase in hydrocarbon portion of the
molecule. Ethers are, however, fairly soluble in common organic solvents such as alcohol, benzene,
chloroform, acetone etc.
Diethyl ether is itself a good solvent for organic solutes. Apart from the polar character
of C–O bond in ether, ether has the ability to solvate cations (electrophile) by donating an electron
pair from their oxygen atom. These properties make diethyl ether a good solvent.
5. Density : All ethers are lighter than water. Their density and boiling points show a
gradual increase with increase in molecular masses.
17.6 CHEMICAL PROPERTIES :

In ethers two alkyl (or aryl) groups are linked to an oxygen atom.
R O R¢
Alkyl or Ethereal Alkyl or
aryl group oxygen aryl group
The aryl – oxygen bond is more stable than the alkyl–oxygen bond. Owing to the absence
of active groups and multiple bonds, ethers are comparatively inert substances. The reagents like
ammonia, alkalies, dilute acids and metallic sodium have no action upon them in cold. They are
not readily oxidised or reduced. However, under specific conditions, ethers undergo the following
reactions in accordance with their structural features.
I. Reactions of ethereal oxygen :
Ethers behave as Lewis bases on account of the presence of two lone pairs on the oxygen
atom.
1. Formation of oxonium salts : Ethers like alcohols are weakly basic and thus dissolve
in strong inorganic acids (e.g. H2SO4, HClO4, HBr etc.) to form stable oxonium salts. thus,
ETHERS 509
R .. R +
O + HBr O
.. – H Br–
..
..
R R
Ether Dialkyloxonium bromide
Oxonium salts are stable in high concentration of acids. When their acid solutions are
diluted with water, the oxonium salts are dissociated into original ether and acid because water
is a stronger base than ether.
2. Formation of coordination complexes : Ethers form relatively stable coordinate
complexes with Lewis acids (e.g. BF3, AlCl3 and RMgX etc.) The complexes are known as
etherates.
CH3CH2 CH3CH2
.. ..
O + BF3 O BF3
..
CH3CH2 CH3CH2
Diethyl Ether Boron trifuoride etherate
.. R R O(CH2 CH3 )2
2 (CH3CH2)2O + Mg Mg
..
X (CH3CH2)2O X
Diethyl ether Grignard reagent Grignard reagent etherate
Due to the formation of these complexes, Grignard reagents dissolve in ether. That is
why Grignard reagents are usually prepared in ethers.
II. Reactions involving the cleavage of C–O bonds in ethers :
1. Action of Halogen acids : The cleavage of C–O bond in ethers takes place under
drastic conditions with excess of hydrogen halides. First, the ethers are cleaved to form alkyl
halide and alcohol. The alcohol thus formed reacts with excess of the halogen acid to form the
corresponding halide.
R – O – R + HX R–X + R – OH
Ether Alkyl halide Alcohol
R – O – H + HX R – X + H2O
Thus, dialkyl ether gives two alkyl halide molecules.
Mechanism : The cleavage of ethers by halogen acids occurs by the following mechanism:
Step 1 : Ethers being Lewis bases, undergo protonation to form oxonium ion.
H
—
.. + – + –
CH3—O—CH
.. 2CH3 + H I CH3—O
.. —CH2CH3 + I
Ethyl methyl ether Oxonium ether
Step 2 : Iodide ion is a good nucleophile. Due to steric hindrance, it attacks the smaller
alkyl group of the oxonium ion formed in step 1 and displaces the alcohol molecule by SN2
mechanism as shown below :
–
H
– + S N2 +
I + CH3—O —CH2CH3 I CH3 O
.. —CH2CH3 CH3—I + CH3CH2—OH
Slow
Oxonium ion Transition state Methyl iodide Ethanol
Step 3 : When axcess of HI is used, ethanol thus formed reacts with another molecule of
HI of form ethyl iodide.
—
.. + – + –
CH3CH2—O—H
.. + H I CH3CH2—O
.. —H + I
H
—
– +
I + CH3CH2—O —H CH3CH2— I + H2O
Ethyl iodide
Reactivity of halogen acids : The order of reactivity of halogen acids follows the
sequence:
HI > HBr > HCI.
Greater the nucleophilicity of the halide ion, more reactive is the halogen acid. Since the
nucleophilicity of the halide ions follows the sequence I – > Br– > Cl–, the reactivity of of halogen
acids follows the same sequence i.e. HI > HBr > HCl.
Site of cleavage :
(a) However, when one of the alkyl groups is a tertiary group the halide first formed is a
teritiary halide.
CH3 CH3
— —
— —
CH3—C—O—CH3 + HI CH3 OH + CH3 —C—I

CH3 CH3
It is because in step 2 of the reaction, the departure of leaving group (HO–CH 3) creates
a more stable carbocation [(CH3)3C+] and the reaction follows SN1 meachanism.
CH3 CH3
— —
— —
+
CH3—C — O—CH3 slow
+
CH3—C + CH3 OH
—
CH3 H CH3
ETHERS 511
CH3 CH3
— —
— —
+ – fast
CH3—C + I CH3—C— I
CH3 CH3
Ethers with two different alkyl groups are also cleaved in same manner and the mechanism
of the cleavage is ascertained by the nature of the leaving group and the stability of intermediate
carbocation ion.
R – O – R¢ + HX R – X + R¢ – OH
(b) Cleavage of alkyl aryl ethers : Alkyl aryl ethers (or phenyl) ethers are cleaved at the
alkyl-oxygen bond due to the more stable aryl-oxygen bond.
In case of phenolic ethers, the products are always phenol and an alkyl halide.
O–R OH
+ HX +R–X
Aryl ether Phenol Alkyl halide
Thus, in case of anisole, when it reacts with HI, the products are phenol and methyl
iodide.
O–CH3 OH
+ HI + CH3 I
+
C6 H5 —O—CH3
In the first step, as per the mechanism, the methylphenyl oxonium ion,
H
is formed by protonation of anisole. The bond between O–CH3 is weaker than the bond between
O–C6H5 because the carbon of phenyl group is sp2 hybridised and there is a partial double bond
character. Therefore attack by I– ion exclusively breaks the weaker O–CH3 bond forming methyl
iodide and phenol. Phenols thus formed, do not react further to give aryl halides because sp2
hybridised carbon of phenol does not undergo nucleophilic substitution reaction by the halide
ion to form the corresponding aryl halides.
Cleavage of benzyl alkyl ethers : In case of benzyl alkyl ethers containing a primary
alkyl group such as benzyl ether, the reaction proceeds by S NI mechanism. Since the benzyl
carbocation is more stable than the methyl carbocation, therefore, cleavage of C–O bond gives
methyl alcohol and benzyl carbocation. This carbocation then reacts with I – ion to form benzyl
iodide as shown below :
.. + – –I
–
+.. C–O cleavage
CH2 —O—CH
.. 3+ H I – CH2 —O—CH3
–I Slow
—
Benzyl methyl ether H
Oxonium ion
+
CH2 + CH 3OH I– CH2 I + CH 3OH
Nucleophilic attack,
Benzyl carbocation Methyl alcohol Fast Benzyl iodide Methyl alcohol
Cleavage of diaryl ethers : Diaryl ethers such as diphenyl ether are, however, not
cleaved by HI. The reason being that the C–O bond has some double bond character due to
resonance between the lone pairs of electrons on the O atom and the C atoms of the aryl groups
directly linked to the O atom.
2. Hydrolysis : On heating with dilute sulphuric acid under presence, ethers are hydrolysed
to alcohols.
Dil H 2SO4 , D
R–O–R + H2O 2R – OH
under pressue
Alcohol
3. Action of Sulphuric Acid : Cold concentrated sulphuric acid has no action on ethers
except that it dissolves them forming oxonium salts. However, if the solution is heated, cleavage
of carbon-oxygen bond takes place leading to the formation of alcohol and alkyl hydrogen sulphate.
Conc. H2SO4
C2H5–O–C2H5 C2 H5 –OH + C2 H5 HSO4
D
Diethyl ether ethyl alcohol ethyl hydrogen sulphate
4. Action of Phosphorus Pentachloride : Phosphorus pentachloride brings about the

cleavage of both the carbon oxygen bonds of ethers forming alkyl chlorides.
D
CH3CH2 – O – CH2CH3 + PCl5 ¾¾® 2CH3CH2Cl + POCl3
Diethyl ether Ethyl Chloride
5. Reaction with acid chlorides and anhydrides : Acid chlorides react with ethers
when heated in the presence of anhyd. ZnCl2 or AlCl3 to form alkyl halides and esters.
Anhyd.ZnCl2
C2H5 – O – C2H5 + CH3COCl C2H5Cl + CH3COOC2H5
D
Diethyl ether Acetyl chloride Ethyl chloride Ethyl acetate
ETHERS 513
However, with anhydrides only esters are formed

Anhyd.ZnCl2
C2H5 – O – C2H5 + (CH3CO)2O 2 CH3COOC2H5
D
Diethyl ether Acetic anhydride Ethyl acetate
III. Reactions involving the alkyl group :

1. Action of air and light : Formation of peroxides. When exposed to air and light for a
long time ethers are oxidised to form hydroperoxides or simple peroxides.
OOH
—
Light
CH3CH2 – O – CH2CH3 + O2 CH 3 – CH – O – CH2CH3
Diethyl ether 1-Ethoxyethyl hydroperoxide
It is a free radical reaction and oxidation occurs at the carbon atom next to the ethereal
oxygen to form hydroperoxides. These peroxides are very dangerous compunds since they
decompose violenly at high temperatures. Therefore, serious explosions may occur during
distillation of old samples of ethers if peroxides are not removed.
A simple method to remove peroxide is to shake the old sample with ferrous salt solution
when the ether peroxides are reduced to ethers and Fe 2+ salts are oxidised to Fe3+ salts. The Fe3+
ions thus formed are removed by washing with water.
2. Halogenation : Ethers react with Cl2 or Br2 to give substitution products. The extent
of halogenation, however, depends upon the reaction conditions. For example, diethyl ether
reacts with chloride in the dark to give a, a¢ -dichlorodiethyl ether.
Cl Cl Cl
—
—
Cl2 dark a Cl2 dark a¢ a
CH3CH2 – O – CH2CH3 CH3CH2 – O – CH–CH3 CH3 – CH – O – CH–CH3
–HCl –HCl
Diethyl ether a Chlorodiethyl ether a, a¢ -Dichlorodiethyl ether
However, in the presence of light and excess of chlorine, all the hydrogen atoms are
substituted to give perchlorodiethyl ether.
hv
CH3CH2 – O – CH2CH3 + 10 Cl2 ¾¾® CCl3CCl2 – O – CCl2CCl3 + 10 HCl
Diethyl ether (excess) Perchlorodiethyl ether
3. Electrophilic substitution : In aryl alkyl ethers the alkoxy group (–OR) is ortho, para
directing and activates the aromatic ring towards electrophilic substitution in the same way as in
phenol. However, aromatic ethers are less reactive than phenols.
.. .. .. + ..
OR + OR + OR OR OR
..
..
I II III IV V
(i) Halogenation : Phenylalkyl ethers undergo usual halogenation in the benzene ring,
e.g., anisole undergoes bromination with bromine in ethanoic acid even in the absence of iron (III)
bromide catalyst. It is due to the activation of benzene ring by the methoxy group. Para isomer
is obtained in 90% yield.
OCH3 OCH3 OCH3
Br
Br 2 in
+
Ethanoic acid
Anisole o-Bromoanisole
Br (minor)
p-
o-Bromoanisole
(major)
(ii) Friedel-Crafts reaction : Anisole undergoes Friedel-Crafts reaction, i.e. the alkyl and
acyl groups are introduced at ortho and para positions by reaction with alkyl halide and acyl
halide in the presence of anhydrous aluminium chloride (a Lewis acid) as catalyst.
OCH3 OCH3 OCH3
CH3
Anhyd, AlCl 3
+ CH3Cl +
CS2
CH3
2-Methoxy- 4-Methoxy-
toluene toluene
(Minor) (Major)
OCH3 OCH3 OCH3

COCH3
Anhyd. AlCl 3
+ CH3COCl +
Ethanoyl
chloride
COCH3
2-Methoxy 4-Methoxy
acetophenone acetophenone
(Minor) (Major)
(iii) Nitration : Anisole reacts with a mixture of concentrated sulphuric and nitric acids
to yield a mixture of ortho and para nitroanisole.
OCH3 OCH3 OCH3
NO2
H2SO4
+
HNO 3
NO2
2-Nitroanisole 4-Nitroanisole
(Minor) (Major)
ETHERS 515
17.7 USES OF ETHERS :

Important uses of diethyl ethers :
1. As a solvent both in laboratory and industry. Ethers are almost inert in nature and
have good dissolving power. In industry it is used as solvent for oils, resins, gums
etc.
2. As an extracting solvent in laboratory and industry.
3. As a reaction medium for the preparation of Grignard and organometallic reagents,
also for carrying out LiAlH4 reductions.
4. Diethyl ether finds its use as an anaesthetic agent in surgery.
5. A number of naturally occurring ethers are used as perfumes and flavouring agents
because of their pleasant odour.
6. Diphenyl ether is used as a heat transfer medium because of its high boiling point,
531K.
7. Lower ethers are volatile liquids which on evaporation produce low temperatures.
They are therefore, used as refrigerants.
Diethyl Ether, Ether, C2H5OC2H5 :
This is the most important representative of this class and often referred to as simply
ether. It can be prepared in the laboratory by:
(i) Williamsons synthesis
(ii) On a large scale by dehydration reaction of ethyl alcohol by Conc. H 2SO4
Equal volumes of alcohol and conc. H2SO4 are heated in a flask fitted with a dropping
funnel and cold water running condenser. When the temperature of the content in the flask
reaches 413K, ether begins to distil over. Alcohol is now run in from the dropping funnel at the
same rate at which ether distills over. The process is continuous and hence the name Continous
Etherfication Process.
Estimation of Methoxy (or Ethoxy) Groups :
The methoxy (or ethoxy) groups are estimated by Zeisel's method. A known mass of the
sample is heated with conc. HI to form methyl iodide (or ethyl iodide). The iodide is then treated
with alcoholic silver nitrate to give a precipitate of AgI
ROCH3 + HI ® ROH + CH3I
CH3I + AgNO3 ® AgI + CH3NO3
In this reaction : – OCH3 is equivalent to AgI, mass of methoxy group is 31 and that of
31 × mass of AgI × 100
AgI 234.88. Thus, % of methoxy group =
234.88 × mass of ether
1. Two important methods of preparation of ethers are :

(i) Dehydration of alcohol and
(ii) Williamson synthesis
2. Weakly polar ethers have much lower boiling points compared to their isomeric alcohols.
3. The lower members are fairly soluble in water due to the formation of hydrogen bonding.
4. Diethyl ether is a good solvent and all the ethers are lighter than water.
5. Owing to the absence of of active groups and multiple bonds, ethers are comparatively
inert. However, under specific conditions ethers undergo the following reactions in
accordance with their structural features.
(i) Reaction at ethereal oxygen
(ii) Reactions involving cleavage of C–O bonds particularly with HI, HBr and PCl 5
(iii) Reactions involving the alkyl group.
Ethers undergo halogenation at the alkyl groups. In aryl alkyl ethers the alkoxy group
activates the aromatic ring and directs the incoming group to ortho and para positions in
electrophilic substitution reactions.
QUESTIONS
I. Multi choice type questions. (one mark) :
1. Which of the following will exhibit highest boiling point ?
(a) CH3CH2O CH2CH3 (c) CH3O CH2CH2CH3
(b) CH3CH2CH2CH2OH (d) CH3CH2CH2CH2CH2OH
2. Which of the following cannot be prepared by Williamson synthesis ?
(a) Methoxybenzene (c) Di-tert-butyl ether
(b) Methoxy ethane (d) tert-butyl methyl ether
Br2
3. In the reaction, OCH3
Acetic acid the products are
(a) Br OCH3 + H2 (c) Br + CH3OH
(b) Br + CH3Br (d) OH + CH3Br

ETHERS 517
4. The ether C6H5 – O – CH2C6H5 when treated with HI produces

(a) C6H5CH2I (c) C6H5CH2OH
(b) C6H5I (d) C6H5 – O – C6H5
5. Which of the following ethers is not cleaved by HI ?
(a) Methyl phenyl ether (c) Ethyl methyl ether
(b) Diphenyl ether (d) Ethyl phenyl ether
6. The molecular formula of alkyl ethers is
(a) CnH2nO (c) CnH2n + 2O
(b) CnH2n + I (d) CnH2nO CnH2n
7. Ethers react with Conc. H2SO4 to form
(a) Alkyl free radicals (c) Oxyanion
(b) Zwitter ion (d) Oxonium ion
8. Ether gives chemical reactions due to
(a) C – O bond cleavage (c) Lone pair present on oxygen
(b) C – H bond cleavage (d) All of the above
9. Which of the following pairs will give ether ?
Dry Ag2 O
(a) C2H5ONa and C2H5I (c) C2H5I
+
H
(b) C2H5OH (d) All of the above
373K
10. Which of the following solvents is used for the preparation of Grignard reagent.
(a) Ethyl alcohol (c) Cyclohexonol
(d) Diethyl ether (d) Benzene
11. When (CH3)3 COCH3 is treated with hydriodic acid, the fragments after the reaction
obtained are :
(a) (CH3)3C – I + HOCH3 (c) (CH3)3 CH + CH3OCH3 + I2
(b) (CH3)3C – OH + I – CH3 (c) (CH3)3 C – OH + CH4 + I2
12. C6H5COCH3, when treated with HI at 373K the following are the products.
(a) CH3OH and C6H5I (c) C6H5I and CH3I
(b) CH3I and C6H5OH (d) C6H5OH and CH3OH
ANSWERS
1. (d), 2. (c), 3. (a), 4. (a), 5. (b), 6. (c), 7. (d), 8. (d), 9. (d), 10. (b), 11. (a), 12. (b)
II. Fill in the blanks

1. Ethers exhibit functional isomerism with ______ .
2. C4H10O has ______ metamers, one of them is diethyl ether while the others are ______
and ______.
3. Williamson's synthesis involves the reaction of an ______ with an ______.
4. Ethers behave as weakly ______ substances due to the presence of two lone pairs of
electrons on the oxygen atom.
5. ______ is widely used as a solvent for the preparation of Grignard reagent.
6. Aliphatic ethers are purified by shaking with a solution of ferrous salt to remove ______
which are formed on prolonged standing in contact with air.
7. Cleavage of phenolic ether, anisole, by HI, gives ______ and ______.
8. Alkyl aryl ethers are best prepared by treating sodium salt of ______ with ______ halide.
ANSWERS
1. alcohols, 2. three, methyl n-propyl ether, isopropyl methyl ether, 3. alkoxide, alkyl halide,
4. basic, 5. Diethyl ether, 6. peroxides, 7. Phenol, methyl iodide, 8. phenol, alkyl.
III. Choose the True (T) and Flase (F) statement : (one mark)
1. Cleavage of ethyl methyl ether with HI at 373K gives methyl iodide and ethanol.
2. Phenetole reacts with HI at 373K to give iodobenzene and ethanol.
3. Dimethyl ether and ethyl alcohol have the some boiling point as both have same molecular
masses.
4. tert-Butyl ether can be prepared by heating sodium ethoxide with tert-butyl bromide.
5. Alkyl aryl ethers are less reactive than phenols towards electrophilic substitution reactions.
6. Both symmetrical and unsymmetrical ethers can be prepared by Williamson's synthesis.
ANSWERS
1. (T), 2. (F), 3. (F), 4. (F), 5. (T), 6. (T).
IV. Very short answer type questions (one mark) :

1. Give the IUPAC names the following :
(i) CH3CH2CH2OCH3
(ii) CH3COCH2CH2Cl
(iii) C6H5OC2H5
(iv) CH3 – O – CH2 – CH – CH3
|
CH3
ETHERS 519
2. Write the structure of the compounds whose names as follows :

(i) 2-Ethoxy-3-methyl pentane
(ii) 1-Ethoxypropane
(iii) 1-Phenoxyheptane
(iv) Anisole and phenetole
3. Name one metamer of diethyl ether.
4. Which method is used for the estimation of a methoxy group in organic compounds.
5. Which class of ethers are not cleaved by HI.
6. Which product is formed by the Friedel crafts reaction of anisole with CH 3Cl.
7. Between anisole and phenol, which is more reactive towards electrophilic substitution
reaction.
8. Give the order of reactivity of halogen acids towards the cleavage of carbon-oxygen
bond of ethers.
9. Which reagent brings about the cleavage of carbon-oxygen bond of ethers leading to the
formation of only alkyl halides.
10. Give the order of polarity of alcohol, phenol and ether.
V. Short answer type questions (two marks) :

1. Give the reason of the higher boiling point of ethanol in comparision to methoxy methane.
2. Write the names of reagents and equation for the preparation of the following ethers by
Williamson's synthesis:
(i) Ethoxy ethane (iii) 1-Methoxyethane
(ii) Ethoxy benzene (iv) 1-Propoxypropane
3. Write the equations for the following reaction
(i) Nitration of anisole
(ii) Bromination of anisole in ethanoic acid medium.
4. Give tthe major products that are formed by heating each of the following with HI
CH3
(i) CH3 – CH2 – CH – CH2 – O – CH2– CH3

CH3
(ii) CH3 – CH2 – CH2 – O – C – CH2 – CH3
CH3
(iii) – CH2 – O –
5. Predict the product of the following reactions :

(i) CH3 – CH2 – CH2 – O – CH3 + HI
(ii) (CH3)3 C – O – C2H5 + HI
OC 2 H5
(iii) + HBr
OC 2 H5
Conc.H2 SO4
(iv) Conc.HNO3
6. Explain why diphenyl ether is not cleaved by HI.

7. (CH3)3 C – O – CH3 + HI (CH3)3 CI + CH3OH
Justify the preferential formation of the products.
8. Predict the products A and B
OCH3 HI
A+ B
373K
9. Which of the following is an appropriate set of reactants for the preparation of

1-methoxy-4-nitrobenzene and why ?
Br ONa
(i) + CH3ONa (ii) + CH3Br
NO 2 NO 2
10. How you will distinguish C2H5– O – C2H5 and C6H5 – O – C6H5 by treating with HI ?
11. Why can ethers be cleaved preferentially by hot conc.HI and HBr but not by conc.HCl.
VI. Short answer type questions (3 marks) :
1. Illustrate with examples the limitations of Williamson sysnthesis for the preparation of
certain type of ethers.
2. How is 1-propoxypropane synthesised from propan-1-ol ? Write the mechanism of this
reaction.
3. Preparation of ethers by acid dehydration of secondary and tertiary alcohol is not suitable
method. Give reason.
4. Write the mechanism of the reactions of HI with methoxymethane.
5. Write the equations of the the reactions of hydrogen iodide with :
(i) methoxybenzene
(ii) benzyl ethyl ether
(iii) 1-propoxypropane
ETHERS 521
6. Explain how the alkoxy group (–OR) is ortho and para directing and activates the aromatic
ring towards electrophilic substitution reactions.
7. Give an example for the synthesis of unsymmetrical ether by Williamson synthesis.
8. Write the reaction of Williamson synthesis of 2-ethoxy-3-methyl-pentane starting from
ethanol and 3-methylpetan-2-ol.
9. Explain why is bimolecular dehydration not appropriate for the preparation of ethyl methyl
ether.
10. Compound (A), C4H10O, is found to be soluble in sulphuric acid. (A) does not react with
metallic sodium or potassium permanganate solution. When (A) is heated with excess of
HI, it is converted to a single alkyl halide. What is the structural formula of (A).
11. Write the equation of the reaction of hydrogen iodide with
(i) 1-propoxypropane
(ii) methoxy benzene
(iii) benzyl ethyl ether
12. Write a suitable reaction for the preparation of t-butyl ethyl ether.
13. Give the majo products that are formed by reacting each of the following ether with HI.
(i) methyl propyl ether
(ii) phenyl methyl ether
(iii) benzyl phenyl ether
14. Preparation of ethers by acid dehydration of secondary and tertiary alcohol is not suitable
method. Give reason.
VII. Long answer type question (7 marks) :
1. Outline two important methods of prepration and three properties of dialkyl ethers.
2. How does diethyl ether react with
(i) PCl5, (ii) Conc.H2SO4 (iii) Conc.HI (iv) O2
3. Describe Williamson synthesis of ethers. What are its limitations? Discuss the mechanism.
4. How is diethyl ether prepared in the laboratory? How will you distinguish it from ethanol
and diphenyl ehter. What happens when it is treated with hot HI?
5. Explain the following with an example.
(i) Unsymmetrical ether
(ii) Cleavage of benzyl alkyl ethers by HI
(iii) Williamson ether synthesis
6. Discuss the electrophilic substitution reaction like halogenation, nitration and Friedel-
Crafts reactions of aryl alkyl ethers.
7. Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates the benzene ring
towards electrophilic substitution and (ii) it directs the incoming group to ortho-and
para-positions in the benzene ring.
qqq
UNIT - XII
CHAPTER - 18
ALDEHYDES AND KETONES
18.1 INTRODUCTION :
The aldehydes and ketones belong to the class of oxygen containing organic compounds
that have a C = O group, for which they are termed as carbonyl compounds.
(i) In aldehydes, the carbonyl group is attached to one hydrogen atom and one alkyl or
aryl group or another hydrogen atom, whereas in ketones, the carbonyl group is
attached to either one alkyl and one aryl group or to two alkyl (or aryl) groups.
O O
(a) R—C—H Examples : H—C—H
Aldehyde Formaldehyde
(Where R = H or any O
alkyl or aryl group) H 3C — C — H
Acetaldehyde
O
O —C—H
Benzaldehyde
O O
(b) R — C — RI Examples : H3C — C — CH3
Ketone Acetone
(Where R and R¢ may be O
same or different alkyl
or aryl groups) O — C — CH3
Acetophenone
(ii) When two alkyl (or aryl) groups i.e. R and R¢ are same, the ketone is termed as a
simple ketone, where as when R and R¢ are different, the ketone is named as a
mixed ketone.
ALDEHYDES AND KETONES 523
O O
H3C — C — CH3 O — C — CH3 Acetophenone

Acetone R=— O
R = RI = — CH3 RI = — CH3
Simple ketone Mixed ketone
H
(iii) Aldehydes are characterised by the functional group — C = O (aldehydic group)
and the functional group of ketones is C = O (ketonic group).
(iv) Aldehydes and ketones have some similar characteristics because of the presence
of same carbonyl group, but differ in some properties due to the presence of a
hydrogen atom on the carbonyl group of aldehydes.
(v) In case of aldehydes the —CHO group always occurs at the end of the carbon
O
chain, where as the — C — group in case of keones occurs within the carbon
chain.
(vi) Carbonyl compounds may be aliphatic or aromatic in nature depending on the
presence of only alkyl group or an aryl group (may be in addition to alkyl or aryl
group in case of ketones).
(a) Aliphatic aldehydes and ketones
O O O
H—C—H CH3 — C — H CH3 — C — CH3

Formaldehyde Acetaldehyde Acetone
(b) Aromatic aldehydes and ketones
O O O
O —C—H O — C — CH3 O —C— O

Benzaldehyde Acetophenone Benzophenone
18.2 NOMENCLATURE OF CARBONYL COMPOUNDS :

A. Nomenclature of Aldehydes :
(i) Common system :
(a) In the common system, the names of aliphatic and aromatic aldehydes are derived
from the common names of the acids which they form on oxidation by replacing
the terminal ‘ic acid’ by the suffix aldehyde.
O O
H—C—H+O H — C — OH
Formaldehyde Formic acid
Formic acid – ic acid + aldehyde = formaldehyde
(b) In case of substituted aldehydes, the positions of the substituents are indicated by
Greek letters a, b, g, d etc with the carbon atom next to the —CHO group being
designated as a.
g b a
CH3 — CH — CH2 — CHO
CH3
b – Methylbutyraldehyde
(ii) IUPAC system :

(a) In IUPAC system the aliphatic aldehydes are named as alkanals which are derived
from the names of the corresponding alkanes by replacing the ending – e with – al.
O O O
H—C—H CH3 — C — H CH3 — CH2 — CH2 — C — H

Methanal Ethanal Butanal
(b) In case of substituted aldehydes, the longest carbon chain is choosen having
—CHO group and the substituents are prefixed in the alphabetical order along with
numerals indicating their positions in the carbon chain with the carbon atom of the
—CHO group given number 1.
CH3 Br CH3 O
CH3 — CH — CH2 — CHO CH3 — CH2 — CH — CH — C — H

4 3 2 1 5 4 3 2 1
3-Methylbutanal 3-Bromo-2-methylpentanal
5 4 3 2 1
OHC — CH2 — CH2 — CH2 — CHO
Pentan - 1, 5 - dial
(c) When aldehyde group is attached to an alicyclic ring, the suffix carbaldehyde is
added after the full name of the cycloalkane, with the numbering starting from the
carbon atom containing –CHO group.
O
CH3 O
C H 2 H
C
1
Cyclohexanecarbaldehyde 2-Methylcyclohexanecarbaldehyde
(d) The suffix carbaldehyde is used when an unbranched carbon chain is attached to
more than two aldehyde groups, where the compound is considered as a derivative
of the parent alkane which does not include the carbon atom of the functional groups.
CHO
OHC — CH2 — CH2 — CH — CH2 — CH2 — CHO

5 4 3 2 1
Pentane - 1, 3, 5 - tricarbaldehyde
But :
CH2—CHO
OHC — CH2 — CH — CH2 — CH2 — CHO

1 2 3 4 5 6
3 - (Formylmethyl) hexan - 1, 6- dial

(e) The name benzenecarbaldehyde or simply benzaldehyde is given to the simple
aromatic aldehyde where aldehyde group is attached directly to the benzene ring.
In case of substituted benzaldehydes, the positions of substituents in the benzene
ring with respect to the –CHO group are indicated by the prefixes ortho(o) meta(m)
and para(p) or by the numbers 1, 2, 3 etc. with the carbon having –CHO group
being considered as number 1.
C—H CHO
OH
Benzaldehyde 2- Hydroxybenzaldehyde
(o-Hydroxybenzaldehyde
or Salicylaldehyde)
The common and IUPAC names of some aldehydes are given in the Table 18.1
Table 18.1: Common and IUPAC names of some Aldehydes.
Formula Common Name IUPAC name

O
||
H–C–H Formaldehyde Methanal
O
||
CH3 – C – H Acetaldehyde Ethanal
CH3CH2CHO Propionaldehyde Propanal
CH3CH2CH2CHO Butyraldehyde Butanal
3
CH3 2
CH –1CHO Isobutyraldehyde 2-Methylpropanal
CH3
CH3
|
CH3 – CH – CH2 – CHO b-Methyl butyraldehyde 3-Methylbutanal
b a
O
||
3
CH2 = 2CH – 1C – H Acraldehyde. Prop-2 - enal
(Acrolein)
CH3 – CH = CH – CHO Crotonaldehyde But-2 - enal

b
3
CH a CHO g-Methylcyclohexane 3-Methylcyclohexanecarb-
g3 2 1
-carbaldehyde aldehyde
CHO
Phthaldehyde Benzen-1, 2-dicarbaldehyde
CHO
CHO
P-Bromobenzaldehyde 4-Bromobenzaldehyde
Br
A. Nomenclature of Ketones :
(i) Common system :
(a) In the common system, the names of aliphatic and aromatic ketones are derived by
naming the two alkyl or aryl groups bonded to the carbonyl group in alphabetical
order as two separate words and adding the suffix ketone. In case of symmetrical
ketones the prefix di is attached to the name of the alkyl group.
COCH3
O O
CH3 — C — C2H5 CH3 — C — CH3

Ethyl methyl ketone Dimethyl ketone Methyl phenyl ketone
(Acetone)
(b) The positions of the substituents are indicated by Greek letters, aa¢, bb¢ etc starting
from the carbon atoms next to the carbonyl group taken as aa¢.
CH3 O
CH3 — CH — C — CHI 2 — CHI 3

b a a b
a -Methyl diethyl ketone
(c) In case of aromatic ketones generally the namings are done by adding the acyl
group as prefix to phenone.
O O
O
C–CH3 C–CH2–CH 3
C
Acetophenone Benzophenone Propiophenone
(ii) IUPAC System :

(a) In the IUPAC system, ketones are named as alkanones, which are derived by
replacing the terminal -e of the corresponding alkanes by the suffix - one.
(b) During the naming the longest chain carrying the carbonyl group is choosen and
the numbering begins from the end giving lowest number to the carbonyl group. If
the chain carries two keto groups, prefix di is attached to -one.
O O O O
CH3 — C — CH3 CH3 — CH2 — C — CH3 CH3 — C — CH2 — C — CH3

1 2 3 4 3 2 1 1 2 3 4 5
Propan-2-one Butan-2-one Pentan-2, 4-dione
(c) In case of substitued ketones, the parent chain containing the keto group and the
substituents are prefixed in alphabetical order along with numerals indicating their
positions in the carbon chain.
CH3 O O
CH3 — CH — C — CH2 — CH3 CH3 — CH = CH — CH2 — C — CH3

1 2 3 4 5 6 5 4 3 2 1
2-Methylpentan-3-one 4-Hexen-2-one
The same principle is applied to cyclic ketones, the O

1
number 1 being given to the carbonyl group. 2
(d) When both aldehyde and keto groups are present in 3 CH
3
the same compound, aldehyde group is given 3-Methylcyclopentanone
importance because of its higher reactivity and will be assigned number 1. Keto
group will be given the name oxo prefixed by its position. For example.
CH3 — C — CH2 — CH2 — CHO

5 4 3 2 1
4-Oxopentanal
Common and IUPAC names of some ketones are given in Table 18.2.
Table 18.2 : Common and IUPAC names of Ketones
Formula Common name IUPAC name
O
||
CH3 – C – CH3 Acetone Propanone
O
||
CH3 – C – CH2 – CH3 Ethyl methyl ketone Butan - 2 - one.
O
||
CH3 – CH2 – C – CH2CH3 Diethyl ketone Pentan - 3 - one.
O
||
CH3 – C – CH2CH2CH3 Methyl n-propyl ketone Pentan-2-one
O CH3
|| |
CH3 – C – CH – CH3 Isopropyl methyl ketone 3-Methylbutan-2-one
CH3 O
5 4 | 3 2 || 1
CH3 – C = C H – C– C H3 Mesityl oxide 4-Methylpent-3-en-2-one.
O
a-Methylcyclohexanone 2-Methylcyclohexanone
CH3
O O
Biacetyl Butan-2, 4-dione
CH3 — C — C — CH3
COCH3
m-Bromoacetophenone 3-Bromoacetophenone
Br
O
CH3 — CH2 — C — CH2 — CHO Propionylacetaldehyde 3-Oxopentanal
18.3 ISOMERISM IN ALDEHYDES AND KETONES :

1. Aldehydes: Aldehydes show three types of structural isomerism i.e. chain,
functional isomerism and position isomerism.
(a) Chain isomerism: The molecular formula C4H8O represents compounds like
(i) CH3 CH2 CH2CHO Butanal (Straight chain)
(ii) CH3 – CH – CHO 2– Methylpropanal. (Branched chain)
|
CH3
(b) Functional isomerism: Aldehydes exhibit functional isomerism with ketones.
The molecular formula C3H6O represents two compounds.
(i) CH3CH2CHO
Propanal
(ii) CH3COCH3
Propanone.
(c) Position isomerism : Aromatic aldehydes exhibit position isomerism.
CHO CHO CHO
CH3
CH3
CH3
o-Methylbenzaldehyde m-Methylbenzaldehyde p-Methylbenzaldehyde
2. Ketones: Ketones exhibit chain isomerism, functional isomerism and metamerism.
(i) Chain isomerism:
Molecular foumula C5H10O represents the following compounds.
O
||
CH3 – CH2 – CH2 – C – CH3
Pentan -2-one
O
4 3 2|| 1
CH3 – CH – C – C H3
|
CH3
3 –Methylbutan - 2- one.
(ii) Functional isomerism:
Ketones exhibit functional isomerism with aldehydes.
O
||
CH3 – C – CH3 CH3 – CH2 – CHO
Propanone Propanal
(iii) Metamerism: The same molecular formula represents two ketones which differ
in the nature of alkyl groups linked to the divalent keto group. This is also termed
as position isomerism.
O O
|| ||
CH3 – CH2 – CH2 – C – CH3 CH3 – CH2 – C – CH2 – CH3
Pentan -2-one Pentan-3-one
18.4 STRUCTURE OF CARBONYL GROUP :
Electron diffraction and p bond p bond

spectroscopic studies confirm that 1200
carbonyl group is planar in nature. The s bond s bond O120º
0
2 C C=O
carbon atom of carbonyl group is sp
hybridised, thus it has three sp 2 hybrid 1200
p bond
orbitals. It forms three sigma bonds, one p bond
with oxygen and other two with other Fig.18.1 Structure of Carbonyl group
two atoms or groups. All these sigma bonds lie in one plane at an angle of 120 0 to each other.
The unhybridised p–orbital of carbon laterally overlaps with half filled p–orbital of oxygen,
thereby forming a p bond. The electron cloud of p bond. lies both above and below the C – O
bond. Since oxygen atom is more electronegative the electron cloud is displaced more towards
oxygen. This results in polarisation of C – O bond. The carbon end becomes slightly +ve whereas
the oxygen end, slightly –ve. Hence the carbonyl carbon is an electrophilic (Lewis acid) and
carbonyl oxygen, a nucleophilic (Lewis base) centre.
+d -d
C=O
Due to polarity of C – O bond, the aldehydes and ketones are associated with large values
of dipole moment ( m =2.3 – 2.8 D) and are more polar than ethers. Due to its polar nature, the
carbonyl group can be represented as a resonance hybrid of the following two structures.
+ –
C=O C–O
(I) (II)
COMPARISON BETWEEN C = O GROUP AND C=C BOND

Similarities:
(i) In both the cases ‘C’ atom is sp2 hybridised.
(ii) Both consist of a s bond and p bond.
(iii) Both have planar structure.
(iv) Both exhibit addition reactions.
Differences:
(i) C = O is polar whereas C=C is nonpolar..
(ii) C = O group undergoes nucleophilic addition reactions whereas C= C

undergoes electrophilic addition reactions.
(iii) Bond length and bond strength are different in both the cases. Due to small size of
oxygen C = O length is shorter (1.23A°) than C = C bond length (1.34A°)
(iv) Geometrical isomerism is possible with C=C whereas no such isomerism in
case of C = O group.
18.5 GENERAL METHODS OF PREPARATION OF ALDEHYDES AND KETONES :
1. From Alcohols
(a) By oxidation:
(i) Aldehydes and ketones can be prepared by the oxidation of alcohols.
Primary alcohols upon oxidation give aldehydes whereas secondary
alcohols give ketones. The most commonly used oxidants are KMnO 4 or
K 2 Cr 2 O 7 acidified with sulphuric acid.
O
K2Cr2O7 / H2SO4 ||
R– CH2OH + [O] R – C – H + H2O
Primary alcohol Aldehyde
O
K2 Cr2O7 / H2SO4 ||
CH3– CH2OH + [O] CH3 – C – H + H2O
Ethyl alcohol Acetaldehyde
CH2 OH CHO
K2 Cr2O7 + H2SO4
+ [O] + H2O
Benzyl alcohol Benzaldehyde

K2Cr2O7 / H2SO4
R R
CHOH + [O] C = O + H2O
R R
Secondary alcohol Ketone
CH3 K2Cr2O7 / H2SO4 CH3

CHOH + [O] C=O + H2O
CH3 CH3
Acetone
Isopropyl alcohol
Aldehydes formed by this process are to be removed from the reaction mixture as soon as
they are formed. This is because aldehydes are prone to oxidation further to carboxylic acid. The
removal of aldehyde from the reaction mixture is usually made by distillation since aldehydes are
having lower boiling points than alcohols from which they are formed.
(ii) Ketones can also be prepared from secondary alcohols by an alternate method.
The secondary alcohol is refluxed with excess of acetone (solvent) in presence of
catalyst aluminium tertiary butoxide [Al(O – tert – Bu) 3]producing ketone. This
is known as Oppenauer oxidation. In this case secondary alcohol is oxidised to
ketone whereas acetone is reduced to isopropyl alcohol.
R CH3 [(CH3) 3CO]3 Al R CH3

CHOH + C=O C=O + CHOH
R1 CH3 R1 CH3
Secondary Acetone Ketone
alcohol
In this case secondary alcohol is oxidised to ketone even in the presence of carbon-
carbon double bond whereas acetone is reduced to isopropyl alcohol.
OH O
[(CH 3)3CO]3 Al
(CH3)2CO
Cyclohex-2-enol Cyclohex-2-enone
(iii) Alcohols can be better oxidised to carbonyl compounds by mild oxidsing agents
Collin’s reagent (chromium trioxide-pyridine complex, (CrO3.2C5H5N) and PCC
i.e.. Pyridinium chlorochromate (CrO3.C5H5N.HCl) which are more advantageous
than acidified K2Cr2O7 as using these reagents oxidation can be stopped at the
aldehyde stage preventing further oxidation to carboxylic acids. These reagents
do not attack double bonds.
Collin’s reagent
CH3 CH2 CH2 OH CH3 – CH2 – CHO
or
PCC
H O
PCC
CH3 — CH = CH — C — CH3 CH3 — CH = CH — C — CH3
or
OH Collin’s reagent
Pent - 3 - en - 2 - ol Pent - 3 - en - 2 - one

(b) By catalytic dehydrogenation of alcohols.
When vapours of alcohols are passed over hot reduced Cu at 573 K, dehydrogenation
takes place. Primary alcohols produce aldehydes whereas secondary alcohols produce
ketones.
O
Cu ||
R– CH2 OH R – C – H + H2
573K
Primary alcohol Aldehyde
Cu
CH3 – CH2 OH CH3 CHO + H2
Ethyl alcohol 573K Acetaldehyde
R Cu R
CHOH C = O + H2
R 573K R
Secondary alcohol Ketone
CH3 CH3
Cu
CHOH C = O + H2
CH3 573K CH3 Acetone
Isopropyl alcohol
2. By dry distillation of Ca-salt of fatty acids.
Dry distillation of Ca-salts of fatty acids yield aldehydes and ketones.
(a) Aldehydes
Formaldehyde is obtained by the dry distillation of calcium formate at 670 K.
O
|| O
H—C—O ||
Ca H–C–H + CaCO3
H — C —O
|| Formaldehyde
O
Calcium formate
A mixture of calcium formate and calcium salt of any other carboxylic acid on dry
distillation yields aldehydes.
O O
|| ||
CH3— C — O O—C—H
Ca + Ca
CH3— C — O O—C—H 2CH3 CHO + 2CaCO3
|| || Acetaldehyde
O O
Calcium acetate Calcium formate
(b) Ketones
Calcium salt of any fatty acid other than formic acid on dry distillation yields
ketone.
O
|| O
CH3 — C — O ||
Ca CH3 – C – CH3 + CaCO3
CH3 — C — O Acetone
||
O
Calcium acetate
Mixed ketones can be obtained by dry distillation of a mixture of calcium salt of fatty
acids other than HCOOH.
e.g. Ethylmethyl ketone can be obtained by dry distillation of a mixture of calcium acetate
and calcium propionate.
O O
|| ||
CH3— C — O O — C — CH2CH3
Ca + Ca
2CH3COC2H5 + 2CaCO3
CH3— C — O O — C — CH2CH3
|| || Ethylmethyl ketone
O O
However, this method is not suitable for the preparation of mixed ketones. This is because
three products are expected when a mixture of two calcium salts are heated. For example, in the
above case the dry distillation of a mixture of calcium acetate and calcium propionate yields a
mixture of acetone, diethyl ketone and ethylmethyl ketone.
3. From carboxylic acid:
When vapours of fatty acid are passed over heated MnO at 573K, aldehydes or ketones
are formed. Formic acid gives formaldyhyde whereas acids other than HCOOH produce ketones.
A mixture of formic acid and other fatty acids produces aldehydes.
O O O
|| || MnO ||
H – C – OH + H – C – OH H–C–H + CO2 + H2O
573K
O O Formaldehyde
|| || MnO
CH3 – C – OH + H – C – OH CH3CHO + CO2 + H2O
573K
O Acetaldehyde
||
CH3— C — OH MnO CH3
+ C = O + CO2 + H2O
CH3— C — OH 573K CH3
|| Acetone
O
4. From acid chlorides.

Both aldehydes and ketones can be prepared from acid chlorides.
(a) Aldehydes:
Acid chlorides can be reduced to aldehydes with H2 in boiling xylene using palladium as
catalyst supported by BaSO4 and partially poisoned by addition of sulphur or quinoline.
O O
|| Pd / BaSO4,S ||
R – C – Cl + H2 R – C – H + HCl
Acid chloride. Boiling xylene Aldehyde
O O
|| Pd / BaSO4,S ||
CH3 – C – Cl + H2 CH3 – C – H + HCl
Acetyl chloride Boiling xylene Acetaldehyde
O
C Cl H2 CHO
Pd–BaSO4,S
Benzoyl chloride Benzaldehyde
The partial poisoning of catalyst is made in order to avoid the further reduction of aldehyde
to primary alcohol. This reaction is known as Rosenmund reduction.
Mechanism: The following mechanism seems to operate.
..
O ..O–H + –H
O
|| | || –
Pd
R – C – Cl + H2 R – C – Cl R–C + Cl
| |
Acidchloride
H H
O
||
R – C – H + HCl
Aldehyde
However, formaldehyde can not be prepared by this method since formyl chloride HCOCl
is unstable at room temperature.
(b) Ketones:
Ketones can be prepared easily by the action of dialkyl cadmium on acid chlorides.
O O
|| ||
/ Dry
2R – C – Cl + Cd R 2 2R – C – R/ + CdCl2
ether
Acid chloride Dialkyl cadmium Ketone
O O
|| ||
Dry
2CH3 – C – Cl + Cd(C2H5)2 2CH3 – C – C2H5 + CdCl2
ether
Acetyl chloride Diethyl cadmium Ethylmethyl ketone.
O O
2 – C – Cl Dry ether 2 – C – CH3

+ Cd (CH3)2 + CdCl2
Benzoyl chloride Dimethylcadimium Acetophenone

Dialkyl cadmium can be prepared from Grignard’s reagent by the action of CdCl 2
R Br
2RMgBr + CdCl2 Cd + 2Mg
R Cl
Dialkyl cadmium
5. From alkynes:
Hydration of alkynes in presence of HgSO4 and H2SO4 yields enols which readily
tautomerise giving aldehydes or ketones. The addition of water to unsymmetrical alkynes
is in accordance with Markownikoff’s rule.
CH CH2 CH3
||| 1%HgSO4 || |
Tautomerise
e.g. CH + H – OH CH – OH CHO
42%H2SO4
Acetylene 340K Vinyl alcohol Acetaldehyde
(Ethyne)
OH
O
1%HgSO4 3 2| 1 Tautomerise ||
CH3 – C º CH + H – OH CH3 – C == CH2 CH3 – C – CH3
42%H2SO4
Propyne Acetone
340K
Prop - 1-en-2-ol
Note: However, aldehydes other than acetaldehyde cannot be prepared by this method.
6. From alkenes:
Alkenes add on a molecule of ozone forming the corresponding ozonides. The ozonides
are highly unstable due to the peroxide linkage so that these are shortlived, and explosive in
nature. On boiling with zinc dust and water ozonides undergo reductive cleavage producing
aldehydes or ketones or a mixture of both depending on the substitution pattern of the alkene.
Zinc dust helps in removing H 2O2, else the aldehydes or ketones formed may be oxidised to
carboxylic acids.
O
O
H H O3 H2C CH2 ||
Zn dust
C=C 2H – C – H + H2O+ZnO
H H CCl4 O O H2O
Formaldehyde
Ethylene
196K Ethylene ozonide
CH3 O3 CH3 O CH3 CH3

H Zn dust
C=C C CH C=O
CH3
CH3 CH3 CCl4 H2O CH3
196K O O
2-Methylbut -2-ene Acetone
+ CH3CHO
Acetaldehyde
+ ZnO + H2O
CH3 CH3 O3 CH3 O CH3

C=C Zn dust CH3
C C C=O
CH3 CH3 CCl4 CH3 CH3 H2O CH3
2,3-Dimethylbut-2-ene 196K O O Acetone
CH3
+ C=O
CH3
Acetone
O + ZnO + H2O
CH3 CH3
O3 CH CH Zn dust
CH3 – CH = CH – CH3 2CH3CHO +
CCl4 H2O
O O Acetaldehyde
But-2-ene 196K + ZnO + H2O
7. From gem - Dihalides:

A gem-dihalide is a compound containing two halogen atoms attached to the same
X
carbon. C (X = Cl, Br). The hydrolysis of a gem-dihalide yields a carbonyl group.
X
Thus, 1.1 dihaloalkanes on hydrolysis with aqueous KOH yield aldehydes whereas
2, 2-dihaloalkanes under similar condition yield ketones.
Cl OH --H2O
CH3 — CH + 2KOH(aq) CH3 CH CH3CHO
Cl OH
(1, 1 -Dichloroethane) unstable Acetaldehyde

CH3 Cl CH3 OH --H2O CH3

C + 2KOH(aq) C C=O
CH3 Cl CH3 OH CH3
(2,2 -Dichloropropane) unstable Acetone
8. From Grignard Reagent

(i) Preparation of Aldehydes
(a) When Grignard reagents react with hydrocyanic acid (HCN) and the products are
hydrolysed, aldehydes are formed. For example,
+ O
d- d+ d+ d- Dry
[CH3 – CH =NMgBr] H3O
ether CH3-C-H
Methylmag. bromide Hydrocyanic acid Addition product Acetaldehyde
+ Mg (OH) Br + NH3
(b) Aldehydes can also be prepared by the action of Grignard reagents on orthoformic
esters. For example,
dry ether OC2H5

CH3-CH + Mg (OC2H5)Br
Ethylmag. bromide
OC2H5
Ethyl orthoformate Diethyl acetaldehyde acetal
O H3O+, hydrolysis
CH3-C-H + 2 C2H5OH
(ii) Preparation of Ketones Acetaldehyde
(a) From acid chlorides
Acid chlorides react with Grignard reagents in equimolecular proportion (why ?) and the
products formed on hydrolysis with dilute mineral acid yield ketones. For example,
O OMgX + R'
dry ether H3O
R' — C — Cl + RMgX R' — C — Cl C = O + Mg (Cl) X
R
R (Ketone)
Choosing R, R¢ suitable ketones can be prepared using Grignard reagents. For example,
methyl magnesium bromide can react with propanoyl chloride (R¢ = C2H5) to give ethyl methyl
ketone (butanone) after hydrolysis of the intermediate addition product with dilute mineral acid.
O OMgBr
+ C 2 H5
Dry ether
C2H5 – C – Cl + CH3 Mg Br C2H5 – C – Cl H3O C=O
(Propanoyl chloride) CH3 CH 3
(Butanone) + Mg (Cl) Br
(b) From nitriles

Ketones can be prepared by the action of a suitable Grignard reagent on an alkane nitrile
followed by acid hydrolysis of the intermediate addition product.
For example,
Addition product
Ethylmag. bromide Methyl cyanide
or
Ethane nitrile
Butanone
18.6 SPECIAL METHODS OF PREPARATION FOR AROMATIC CARBONYL

COMPOUNDS :
A. Preparation of Benzaldehyde
Benzaldehyde may be prepared by the following methods which are applicable to aromatic
aldehydes in general
(1) Oxidation of Toluene
(a) By Etard’s reaction :
This reaction involves the preparation of benzaldehyde by the oxidation of toluene.
Toluene, when treated with chromyl chloride (CrO2Cl2) in presence of CCl4 or CS2, a
brown complex is precipitated as intermediate, which on hydrolysis gives benzaldehyde. Here,
chromyI chloride is used as oxidising agent. The reaction is called Etard’s reaction.
OCrCl2OH
CH3 CH CHO
| | OCrCl2OH + |
2CrO2Cl2 / CCl4 H3O
Toluene Brown complex (Benzaldehyde)
In case of derivatives of benzene having side chain longer than —CH 3, the end carbon is
oxidised by chromyl chloride to —CHO group. For example,
CH2CH3 CH2CHO
| |
CrO2Cl2/CCl4
+
H3O
Ethylbenzene Phenyl ethanal
(b) Oxidation by Chromium trioxide

Other than Etard’s reaction benzaldehyde can also be prepared by the oxidation of toluene
with chromium trioxide in acetic anhydride. The gem-diacetate first formed is isolated which
upon hydrolysis with dil.alkali or dil. HCl or dil. H2SO4 yield benzaldehyde.
OCOCH3
CH3 CH
CrO3/(CH3CO) 2O
OCOCH3
273-283K
toluene gem-diacetate
+ CHO
H3O, D
+ 2 CH3COOH
(hydrolysis)
benzaldehyde
(2) From Acid Chlorides (Rosenmund Reduction)
Benzaldehyde may be prepared by passing hydrogen gas through boiling xylene solution of
benzoyl chloride in the presence of palladium catalyst supported over BaSO 4 and partially poisoned
by the addition of sulphur or quinoline.
O
C Cl CHO
+ H2 Pd-BaSO4, S + HCl
Boiling xylene
benzoyl chloride benzaldehyde
(3) From nitriles (Stephen reduction)
When an ethereal solution of benzonitrile is reduced with stannous chloride in presence of
hydrogen chloride gas at room temperature, benzaldimine hydrochloride is precipitated. This
upon hydrolysis with boiling water gives benzaldehyde.
C N Dry ether CH = NH. HCl
+ 2 [H] + HCl
290-295K
benzonitrile benzaldimine hydrochloride
+ CHO
H 3O
+ NH4Cl
D
benzaldehyde
This process is called Stephen reduction.
Nitrites can also be selectively reduced by diisobutylaluminium hydride (DIBAL – H) to
imines followed by hydrolysis to aldehydes.
1. AlH (i-Bu) 2
RCN 2. H2O RCHO
1. AlH (i-Bu) 2
CH2 = CH – CH2 – CN 2. H2O CH2 = CH – CH2 – CHO
(4) By side chain halogenation followed by hydrolysis

Side chain chlorination of toluene gives benzal chloride which upon hydrolysis gives
benzaldehyde. This method is used for the manufacture of benzaldehyde.
CHCl2 H2O, 373K
CH3 2Cl2 , hn CH(OH)2
(Hydrolysis)
(-2HCl) (-2HCl)
Toluene
CHO
H2O
benzaldehyde
(5) By Gattermann – Koch reaction
When a mixture of carbon monoxide and HCl gas is passed through a solution of benzene
in nitrobenzene at 323K in presence of a catalyst consisting of anhydrous AlCl 3 and a small
amount of CuCl, benzaldehyde is formed.
CO + HCl [HCOCl]
Formylchloride (unstable)
CHO
+ HCOCl AlCl3 + CuCl + HCl
benzene benzaldehyde
This reaction is known as Gattermann - Koch reaction.
B. Preparation of Aryl Ketones :
(1) From Nitriles :
When phenyl magnesium bromide (Grignard reagent) reacts with an alkane nitrile in the
presence of dry ether, an intermediate is formed which on acid hydrolysis produces aryl keton.
NMgBr
CH3 – C º N + C6H5MgBr ¾dry

¾¾¾
ether
¾® CH3 — C
C 6H 5
Ethane nitrile Phenyl H3O+
magnesium
bromide O
CH3 — C
C6H5
Acetophenone
(2) From benzene or substituted benzene by Friedel-Crafts acylation reaction :
Friedel-Crafts acylation reaction involves the conversion of benzene or substituted benzene
to aryl ketone on reaction with acid chloride or acid anhydride in the presence of a Lewis acid as
catalyst like anhydrous aluminium chloride.
C – CH3
O Anhydrous
AlCl3
+ CH3 – C – Cl + HCl
Benzene Acetyl chloride Acetophenone
O Anhydrous O
Alcl 3
+ C6H5 – C – Cl C + HCl
Benzene Benzoyl chloride Benzophenone

O
COCH3
Anhydrous
CH3 C Alcl3
+ O + CH3 COOH
CH3 C
Benzene Acetophenone Acetic acid
O
Acetic anhydride
18.7 PROPERTIES OF ALDEHYDES AND KETONES :
(a) Physical Properties:

1. Physical State: Formaldehyde is a gas at room temperature. Other aldehydes and
ketones up to C11 are liquids and higher ones are solids.
2. Odour: Lower aldehydes have unpleasant odour whereas higher members have
pleasant odour. Ketones are generally sweet smelling.
3. Solubility: Lower members are soluble is water, but solubility decreases with increase
in molecular mass. However, all aldehydes and ketones are soluble is organic solvents
like alcohol, ether etc.
Explanation : The lower members are capable of forming hydrogen bond with water.
So they are soluble in water.
+d -d +d -d
R – C = O....H –– O
| +d -d +d
H H....O = C – R
|
H
Hydrogen bonding of aldehydes with water
R +d -d +d -d
C = O....H –– O
R +d d- +d R
H....O = C
R
Hydrogen bonding of ketones with water
As the hydrocarbon portion of alkyl group increases with increase in molecular

mass, the solubility rapidly decreases since the hydrogen bonding is prevented.
4. Boiling poiont : Boiling points of aldehydes and ketones are more than those of
alkanes but less than those of alcohols of comparable molecular mass. The boiling
points of ketones are slightly higher than those of isomeric aldehydes.
e.g Compound Molecular mass Boiling point(K)
CH3CH2CH2CH3 58 309
CH3CH2CHO 58 322
CH3CH2CH2OH 60 371
CH3COCH3 58 329
Explanation:
Boiling point depends upon molecular association. The stronger the intermolecular forces
the more is the boiling point. In case of alkanes the molecules are held together by weak vander
Waal’s forces. But in case of aldehydes and ketones the association is due to electrostatic attraction
between two opposite ends of carbonyl dipoles.
Thus, the boiling points of aldehydes and ketones
-dO C +d are more than those of alkanes. In case of alcohols there
|| || is intermolecular hydrogen bonding which is stronger than
+dC O -d dipole-dipole interaction. Hence, the boiling points of
alcohols are more than those of aldehydes and ketones.
(Dipole-dipole interaction in case of
In case of ketones the carbonyl group is attached to
aldehydes and ketones)
two electron releasing alkyl groups. As a result the
H –– O ..... H –– O ..... H –– O carbonyl group in ketones becomes more polar than in
| | | isomeric aldehyde. The more the polarity the more is
R R R the dipole-dipole interaction. Thus, ketones boil at
(Hydrogen bonding in case of alcohols)
comparatively higher temperature.
(b) Chemical Properties:
(1) Nucleophilic addition reactions: (AdN)
These reactions are due to the presence of a polar carbonyl group. The attacking agent
is a nucleophile (nucleus loving) and the reaction is of addition type. Since oxygen atom is
more electronegative, there develops an infinitesimal small positive charge over ‘C’ atom
and a small -ve charge over ‘O’ atom of the carbonyl group. The nucleophile attacks at the
+vely charged carbonyl carbon and as a result the double bond breaks in the direction of ‘O’
atom resulting in the formation of an anion. The anion thus formed takes up a proton from
the solvent (usually water) or from the reagent forming the addition product. The reaction
may be represented as follows.
Nu Nu
d-
| Fast |
d+ Slow —
C = O + : Nu — C — O — C — OH
| + + |
E (H )
Carbonyl Nucleophile Addition product
compound
(Planar) (Tetrahedral) (Tetrahedral)
Nucleophilic addition reactions are usually carried out in weakly acidic medium in case
of weak nucleophiles like NH3 or its derivatives. The protonation of ‘O’ atom of carbonyl group
in presence of acids increases the positive charge on the carbon atom thereby facilitating the
attack of the weak nucleophile.
+
..
C = O + H+ C –O–H
..
C = O+ – H
(2) Relative reactivities of Aldehydes and Ketones towards nucleophilic addition reactions.
Aldehydes are found to be more reactive than the ketones. This can be explained by two
effects i.e. electronic effects (resonance effect and inductive effect) and steric effect.
A. Aliphatic aldehydes and ketones.
(i) Inductive effect:
Alkyl groups are electron releasing. The presence of alkyl group at the carbonyl carbon
decreases the magnitude of the positive charge over ‘C’ atom thereby decreasing its tendency to
accept the nucleophile. Thus, the more the number of alkyl groups attached to the carbonyl group
the lesser is its reactivity towards nucleophilic addition reaction. The reactivity basing upon +l
effect thus follows the order.
O
||
HCHO > RCHO > R – C – R/
Formaldehyde Aldehyde Ketone
Again, presence of electron withdrawing groups at the carbonyl carbon (-l effect) increases
the magnitude of the positive charge over ‘C’ atom thereby facilitating the nucleophilic attack.
Thus, reactivity of substituted acetaldehyde follows the order,
NO2 CH2 CHO > ClCH2 CHO > CH3CHO

Nitroacetaldehyde Chloroacetaldehyde Acetaldehyde.
Further, the size of the alkyl groups also affects the reactivity. With increase in size of the
alkyl group the reactivity decreases. Thus, the order of reactivity of various ketones is as follows.
CH3COCH3 > CH3 COCH2CH3 > CH3CH2 COCH2CH3

Acetone. Ethylmethyl ketone Diethyl ketone.
(ii) Steric effect:

The approach of the nucleophile is prevented by the presence of bulky alkyl groups at the
carbonyl carbon. This effect is known as steric effect. The attack of the nucleophile at the carbonyl
carbon becomes more and more difficult as the number and size of the alkyl groups increase.
Hence, the reactivity of aldehydes and ketones follows the following order,
H CH3 CH3 CH3 CH2
H
C=O > H
C=O > CH3
C=O > CH3 CH2
C=O >
(CH3)2CH (CH3)3C
C=O > (CH3)3C
C=O
(CH3)2CH
Di-isopropyl ketone Ditert-butyl ketone
B. Aromatic aldehydes and ketone :

(i) Aromatic aldehydes and ketones are less reactive towards nucleophilic addition reactions
than the aliphatic ones due to negative resonance effect (–R) decreasing the nucelophilic character
of the carbonyl carbon atom as carbony group is an electron withdrawing group. This in turn
decreases its tendency to be attacked by the nucleophile.
R R R
d+ d- - -
–R C=O C–O C–O
R R R
d- -
C O C=O C O
+
d+
Resonance hybrid Resonating structures

(ii) Again aromatic aldehydes are more reactive than aryl ketones due to +I effect of the alkyl
group.
C6H5CHO > C6H5COCH3 > C6H5COC6H5
3. Examples of Nucleophilic addition reactions :

(a) Addition of HCN
Both aldehydes and ketones react with HCN forming the corresponding cyanohydrins.
O OH
|| |
R – C – H + HCN R — C –– CN
|
Aldehyde H Aldehyde cyanohydrin
O OH
|| |
CH3 – C – H + HCN CH3 — C — CN
|
H
Acetaldehyde. Acetaldehyde cyanohydrin.
O OH
|| |
R – C – R/ + HCN R — C –– CN
|
Ketone R/ Ketone cyanohydrin
O OH
|| |
CH3 – C – CH3 + HCN CH3 — C — CN
|
Acetone CH3
Acetone cyanohydrin
O OH
C H C CN
OH–
+ HCN
H
Benzaldehyde Benzaldehyde
Cyanohydrin
Since HCN is a poisonous substane the reaction is often carried out by mixing the carbonyl
compound with aqueous sodium cyanide and then slowly acidifying the solution by adding mineral
acid. This reaction is a base catalyzed reaction proceeding through the following mechanism.
-- --
HCN + OH CN + H2O
CN CN
R +d -d -- | -- H2O | --
C = O + CN R—C—O R — C — OH + OH
H | |
H H
Aldehyde. Nucleophile Cyanohydrin
Cyanohydrins are nitriles. They, upon hydrolysis yield a-hydroxy acids which undergo
subsequent dehydration forming a, b unsaturated acids.
O OH
HCN HOH
e.g. CH3CH2 — C — CH3 CH3 — CH2 — C — CN
HCl
Ethylmethyl ketone
CH3
OH O
b a| || H2SO4 b a
CH3–– CH2 –– C –– C –– OH CH3 –– CH = C –– COOH
| |
CH3 –H2O CH3
a- hydroxy acid a, b-unsaturated acid
(b) Addition of NaHSO3

Both aldehydes and ketones (specially methyl ketones) react with NaHSO 3 forming
the corresponding crystalline bisulphite compounds.
O OH
|| |
CH3 – C – H + NaHSO3 CH3 — C — H
|
SO3Na
Acetaldehyde sodium bisulphite
O OH
|| |
CH3 – C – CH3 + NaHSO3 CH3 — C — CH3
|
SO3Na
Acetone sodium bisulphite
The reaction is carried out by adding carbonyl compound to a concentrated aqueous

solution of sodium bisulphite when a crystalline solid bisulphite compound separates out.
Machanism: There is initial nucleophilic attack by bisulphite ion on carbonyl carbon followed
by proton transfer.
– +
O Na Proton OH
C=O C C –
+ .. – SO3H transfer SO3Na+
Na SO3H
Bisulphite
compound
The crystalline bisulphite addition product can be decomposed with dilute mineral acids
or aqueous alkalies to regenerate the original aldehyde or ketone.
OH
C + HCl C=O + NaCl + SO2 + H2O
–
SO3Na+ Carbonyl compound
OH
C + NaOH C = O + Na2SO3 + H2O
–
SO3Na+
The reaction is employed for separation and purification of carbonyl compounds from noncarbonyl
impurities or compounds.
(c) Reaction with Alcohols
Alcohols add to the carbonyl group of aldehydes in the presence of dry HCl gas acid to
yield hemiacetals, which further react with alcohols to give a gemdialkoxy compound known as
acetal.
H H
| dry HCl |
R¢ – C = O + ROH R¢ – C – OR
H+
Aldehyde |
OH
Hemi acetal (Unstable)
H H
| |
H+
R¢ – C – OR + ROH R¢ – C – OR + H2O
| |
OH OR
Hemiacetal Acetal
(An alcohol) (An ether)
MECHANISM
This reaction proceeds through the following steps.
H H H
+
(i) R—C=O + H+ R—C=O—H R — C — OH
+
H H H
(ii) R — C — OH + HO — RI R — C — OH R — C = OH
+
+ O—H –H+ ORI
RI
H H
+ H
(iii) R — C — OH + H+ R—C—O
H
I
OR OR
H H H H
(iv) R—C—O—H + HO — RI R — C — O — RI
+ –H2O +
I I
OR OR
–H+
R — C — ORI
ORI
For example, acetaldehyde is converted to acetal as follows. The forward reaction is

catalysed by dry HCl, while the reverse reaction is catalysed by aqueous HCl.
H
CH3 |
HCl
C = O + C2 H5 OH CH3 – C – OC2 H5
H |
OH
Acetaldehyde Hemiacetal
H H
| HCl |
CH 3 – C – OC2H5 + C2H5OH CH3 – C – OC2H5 + H2O
| |
OH OC2H5
Hemiacetal Acetaldehyde diethyl acetal
Ketones would react similarly to form hemiketals and ketals.
R R OR'
'
C = O + ROH C
R
R OH
Hemiketal
R OR' R OR'
C + R¢ OH C + H2O
R OH R OR'
ketals
The above equilibria lie far to the left and are unfavourable to the formation of ketals.
However, if the equilibria are tilted to the right by removing water produced during the reaction,
ketals are prepared with better yield. This is done by the addition of orthoformic ester.
OC2H5
H+
H-C OC2H5 + H O 2C2H5OH + HCOOC2H5
2
OC2H5
ethyl orthoformate ethyl formate
PROTECTION (BLOCKING) OF CARBONYL GROUP BY CYCLIC ACETAL

FORMATION
In the course of organic synthesis it is sometimes necessary to protect or mask a carbonyl
group in a molocule by preventing it from reacting during the course of a transformation of some
other functional group in the molecule. This is done by converting the carbonyl group into an
acetal or cyclic ketal which is regenerated by acid hydrolysis.
+
2C2H5OH OC2H5 H3O OH
C=O C= O
C C=O
dry HCl OC2H5 –2C2H5OH OH
–H2O
(Protected as acetal or ketal)
–H2O C=O
regenerated
Cyclic acetals or ketals are obtained by reaction with glycol in the presence of acid and in
the absence of alkyl formate. The carbonyl group is regenerated from the cyclic acetals or ketals
by acid hydrolysis.
HO – CH2 R O CH2
HCl C
C=O +
HO – CH2 R O CH2
–H2O
aldehyde/ketone glycol cyclic acetal/ketal
CH2 OH
HOH/H + C=O +
CH2 OH
aldehyde/ketone
(d) Addition of Grignard reagents :
Grignard reagents add to the carbonyl group of aldehydes and ketones forming an adduct
which on acid hydrolysis produce alcohols.
d+ d– d– d+
C=O + R – Mg – X C – O – Mg – X
R +
H 3O
OH
C – OH + Mg
X
R
Alcohol
(i) Formation of primary (I°) alcohol on reaction with formaldehyde.
H H
C = O + CH3 – Mg – Br C – O – Mg – Br
H H
Methanal CH3
H+/H 2O
H OH
C – OH + Mg
H X
CH3
Ethanol
(ii) Formation of secondary (2°) alcohol on reaction with any aldehyde excepting formadehyde.
CH3 CH3
C = O + CH5 – Mg – Br C – O – Mg – Br
H H
Ethanal CH3
H+ /H2O
CH3 OH
C – OH + Mg
H Br
CH3
Propan - 2-01
(iii) Formation of tertiary (3°) alcohol on reaction with a ketones.
H3C CH3
C = O + CH3 – Mg – Br C — O – Mg – Br
H 3C CH3
Propanone CH3
H+/H 2O
CH3
OH
H3C C – OH + Mg
Br
CH3
2-Methylpropan-2-ol
CH3
CH3
C = O + C6H5 – Mg – I CH3 — C — O – Mg – I
CH3
C6H5
H+ /H2O
CH3
I
CH3 C – OH + Mg
OH
C6H5
3° Alcohol
(e) Nucleophilic addition reactions followed by elimination of water (Addition of

ammonia derivaties).
Derivatives of ammonia (H2N–G) such as hydroxyl amine (NH2OH), phenyl hydrazine

(C6H5NHNH2), semicarbazide (NH2NHCONH2) etc. react with carbonyl compounds in weakly
acidic solution to form compound C = N – G..
The reaction proceeds through the initial attack of nucleophile on the carbonyl group to
form addition product, which subsequently loses a molecule of water to give a compound having
a double bond between carbon and nitrogen. The reaction may be represented as follows:
H+ OH
C = O + H2N – G C C = NG + H2O
fast NHG slow
Carbonyl Derivative
compound of NH3
The above reaction is very much helpful in identifying carbonyl compounds since the
compound so formed as final product is an insoluble crystalline solid having sharp melting point.
The reactions of carbonyl compounds with ammonia derivatives are carried out at moderate
acid strength or pH. The protonation of carbonyl oxygen takes place which makes the carbonyl
carbon more prone to nucleophilic attack.
H H
+ .. | |+ | |
C = O + H+ C — OH NH2 — G –C–N –G – C – N –G
| | –H+ |
OH H OH
C = N – G +H2O
Although the reaction is acid catalysed, the solution should not be too much acidic. This is because
the ammonia derivative gets protonated, thereby decreasing its nucleophilicity.
.. +
G — NH2 + H+ G – NH3
Free base Salt
(i) Reaction with Hydroxylamine (NH2OH)

Aldehydes and ketones react with NH2OH in presence of HCl to form corresponding
oximes (aldoximes and ketoximes)
H
e.g. R–C + H2N – OH R – CH = N — OH + H2O
O
Aldehyde Hyxroxylamine Aldoxime
H
H |
H–C + H2NOH H – C = N — OH + H2O
O
Methanal Methanaloxime
CH3 – C = O + H2NOH CH3 – CH = N — OH + H2O

|
H (Ethanal oxime)
Ethanal
R R
C = O + H2NOH C = N – OH + H2O
R R
Ketone Ketoxime
CH3 CH3
C = O + H2NOH C = N – OH + H2O
CH3 CH3
Propanone Propanoneoxime
O H
|| ||
—C–H — C = N – OH
+ H2NOH
Benzaldehyde Benzaldehydeoxime
(ii) Reaction with hydrazine ( NH2 – NH2)

Aldehydes and ketones react with hydrazine in presence of dilute acid forming
corresponding hydrazones.
R H
+ R
C=O + H2N – NH2 C = N – NH2 + H2O
H H
(Aldehyde) Hydrazine (Aldehyde hydrazone)
R H
+ R
C=O + H2N – NH2 C = N – NH2 + H2O
R R
(Ketone) (Ketone hydrazone)
(iii) Reaction with phenylhydrazine (C6H5NHNH2)

Aldehydes and ketones react with phenylhydrazine in presence of dilute mineral acid
forming crystalline phenylhydrazones.
R R
C=O + H2N.NHC6H5 C = N.NHC6H5 + H2O
H H
Aldehyde Phenyl hydrazine Aldehyde phenyl hydrazone
H H
C = O + H2N.NHC6H5 C = N.NHC6H5 + H2O
H H Formaldehyde
Formaldehyde phenyl hydrazone
CH3 CH3
C = O + H2NNHC6H5 C = N.NHC6H5 + H2O
H H
Acetaldehyde Acetaldehyde
phenylhydrazone
R R
R R Ketone
Ketone phenylhydrazone
CH3 CH3
CH3 CH3
Acetone Acetone phenyl hydrazone
O
||
(iv) Reaction with semicarbazide ( H2N – NH – C – NH2)
Aldehydes and ketones react with semicarbazide in acid medium to form the corresponding
semicarbazones.
R H+ R
C = O + H2N – NH – CO – NH2 C = N – NH – CO – NH2+ H2O
1 1
R Semicarbazide R (Semicarbazone)
R = R1 = H, Formaldehyde semicarbazone
R = H, R1 = CH3, Acetaldehyde semicarbazone
R = R1 = CH3, Acetone semicarbazone
R = H, R1 = – C6 C5 Benzaldehyde semicarbazone
Note:
The nitrogen derivatives of carbonyl compounds like oximes. hydrazones, phenyl

hydrazones, and semicarbazones are used primarily to identify aldehydes and ketones. This
is possible because these derivatives are mostly solids with characteristics melting points. 2,
4 - Dinitrophenyl hydrazine (DNPH) is more useful than phenyl hydrazine since the former
forms yellow-orange or red precipitate easily with aldehydes and ketones.
NO2
O2N NH – NH2 + O=C
Carbonyl compound
(2, 4 - Dinitrophenyl hydrazine)
H+
C = N — NH — — NO2 + H2O
2, 4 - Dinitrophenyl hydrozone NO2 (Orange ppt.)
4. Reactions due to a - hydrogen
Acidity of a - hydrogens of aldehydes and ketones :
Hydrogen atom present on the carbon atom next to the carboxyl group, called a - hydrogen
atom is acidic by nature due to the following factors.
(i) Carbonyl group is an electron withdrawing group (– I effect) thus decreasing the electron
density from the adjacent carbon - carbon bond making Ca - carbon electron deficient.
This in turn results with the decrease of electron density of a - H bond. Hence a - H atom
becomes acidic by nature and can be easily abstracted by a base forming enolate anion.
d– d+
O H O
—C— C — + OH —C— C —
d+ a H 2O
Enolate anion
(ii) Enolate anion i.e. conjugate base is resonancce stablilized.
O O
—C— C — — C= C —
Due to acidic nature of a - hydrogen atoms aldehydes and ketones undergo the following
reactions.
A. Aldol condensation: Two molecules of same or different carbonyl compounds each

containing a -H -atom, condense together in presence of dilute alkali like NaOH, KOH,
Ba(OH)2 or Na2CO3 to form a syrupy liquid known as Aldol. This aldol which shows the
properties of alcohol, aldehyde or ketone is b-hydroxy aldehyde or b-hydroxy ketone.
dil b a
e.g. CH3 CHO + HCH2CHO CH3CH(OH)CH2CHO
NaOH
Aldol
b -Hydroxy butyraldehyde
Mechanism :
(i) Formation of carbanion due to the abstraction of a - hydrogen by OH
O O
|| – – ||
CH2 - C - H + OH CH2 - C - H + H2O
|
H Carbanion.
(ii) Nucleophilic attack of carbanion on the electron deficient carbonyl carbon of other
molecule of acetaldehyde to form an anion
–
O O O
|| – || |
CH3 - C - H + CH2 - C - H CH3 - C - CH2CHO
|
H
(iii) The anion finally abstracts a proton from water to form aldol.
O OH
| |
CH3 — C — CH2CHO + H — OH CH3 - C - CH2CHO + OH
| |
H H
Aldol
Restrictions
(i) When concentrated alkali is used the aldol formed undergoes base catalysed dehydration
forming a, b-unsaturated aldehyde.
H – H
b| a OH
|
e.g. CH3 - C - CH2 - C - H CH3 - C - HC - C - H + H2O
| || –H2O | – ||
OH O OH O
–OH–
b a
CH3 - CH = CH - CHO
a, b -Unsaturated aldehyde
(Crotonaldehyde)
(ii) When a trace of mineral acid is there the aldol formed is no longer stable. It undergoes
acid catalysed dehydration to form a, b-unsaturated aldehyde.
H H
| H+ |
e.g. CH3 - C - CH2 CHO CH3 - C - CH2CHO
| |
+
OH O
H H
H
| b a
CH3— C — CH CHO CH3 - CH = CH - CHO
– H2O + | --H+ a, b -Unsatd. aldehyde
H
(Crotonaldehyde)
(iii) When two different aldehydes each containing a -hydrogen atom condense together in
presence of dilute alkali the product formed is a mixture of aldols. This is known as
Cross Aldol condensation or Cross Aldolisation. Examples are :–
O O O
dil.NaOH b a
I. CH3 — C — H + H — C — H HO — CH2 — CH2 — C — H
Acetaldehyde Formaldehyde b-hydroxypropionaldehyde
(No a - hydrogen
atom)
II. Here four different aldols are formed, two from condensation of the two aldehydes with
like molecules and the other two from condensation of two different aldehydes in two
different ways.
e.g. CH3CHO + CH3CH2CHO

Acetaldehyde Propionaldehyde
–
OH
OH OH OH OH
| | | |
CH3–CH–CH2CHO+CH3CH–CHCHO+CH3CH2CH–CH–CHO + CH3CH2CH CH2CHO
| |
CH3 CH3
Simple aldol Cross aldol Simple aldol Cross aldol
III. O O OH O
|| || | ||
C6H5 — C — H + CH3 — C — H ¾dil.NaOH
¾ ¾ ¾¾® C6H5 — CH — CH2 — C — H
—H2O
O
||
C6H5 — CH = CH — C — H
Cinnamaldehyde
Cross Aldol condensation is also possible in case of two different ketones and in case of
condensation reaction between an aldehyde and a ketone.
Aldol condensation is case of Ketones:
Two molecules of acetone condense together in presence of Ba(OH) 2 to produce
diacetonealcohol (aldol of acetone)
Ba(OH)2 CH3 OH
CH3 – C = O + H.CH2COCH3 C
| CH3 CH2COCH3
CH3
Acetone Acetone Diacetone alcohol
Diacetone alcohol upon heating loses a molecule of water to form mesityl oxide.
CH3 OH CH3
C C= CHCOCH3
CH3 – H2O CH3
CHCOCH3
| Mesityl oxide.
H
B. Iodoform reaction:
Compounds which contain CH3CO- group or which produce CH3CO group on oxidation
can undergo iodoform reaction. Methyl ketones or acetaldehyde when treated with sodium
hypoiodite (alkaline solution of iodine), iodoform is formed as yellow precipitate along with an
acid which contains one C atom less than the parent compound.
O O
|| NaOH ||
CH3 – C – CH3 + 3I2 CI3 – C – CH3 + 3 HI
Acetone Tri-iodoacetone
O
||
CI3 – C – CH3 + NaOH CHI3 + CH3COONa
Iodoform
(yellow ppt)
Mechanism:
NaOH Na+ + OH–
O O
|| – ||
CH2 – C – CH3 + OH– CH2 – C – CH3 + H2O
|
H Carbanion
Iodoform
This test is used for identification of compounds containing CH 3 CO-group or any other
group like CH3 –– CH –– OH which can be oxidised to CH3 CO-group by sodiumhypoiodite.
|
5. Oxidation reactions
Aldehydes differ from ketones in oxidation reactions. It is a fact that aldehydes can be
easily oxidised to carboxylic acids.
O O
|| ||
R – C – H + [O] R – C – OH
Aldehyde Carboxylic
acid
The easy oxidation of aldehydes is due to the presence of a H –atom attached to carbonyl
group which on oxidation becomes –OH group without breaking any other bond. Aldehydes can
also be oxidised with oxidising agents like Cu2+, Ag+ or bromine water to carboxylic acids. On
the other hand, ketones can be oxidised to carboxylic acids with less number of carbon atoms
under drastic conditions using powerful oxidising agents like acidified KMnO 4 or K2Cr2O7.
Thus, aldehydes are treated as good reducing agents. They can reduce Fehling’s solution and
Tollens’ reagent whereas ketones can not.
Mixed ketones when oxidised under drastic conditions give rise to a mixture of carboxylic
acids which involve cleavage of carbon-carbon bonds. When oxidised with acidified KMnO 4 or
K2Cr2O7 and conc.H2SO4, C--CO bond of the ketones breaks and the a- carbon atom containing
least number of hydrogen atom is attacked preferentially (Popoff’s rule). Thus,
acid. KMnO4
CH3 – CO – CH2 – CH2 – CH3 CH3COOH + CH3 CH2COOH
Pentan -2-one (Acetic acid) (Propionic acid)
If the carbon atoms adjacent to carbonyl group have the same number of hydrogen atoms,
the carbonyl group chiefly remains with the smaller alkyl group. Thus, the oxidation of hexan-3-
one gives propionic acid as the main product with smaller amount of acetic acid and butyric acid.
O
|| CrO3
CH3 – CH2 – C – CH2 – CH2 – CH3 CH3CH2COOH
oxdn.
Hexan -3-one (Propionic acid)
Main product
CH3COOH + CH3CH2CH2COOH
Small amounts
(i) Reduction of Fehling’s solution.
Aldehydes when boiled with Fehling’s solution form a red precipitate of Cu 2O. Fehling’s
solution is alkaline Cu(II) ion complexed with sodium potassium tartrate. It is a mixture of Fehling
A and Fehling B. Fehling A contains CuSO4 whereas Fehling B contains NaOH and sodium
potassium tartrate (Rochelle salt).
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
Cu(OH)2 CuO + H2O

O O
|| ||
R – C – H + 2CuO R – C – OH + Cu2O (Red ppt)
Carboxylic acid
Aldehydes thus reduce Cu2+ ions to Cu+ ion and get oxidised to carboxylic acids. Ionically
the same may be represented as
O
|| –
2+
R – CHO + 2Cu + 5OH R – C – O + Cu2O + 3H2O
Red
The function of Rochelle salt is to dissolve insoluble Cu(OH) 2 by complexing it with
tartrate ion. i.e. it prevents the precipitation of Cu(OH) 2.
Aromatic aldehydes do not reduce Fehling’s solution.

(ii) Reduction of Tollens’ reagent :
When an aldehyde is warmed with Tollens’ reagent a silver mirror is formed which appears
on tha walls of the test tube in which the reaction is carried out. Tollens’ reagent is ammoniacal
solution of AgNO3. It is prepared by adding NH4OH solution to a solution of AgNO3 till the
precipitate AgOH formed first again redissolves.
AgNO3 + NH4OH AgOH + NH4 NO3

AgOH + 2NH4OH [Ag(NH3)2] OH + 2H2O
Tollens’ reagent
O
|| – +
RCHO + 2[Ag(NH3)2OH R – C– ONH4 + 2Ag + 3NH3 + H2O
Silver
mirror
Here also Ag+ ion is reduced to metallic silver. The reaction is accompanied by oxidation
of aldehydes to carboxylic acids. The silver thus deposited shines like a mirror for which this test
is known as silver mirror test. This test is exhibited by both aliphatic and aromatic aldehydes.
6. Miscellaneous reactions:
A. Reaction with NH3:
(i) Formaldehyde reacts with NH3 to form hexamethylenetetramine [CH 2)6N4],
known as Urotropine which is used as urinary antiseptic.
6HCHO + 4NH3 (CH2)6N4 + 6H2O.

Hexamethylenetetramine.
Structure of Urotropine:
N
|
H2C CH2 CH2
|
N
CH2 CH2
N N
CH2
Nitration of urotropine under control conditions produces the explosive RDX (Research
and Development Explosive)
(ii) Other aldehydes react with NH3 to form aldehydeammonias which on heating
undergo dehydration to form aldimine.
O OH
|| | D
R – C – H + HNH2 R — C — NH2 R — C = NH
| – H2O |
H H
Aldehyde. Aldehydeammonia Aldimine
O OH
|| | D
CH3 – C – H + HNH2 CH3 — C — NH2 CH3 — C = NH
| – H2O |
H H
Acetaldehyde. Acetaldehydeammonia Acetaldimine
(iii) Acetone (2 molecules) react with NH3 to form an addition product diacetone -
amine, a complex ketonic amine.
CH3 CO CH2 H
CH3 CH2COCH3
+ H NH2 C + H2O
CH3 CH3 NH2
C=O
CH3
Diacetone amine.
B. Cannizzaro’s reaction:
Aldehydes having no a-hydrogen atom when treated with concentrated alkali undergo
disproportionation i.e. self oxidation-reduction reaction where one molecule of the aldehyde is
oxidised to carboxylic acid and other molecule is reduced to alcohol. This reaction is termed as
Cannizzaro reaction.
e.g. (i) HCHO upon reaction with conc. NaOH undergoes Cannizzaro’s reaction. Out of
two molecules of HCHO, one molecule is oxidised to HCOOH and other is reduced to CH3OH.
2HCHO Conc.NaOH HCOONa + CH3OH

Formaldehyde Sodium formate Methyl alcohol
(ii) Conc.NaOH
— CHO — COONa + — CH2OH
Benzaldehyde Sodium benzoate Benzyl alcohol

Mechanism:
(i) Nucleophilic attack of OH– at the electron deficient carbonyl carbon atom of one molecule
of aldehyde.
–
O d- O
|| – |
H — C — H + OH H—C—H
d+ |
OH
(ii) This step involves the hydride transfer from the above intermdiate to the second mol-
ecule of aldeyde.
– –
O O O O
| || Hydride || |
H—C—H H–C–H H – C –OH + H — C — H
| transfer
|
OH H
(iii) Since HCOO– ion is more stable than HCOOH, there will be H+ ion shift and as a result
formate ion is formed along with methyl alcohol.
O O
|| – H+ transfer || –
H — C — O — H + CH3O H – C – O + CH3OH
Na+
HCOONa
C. Reaction with Phosphorus pentachloride:

PCl5 reacts with simple carbonyl compounds to form dichlorides.
Cl
C = O + PCl5 C + POCl3
Cl
(carbonyl comp) (dichloroalkane)
H H
| |
H — C = O + PCl5 H — C — Cl + POCl3
|
Cl
Formaldehyde Dichloromethane
O Cl
|| |
CH3 – C – CH3 + PCl5 CH3 — C — CH3 + POCl3
|
Cl
(Acetone) (2, 2 -Dichloropropane)
D. Reduction: Aldehydes and ketones yield a variety of products on reduction under different
conditions.
(i) Catalytic reduction: When reduced with hydrogen in presence of a catalyst like Raney
Ni, Pt or Pd, aldehydes give primary alcohols whereas ketones give secondary alcohols.
R – CHO H2 /Ni RCH2 OH

Aldehyde 10alcohol
H – CHO H2 /Ni CH3 OH

Formaldehyde Methyl alcohol
CH3 – CHO H2 /Ni CH3 CH2 OH

Acetaldehyde Ethyl alcohol
R H2 /Ni R
C=O CH — OH
R| R|
(Ketone) 20 -alcohol
CH3 H2 /Ni CH3

C=O CH — OH
CH3 CH3
Acetone Isopropyl alcohol
(ii) Reduction by chemical reducing agents : Alcohols can also be obtained by reducing
cacrbonyl compounds using lithium aluminium hydride (LiAIH 4) or sodium borohydride
(NaBH4) or sodium and ethyl alcohol.
LiAlH4
CH3CHO CH3CH2OH
Ethanal Ethanol
NaBH4 is a mild and selective reducing agent, since it reduces only the carbonyl group
without affecting the carbon-carbon double bonds in the molecule. Thus,
NaBH4
CH3 – CH = CH – CHO CH3 – CH = CH – CH2OH
But -2-en-1-al But -2-en-1-ol
H2 /Ni
But, CH3 – CH = CH – CHO CH3 – CH2 – CH2 – CHO
Butanal
(iii) Reduction to hydrocarbons : The C = O group of aldehydes and ketones may be

converted to CH2 by the following methods.
(I) Clemmensen reduction : This involves the reduction of aldehydes or ketone by zinc
amalgam in the presence of Conc. HCl
H
| Zn/Hg &
R — C = O +4H R – CH3 + H2O
Aldehyde Conc.HCl
alkane
R R
C = O +4H CH2
R/ Zn/Hg & Conc.HCl R/
Ketone alkane
Acetaldehyde forms ethane whereas acetone forms propane on Clemmensen reduction.

Zn/Hg, Conc.HCl
C6H5COCH3 + 4[H] C6H5 – CH2CH3 + H2O
Acetophenone Ethyl benzene
(II) Wolff - Kishner reduction : Carbonyl group of aldehydes and ketones can be reduced
to – CH2– group on reaction with hydrazine followed by heating with sodium or potassium
hydroxide in the presence of ethylene glycol.
KOH/Ethylene
NH2NH2 glycol
C=O C = NNH2 CH2 + N2 (g)
– H2O D
For example :
(i) NH2NH2
CH3CHO CH3CH3
(ii) KOH, Glycol
Ethanal Ethane
D
(i) NH2NH2
C6H5COCH3 C6H5CH2CH3
(ii) KOH, Glycol
Acetophenone Ethylbenzene
D
E. Reaction with primary amines : Aldehydes and ketones react with primary amines in
the presence of acid as catalyst to form Schiff’s bases.
+
CH3CHO + H2NCH3 H CH3CH = NCH3 + H2O
D
Acetaldehyde Methylamine Schiff’s base
+
C6H5CHO + H2NC6H5 H C6H5CH = NC6H5 + H2O
D
Benzaldehyde Aniline Benzal aniline
(A Schiff’s base)
F. Electrophilic Substitution Reactions in aromatic aldehyde and ketones :

Aromatic aldehydes and ketones undergo electrophilic substitution reactions such as
halogenation, nitration and sulphonation at the meta position. Since carbony group is an elctron
withdrawing group, it is a a ring deactivating and m-directing group, it does not undergo Friedel-
Craft’s reaction.
I. Nitration : Benzaldehyde when treated with concentrated nitric acid in the presence of
concentrated sulphuric acid undergoes nitration to form m-nitrobenzaldehyde. The reaction
proceeds through electrophilic substitution reaction. The carbonyl group present in
benzaldehyde behaves as a ring deactivator and meta-director, towards electrophilic
substitution reaction.
CHO CHO
| |
H2SO4
+ HNO3 + H2O
NO2
|
(Conc.)
Benzaldehyde (m-nitro benzaldehyde)
With acetophenone, m-nitroacetophenone is formed.
COCH3 COCH3
| |
Conc..H2SO4
+ HNO3 + H2O
NO2
|
(Conc.)
Acetophenone (m - nitro acetophenone)
Mechanism:
+
Step -1 : Formation of electrophile (NO2)
+
HNO3 + 2H2SO4 NO2 + 2HSO4– + H3O+
Step - 2 : The electrophilic attack and formation of carbocation :
CHO CHO
| |
+ +
+ NO2 H
NO2
Step : 3 Loss of proton and formation of m-nitro benzaldehyde.
CHO CHO
| |
+
HSO 4- + H2SO4
H
NO2 NO2
m-nitro benzaldehyde
II. Halogenation : Like nitration, benzaldehyde and acetophenone undergo halogenation.

For example, benzaldehyde reacts with chlorine in the presence of FeCl 3 or Anhy. AlCl3
at room temperature, to form m-chlorobenzaldehyde. Here, Cl + ion acts as electrophile.
CHO CHO
| |
+ Cl2 Anh. AlCl3 + HCl
Cl
Benzaldehyde m-chloro benzaldehyde
Similarly
COCH3 COCH3
| |
+ Br2 Anh. AlBr3 + HBr
Br
Acetophenone m-Bromoacetophenone
III. Sulphonation : Both aryl aldehydes and ketones undergo sulphonation giving m-
derivative.
COCH3 COCH3
+ Conc. H2SO4 + H2O
Acetophenone SO3H
m-acetylbenzenesulphonic acid
CHO CHO
+ Conc. H2SO4 + H2O
Benzaldehyde
SO3H
m-Benzaldehyde sulphonic acid
18.8 USES OF ALDEHYDES AND KETONES :
Aldehydes and ketones are used as solvents starting materials and reagents for the
synthesis of other products in the chemical industry. Some of the important cases of aldehydes
and ketones are :
(i) 40% aqueous solution of formaldehyde called formalin is used for the preservations of
biological or anatomical specimens. It is also used as disinfectant and as a germicide.
(ii) Formaldehyde is used in the manufacture of bakelite, resins and other polymers.
(iii) Acetaldehyde is used in the preparation of a number of organic compounds such as acetic
acid, ethyl acetate, n-butyl alcohol etc., and in the silvering of mirrors.
(iv) Benzaldehyde is mostly used as a flavouring agent in perfume industry in addition to its
use for the preparation of a number of organic compounds like cinnamic acid, benzoyl
chloride etc.
(v) Acetone is widely known for its use as one of the constituents of the liquid nail polish.
(vi) Compounds like vanillin, acetophenone, camphor etc. are well known for their use as
flavouring and adouring agent.
18.9 SOLVED PROBLEMS :

1. A ketone ‘A’ which undergoes haloform reaction gives compound ‘B’ on heating
with sulphuric acid gives compound’C’ which forms monoozonide ‘D’. ‘D’ on
hydrolysis in presence of zinc dust gives only acetaldehyde. Identify A, B, C and
write down the reactions involved.
Solution : We know that the ketone which undergoes haloform reaction must contain a
O
||
CH3—C— group. So ‘A’ must be methyl ketone. Again since ‘C’ forms a monoozonide,
it must contain a C=C bond. ‘D’ on hydrolysis in presence of zinc dust gives acetaldehyde.
Hence the structure of ‘C’ will be
CH3—CH = CH— CH3

(C)
‘B’ on dehydration gives ‘C’. So the structure of ‘B’ will be

OH
|
CH3—CH — CH2— CH3
(B)
Again ‘B’ is obtained upon reduction of ‘A’. So ‘A’ has the structure
O
||
CH3—C— CH2— CH3
(A) Butanone
The reactions involved may be represented as follows.
O OH
|| | H2SO4
[2H]
CH3—C— CH2— CH3 CH3—CH— CH2— CH3
– H2O
(A) (B)
O
CH
3— CH 3
+O3 CH CH —
CH3—CH = CH — CH3
O O
(C)
Zn/H2O (D)
2 CH3 CHO
2. Compound ‘A’ with molecular formula C 5H12O on oxidation forms compound ‘B’
with molecular formula C 5H10O. The compound ‘B’ gives iodoform test but does
not reduce ammoniacal AgNO 3. ‘B’ on reduction with amalgamated zinc and HCl
gives compound ‘C’ with molecular formula C 5H12. Identify A, B and C. Write down
the chemical reactions involved.
Solution:
‘B’ gives iodoform test but does not reduce ammoniacal AgNO 3 (Tollens’ reagent) Thus
O
||
‘B’ is not an aldehyde, it must be a ketone having CH3 — C — group i.e. it must be a
methyl ketone. So ‘B’ may be
O
||
CH3 – C – CH2 – CH2 – CH3
(B) Pentan -2-one

Again ‘B’ is obtained from ‘A’ on oxidation. So ‘A’ is a secondary alcohol.
OH
|
CH3 – CH – CH2 – CH2 – CH3
(A) Pentan -2-ol
‘B’ upon reduction with Zn/Hg and HCl gives ‘C’ having molecular formula C 5H12. The
> C=O group is converted to > CH2 group.
So it must be a hydrocarbon. CH3 — CH2 — CH2 — CH2— CH3
n — Pentane (C)
The reactions may be represented as
OH O
| ||
[O]
CH3 — CH — CH2 — CH2— CH3 CH3 — C — CH2 — CH2— CH3
(A) (B)
Zn/Hg & HCl
CH3 — CH2 — CH2— CH2— CH3 (C)
3. Compound (A) C5H10O forms phenyl hydrazone and gives negative Tollens’ and
iodoform tests. Compound ‘A’ on reduction gives n-pentane. Give the structure of
(A). Explain the reaction.
Solution:
Compound (A) is a carbonyl compound (Aldehyde or a ketone) since it forms phenyl

hydrazone. Again it gives negative Tollens’ and iodoform test, so it is a ketone but
not methyl ketone. ‘A’ on reduction gives n-pentane, thus ‘A’ is a straight chain
compound.
Keeping in view all the above, the formula of ‘A’ is
CH3 CH2 — C.CH2— CH3

||
O
Pentan — 3 — one (A)
The reaction my be represented as
CH3 CH2 — C — CH2— CH3 + H2N. NHC6H5

||
O
(A)
CH3CH2
C = N.NHC6H5 + H2O
CH3CH2
Phenyl hydrazone
Tollens’
No reaction
reagent
C2H5
C=O
C2H5 Iodoform
No reaction
(A) test
[H]
CH3CH2CH2CH2CH3
n — Pentane
4. An unknown compound of C, H and O contains 69.77% C and 11.63% H and has a

molecular weight of 86. It does not reduce Fehling’s solution but forms a bisulphite
addition compound and gives a positive iodoform test. What are the possible structures?
Solution :
(i) For finding empirical formula
Element % Relative number Simplest

of atoms ratio
C 69.77 5.76 5
H 11.63 11.63 10
O 19.20 1.2 1
\ Empirical formula = C5H10O

Empirical formula = 5 ´ 12 + 1 ´ 10 + 16 = 86
Also molecular weight = 86
\ Molecular formula = C5H10O
The compound forms a bisulphite compound indicates that it is an aldehyde or a
ketone. It does not reduce Fehling’s solution, which indicates it is a ketone. It gives
+ve iodoform test which indicates that it is a methyl ketone i.e. it must contain (CH 3–
CO –) group. Keeping all the above facts in view, the structure of ketone may be
CH3
CH3 CH2 CH2 C — CH3 or CH — C — CH3
|| CH3 ||
O O
Pentan — 2 — one 3 — Methyl butan — 2 — one
5. An organic compound ‘A’ C5H8O adds Br2 to form C5H8Br2O. It does not react with
Tollens’ reagent but reacts with phenyl hydrazine. ‘A’ on ozonolysis gives acetaldehyde
and C3H4O2 which loses CO forming CH3CHO. Identify ‘A’ and explain the reaction.
Solution
Compound ‘A’ adds one molecule of Br 2, therefore contains a double bond. It forms
phenyl hydrazone, hence a carbonyl group is present. Further it does not react with
Tollens’ reagent, hence the carbonyl group is ketone and not aldehyde.
‘A’ on ozonolysis gives CH3CHO and C3H4O2. Keeping in view the above facts the
structure of ‘A’ is
O O O
|| O3 || Zn/H2O
CH3CH=CH—C—CH3 CH3 — CH CH — C—CH3
Pent-3-en-2-oneO O O
||
CH3 CHO + CH3 —C—CHO
CH3CHO + CO
6. Compound A (C6H12O2) on reduction with LiAlH4 yielded two compounds B and C.

The compound B on oxidation gave D, which on treatment with aqueous alkali and
subsequent heating furnished E. The latter on catalytic hydrogenation gave ‘C’. The
compound D was oxidised further of give F which was a monobasic acid (mol. weight
60). Deduce the structures of A, B, C, D and E.
Solution
O
||
F is monobasic acid. The structure is R — C — OH. Mol. wt. is 60 (given)
So, MR + 12 + 2 ´ 16 + 1 = 60
Þ MR + 45 = 60
Þ MR = 15, So the alkyl group is CH3. ‘F’ is obtained by oxidation of D. So ‘D’

must be CH 3 CHO. ‘D’ on treatment with aq. alkali undergoes aldol
condensation which on heating loses a molecule of water giving a, b-
unsaturated aldehyde. So ‘E’ must be crotonaldehyde (CH 3CH = CH CHO)
OH
aq.NaOH |
CH3CHO+H.CH2 CHO CH3 —CH—CH2—CHO
(D) Aldol
H2 /Catalyst
CH3—CH2—CH2— CH2 OH CH3 —CH = CH — CHO
(C) (E)
‘D’ is obtained on oxidation of ‘B’. Since ‘D’ is CH3 CHO, ‘B’ must be CH3CH2OH.
Basing on structure of B ( CH3CH2OH) and that of C(CH3—CH2—CH2—CH2—OH),
the structure of ‘A’ may in deduced as follows.
O
|| LiAlH4
CH3CH2CH2— C — O CH2 CH3 CH3CH2CH2CH2OH+CH3CH2OH
Ethyl butanoate (C) (B) (O)
O
|| (O)
CH3 — C — OH CH3CHO
(F) (D)
7. An organic compound (A) contains 40% carbon and 6.7% hydrogen. Its vapour density
is 15. On reacting with a concentrated solution of KOH, it gives two compounds (B)
and (C). When ‘B’ is oxidised, original compound ‘A’ is obtained. When ‘C’ is treated
with conc. HCl it gives a compound D which reduces Fehling’s solution and Tollens’
reagent and also gives effervescence with NaHCO 3 solution. Write the structures of
A, B, C and D and explain the reactions.
Solution
For empirical formula
Element % Relative number Simplest
of atoms ratio
C 40 3.33 1
H 6.7 6.70 2
O 53.3 3.33 1
\ Empirical formula of (A) = CH2O

Empirical formula weight = 30
Molecular weight = 2 ´ vapour density = 2 ´ 15 = 30
Hence molecular formula = Empirical formula = CH 2O
The reaction path is:
Conc.KOH
CH2O (B)+(C)
oxdn. Conc.HCl
A Fehling
D Cu2O (red ppt)
Na soln.
Amm. HC
AgNO3 O
3
Ag miror Effervescence
(A) is HCHO, Upon treatment with conc. KOH it undergoes Cannizzaro’s reaction forming
CH3OH and HCOOK. Since ‘B’ upon oxidation gives ‘A’, ‘B’ must be CH3OH and ‘C’
is HCOOK. Upon treatment with conc. HCl ‘C’ forms HCOOH
HCOOK + HCl HCOOH + KCl
(D)
‘D’ (HCOOH) reduces Fehling soln, Tollens’ reagent and gives effervescence with
NaHCO3
HCOOH +2CuO H2O + CO2 +Cu2O
Feh.soln red
HCOOH + Ag2O H2O + CO2 + 2Ag
Tollens’ reagent Silver mirror
HCOOH + NaHCO3 HCOONa + H2O + CO2
8. An alkene ‘A’ on ozonolysis yields acetone and an aldehyde. The aldehyde is easily oxidised
to an acid (B). When ‘B’ is treated with Br2 in presence of Phosphorus it yields compound
‘C’ which on hydrolysis gives a hydroxy acid (D). This acid can also be obtained from
acetone by the reaction with HCN followed by hydrolysis. Identify A, B, C and D.
Solution
O3 CH3
Alkene C = O + Aldehyde
Zn/H2O CH3
(A)
Oxdn
HOH Br2/P
D C B
Hydroxy acid
CH3 HCN CH3 OH HOH/H+ CH3 OH

CO C C
CH3 CH3 CN CH3 COOH
(D)
Thus ‘C’ is bromo acid, ‘B’ must be an acid formed by the oxidation of the aldehyde.
Keeping all these things in view, the reactions may be represented as
CH3 H [O] CH3 H Br2/P CH3 Br

C C C
CH3 CHO CH3 COOH CH3 COOH
(B) HOH
CH3 OH
C
CH3 COOH
CH3 (D)
CH3
So, the structure of alkene (A) must be C = CH.CH
CH3
CH3
(A)
18.9 IMPORTANT CONVERSIONS :
1. Formaldehyde Acetaldehyde.
O
|| [H] PCl5 KCN
H—C—H CH3OH CH3Cl CH3CN
LiAlH4
CH3CN
[H] Na/Alc
[O] HNO2
CH3CHO CH3CH2OH CH3CH2NH2
K2Cr2O7 / H2SO4
2. Acetaldehyde Formaldehyde
[O] NaOH NaOH

(i) CH3CHO CH3COOH CH3COONa CH4
CaO,
Cl2 hv
[O] aq.KOH
HCHO CH3OH CH3Cl
[H] ConcH2SO4
(ii) CH3CHO CH3CH2OH CH2 = CH2
LiAlH4 170 0
O3
O
Zn/H2O H2C CH2
2 HCHO
O O
Formaldehyde Ethylene ozonide
3. Acetaldehyde to Acetone :
[O] Ca(OH)2
CH3CHO CH3COOH (CH3COO)2Ca CH3COCH3
4. Acetone to Acetaldehyde :
Cl
PCl5 | AIc
CH3COCH3 CH3 — C — CH3 CH3 — C º CH
| KOH
Cl H2 Lindlar’s
catalyst
CH3— CH = CH2
Propene
O O3
Zn/H2O CH3CH CH2
CH3CHO
O O
Acetaldehyde Propylene ozonide
5. Formaldehyde Acetone
as above as above
HCHO CH3CHO CH3COCH3
6. Acetone Formaldehyde
as above
CH3COCH3 CH3CHO as above HCHO
7. Ethylene Acetaldehyde
HBr aqKOH
CH2 = CH2 CH3 — CH2Br CH2CH2OH
K2Cr2O7 / H2SO4 [O]
CH3CHO
8. Acetaldehyde Ethylene
[H] ConcH2SO4
CH3CHO CH3—CH2OH CH2 = CH2
Na/Alc 1700
9. Acetaldehyde Ethylalcohol
[H]
CH3CHO CH3CH2OH
Na/Alc
10. Acetone Isopropyl alcohol
CH3 LiAlH4 CH3

C=O CHOH
CH3 Reduction CH3
Isopropyl alcohol
11. Acetaldehyde Acetylene

as above
CH3CHO CH2 = CH2 + Br2 CH2 — CH2
| |
Br Br
Alc.KOH
CHºCH
Acetylene
12. Acetylene Acetaldehyde
OH
1% HgSO4 |
CH º CH + H2O CH2 = CH Tautomerise CH3 — CHO
42% H2SO4
600C vinyl alcohol Acetaldehyde
13. Benzene n-propyl benzene

COCH2CH3 CH2CH2CH3
Anhydrous Zn/Hg.Conc.HCL
+ CH3CH2COCl
AlCl3
CHAPTER (18) AT A GLANGE
O
||
1. The general formula of an aldehyde is R — CHO (R—C—H), whereas that of a ketone is
O
||
RCOR/ (R—C—R/). They are known as carbonyl compounds represented by the general
formula CnH2nO.
2. Aldehydes show chain, functional and position (only for aromatic aldehydes)
isomerism whereas ketones show chain isomerism, functional isomerism and
metamerism.
3. The carbon atom of the carbonyl group is sp2 hybridised and the structure is planar.
4. General Methods of Preparation
(a) Oxidation of alcohols: Chemical (K2Cr2O7 & H2SO4) and catalytic (reduced Cu)
[O]
R — CH2OH R — CHO
(10alcohol)
R [O] R
CH — OH C = O (Also by Oppenauer oxidation)
R / R/
(20alcohol)
(b) From acids:
(i) Dry distillation of Ca-salt of the fatty acids —
(HCOO)2Ca HCHO + CaCO3
(RCOO)2 Ca + (HCOO)2 Ca 2R — CHO + 2CaCO3
(RCOO)2 Ca R–CO–R + CaCO3
(ii) Vapours of fatty acids passed over hot MnO or ThO2 at 560K.
MnO
HCOOH HCHO
560K
RCOOH + HCOOH RCHO
RCOOH RCOR
(c) From acid chlorides:-

Rosenmund reduction - Acid chlorides can be converted to aldehydes with
hydrogen in boiling xylene using Pt or Pd as catalyst supported by BaSO4, poisoned
with sulphur.
H2
R — COCl R — CHO
Pd/BaSO4, S
1 dry ether
2R —CO—Cl + Cd R2 2R— CO — R1 + CdCl2
(d) From alkynes :
42% H2SO4
CH º CH CH3CHO
1%HgSO4, 340K
(Acetylene)
R — C º CH RCOCH3
(Propyne) (Methyl ketone)
(e) From alkenes: Ozonolysis

Zndust
R — CH = CH2 + O3 Ozonide RCHO + HCHO
H2O
R Zndust R
C = CHR// + O3 Ozonide C = O + R¢¢CHO
R / H2O R/
(f) From gem-dihalides: Hydrolysis by aq.KOH
X OH
R — CH + KOH (aq) R—CH R —CHO
X OH
R—C—R/ H2O
/
R —C—R +KOH(aq) R—C—R/
OH OH ||
X X O
Physical Properties
5. HCHO is a gas at room temperature.
6. Lower members of carbonyl compounds are soluble is water, but the solubility decreases
with increase in molecular mass.
7. Boiling points of aldehydes and ketones are less than these of the corresponding alcohols.
Reactions:
8. Carbonyl compounds undergo nucleophilic addition reactions. The order of reactivity
follows the following sequence.
HCHO > CH3CHO > CH3 COCH3 > CH3CH2 COCH2CH3 >
O
||
C6H5CHO > C6H5 – C – CH3
OH
(i) HCN :- C = O + HCN C (Cyanohydrin)
CN
OH
(ii) NaHSO3 :- C = O+ NaHSO3 C (bisulphite compound)
SO3Na
(employed for separation and purification of carbonyl compounds)

* Note that only methyl ketones undergo bisulphite addition reaction.
9. Nucleophilic addition followed by elimination of water.

Reactent Product
H2N—OH H+ C = N—OH (oxime)
H2N—NH2 H+ C = N—NH2 (hydrazone)

C=O
H2N—NH—C6H5 H+ C = N—NH—C6H5 (phenyl hydrazone)
H+
H2N—NH—CO—NH2 C = N—NH—CO—NH2 (semicarbazone)
10. Aldol condensation :- Aldehydes & ketones having a-hydrogen atom undergo aldol
condensation in presence of dilute alkali.
OH
dil. alkali | heat
2CH3CHO CH3—CH—CH2CHO CH3—CH=CH—CHO
–H2O
Acetaldehyde acetaldol Crotonaldehyde
OH
Ba(OH)2 | CH3
CH3COCH3 CH3—C—CH2COCH3 C = CHCOCH3
| – H2O CH3
CH3
Mesityl oxide
Acetone Diacetone alcohol
OH
|
dil.NaOH D
C6H5 COCH3 C6H5 — C — CH2 COC6H5 C6H5— C = CHCO C6H5
| –H2O |
CH3 OH CH
| 3
11. Haloform reaction: Acetaldehyde, methyl ketones and CH3—CH—R (R = H, alkyl or
aryl) respond to haloform test.
O O
|| || –
CH3—C—R + X2 + NaOH CX3—C—R OH CHX3 + R—COONa
12. Oxidation Reaction : Aldehydes can reduce both Fehling’s solution (Excepting
aromatic aldehydes) and Tollens’ reagent whereas ketones can not. Aldehydes form a
red precipitate of Cu2O when warmed with Fehling’s solution and form a silver mirror
when warmed with Tollens’ reagent.
Fehling’s solution is a mixture of Fehling A(CuSO 4) solution and Fehling B

(NaOH and sodium potassium tartrate) Sodium potassium tartrate is called Rochelle
salt. Tollens’ reagent is ammoniacal silver nitrate solution
13. Reduction of Aldehydes and Ketones:- Aldehydes and ketones can be catalytically
reduced using Raney nickel or Pt.or by LiAIH 4 to alcohols. NaBH4 can also be used
for this purpose. NaBH4 is a mild and selective reducing agent, since it reduces only
the carbonyl group and leaves the carbon carbon double bond intact. Clemmensen
and Wolff - Kishner reduction converts a > C = O group to —CH 2 group.
14. PCl5 reacts with simple carbonyl compounds forming dichlorides.

Cl
C=O + PCl5 C
Cl
(Carbonyl comp) (Dichloride)
15. Formaldehyde reacts with ammonia forming hexamethylenetetramine or urotropine

which is used as urinary antiseptic. And for the synthesis of RDX.
16. Cannizzaro’s Reaction : Aldehydes having no a-hydrogen atom when treated with conc.
alkali undergo Cannizzaro’s reaction. Two molecules of an aldehyde participate in the
reaction out of which one molecule is oxidised to a carboxylic acid and the other molecule
is reduced to an alcohol.
Conc.NaOH
2R — CHO RCOONa + RCH2OH
Aldehyde Sod. salt of alcohol
the carboxylic
acid
17. Methods of Preparation of Benzaldehyde

CH3 CHO
Etard's Reaction
1. (a)
CH3 CrO3 CHO

(b) Oxidation
COCl CHO
Rosenmund Reduction
2.
CºN CHO
3. Stephen Reduction
CH3 CHCl2 CHO

4. Cl2 (i) Hydrolysis
(ii) -HO
2
CO+HCl,(AlCl3 - CuCl) CHO

5.
Gattermann - Koch Reaction
18. Methods of preparation of Acetophenone.

O
(i) C6H5 MgBr, dry ether ||
(a) CH3 — C º N C6H5 — C — CH3
(ii) H3O+ COCH3
Anh. AlCl3
(b) + CH3 — COCl + HCl
19. Reactions of aryl aldehyde and ketone.

OH OH
CH CH
HCN COOH
CN
C6H5CH = N – NHC6H5
CHO
Nitration m-nitrobenzaldehyde
Benzaldehyde
Halogenations
m-Chlorobenzaldehyde
(Cl2), AlCl 3 (Anh.)
Acetophenone undergoes the same reaction.

CHO
Conc. NaOH CH2OH COONa
20. 2 +
Cannizzaro
Reaction
QUESTIONS
(A) Very short answer type (1 mark each)

(i) What is Tollen’s reagent ?
(ii) What is Fehling’s solution ?
(iii) What is formed if calcium acetate is heated at 400 0C ?
(iv) To what state does ethanal reduce Cu(II) ?
(v) What is the IUPAC name of
CH3 —CH—C—CH2 —CH3
| ||
CH O 3
(vi) The Cannizzaro’s reaction is given by ————
(vii) Write the IUPAC name of the compound
CHO
|
CH3 —CH—CH2 —CH3
(viii) Write the structural formula of the compound 1-bromo-3-pentanone.
(ix) Aldehydes react with hydroxylamine to produce ————
(i) oxime (ii) alcohol (iii) hydrazone (iv) phenyl hydrazone.
(x) Name the functional isomer of propanone.
(xi) The precipitate formed when an aldehyde reacts with Fehling’s solution is———
O
(xii) IUPAC name of compound is ––––––––
CH3
(xiii) Write the structure of the compound 4-Oxopentanal.
(B) Short answer type (2 marks each)
(i) How would you get oxime from acetaldehyde ? Give equation.
(ii) What is Fehling’s solution ? How does it react with acetaldehyde ?
(iii) Write one reaction to distinguish between acetaldehyde and acetone. Give equation
(iv) What happens when acetaldehyde reacts with HCN ? Give equation.
(v) What happens when ethylene reacts with ozone ? Explain with equation.
(vi) What happens when formaldehyde reacts with HCN. ? Give equation.
(vii) Show the iodoform reaction in case of acetaldehyde with equation.
(viii) What is Tollens’ reagent ? What happens when it reacts with benzaldehyde ?
(ix) What is Rosenmund’s reduction ? Explain it giving an example.
(x) What happens when acetone is treated with HCN ? Give equation.
(xi) What happens when benzaldehyde is treated with Fehling’s solution and why ?
Explain.
(xii) Complete the following equation
CH3
C = O + NaHSO3
CH3
(xiii) What happens when HCHO reacts with NH3 ?
(xiv) How will you distinguish acetaldehyde and benzaldehyde.
(xv) Which compound can undergo Cannizzaro’s reaction - Give one example
(xvi) What happens when acetaldehyde reacts with iodine in dilute NaOH solution ?
Give equation.
(xvii) Write with equation what happens when acetone reacts with iodine in presence
of sodium hydroxide.
(xviii) Identify X & Y in the series.
Acidic SOCl2
CH3CHO X Y
KMnO4
(xix) How will you prepare phenyl hydrazone of acetone ? Indicate with equation.
(xx) Write with equation, how urotropine is formed
(xxi) Name the compound in IUPAC system having molecular formula C 3H6O, which
can reduce Tollens’ reagent. What is Tollens’ reagent ?
Δ
(xxii) Calcium acetate ¾¾® [A] ¾I¾ 2 / KOH
¾¾ ¾® [B] yellow ppt. Identify the products A &
B. Name the reaction in Step-II.
(xiii) Explain why methanal in a gas, where as ethanal is liquid
(xiv) Explain why ethanal is having lower boiling point than ethanol.
(C) Short answer type questions (3 marks each)

(i) Distinguish between acetaldehyde and acetone.
(ii) Distinguish between formaldehyde and acetaldehyde.
(iii) Distinction between benzaldehyde and acetophenone
(iv) Name one primary alcohol which gives iodoform test and explain why?
(v) Distinguish between ethyl alcohol and acetone.
(vi) Distinguish between acetaldehyde and benzaldehyde.
(vii) Explain why aldehydes are more reactive than ketones.
(viii) Although both C=C and C = O contain double bond, they differ in their
characteristics. Explain.
(ix) Arrange the following compounds in increasing order of their boiling points with
plausible explation.
CH3CH2OH, CH3OCH3, CH3CHO, CH3CH3
(x) Explain Clemmensen’s reduction giving one example.
(xi) Convert benzene to benzaldehyde.
(xii) Convert Benzoyl chloride to benzaldehyde.
(xiii) Convert benzaldehyde to m-chlorobenzaldehyde.
(D) Long answer type (7 marks each)
(i) Write notes on (a) Aldol condensation
(b) Cannizzaro reaction
(ii) How acetone is prepared ? What happens when acetone reacts with
(a) HCN (b) NH2OH (c) C6H5NH.NH2
(iii) Write notes on (a) Iodoform reaction
(b) Reduction of aldehydes and ketones.
(iv) Describe two general methods of preparation of ketones. State with equations
how acetone reacts with
(a) Phenyl hydrazine
(b) Hydrocyanic acid
(c) Iodine in presence of sodium hydroxide.
(v) How can benzaldehyde be synthesized by the following reaction ?

(a) Etard reaction
(b) Rosenmund reduction
Explain why it is less reactive than CH3CHO towards nucleophilic addition
reaction.
(vi) How is acetaldehyde prepared ? With equation give its reaction with
(a) HCN (b) C6H5NH.NH2 (c) NaOH solution
(vii) (a) What is Haloform reaction ? How will you prepare Iodoform from acetone ?
Can you prepare Iodoform from Formaldehyde ?
(b) How will you prepare acetophenone by Friedel - Craft’s reaction ?
(viii) How will you differentiate
(a) Ethyl alcohol and acetone
(b) Acetaldehyde and acetone
(ix) What happens when (give equation)
(i) C2H5OH is passed over hot reduced Cu at 3000C
(ii) HCHO is treated with NH3
(iii) Acetone is treated with I2 and NaOH solution
(iv) CH3CHO reacts with NH2OH
(v) Calcium acetate is heated
(x) How is acetone prepared ? Give two methods. What happens when acetone reacts
with:
(a) Phenyl hydrazine
(b) Hydroxylamine
(c) Sodium bisulphite
(xi) Explain with equation how aldehydes and ketones can be prepared from calcium
salts of organic acids. What happens when acetaldehyde reacts with the following
substances ?
(a) NH2OH (b) Phenyl hydrazine (c) Hydrogen in presence of nickel catalyst.
(xii) How acetaldehyde can be prepared from the following ?
(a) Acetyl chloride (b) Acetylene
How does it react with (a) Fehling’s solution, (b) Tollens’ reagent ? Give equations.
What is formalin ? How is it used ?
(xiii) How aldehydes and ketones are prepared from dry distillation of calcium salts ?
How aldehydes react with (a) NaHSO3 (b) Phenyl hydrazine ? Describe one test
to distinguish between aldehydes and ketones.
(xiv) Give two methods for the preparation of ketones. How does acetone react with
(i) Iodine in NaOH solution and
(ii) Sodium bisulphite ?
(iii) Hydroxyl amine ?
(xv) How are ketones prepared from (a) salts of carboxylic acids (b) acid chlorides?
How does acetone react with (i) ammonia (ii) barium hydroxide (iii)
hydroxylamine?Explain with equation.
(xvi) Discuss briefly the structure and nature of the carbonyl group. In what respects
the C = C and C = O bonds resemble and differ from each other.
ADDITIONAL QUESTIONS
I. Very short answer type (1mark each)
(i) What type of ketones undergo iodoform test ?
(ii) With which reagent can you distinguish between pentan-2-one and pentan-3-one?
(iii) What happens when calcium acetate is heated?
(iv) Which alkene on ozonolysis gives acetone?
(v) What is Rosenmund’s reduction ?
(vi) Why HCHO does not undergo aldol condensation ?
(vii) Which aldehyde can undergo iodoform test ?
(viii) What is the reagent used for conversion of acid chloride to aldehyde ?
(ix) Name one reagent used to distinguish between acetaldehyde & acetone.
(x) What is IUPAC name of Formaldehyde ?
II. Short answer type Questions (2 marks each)
(i) Explain why HCHO is more reactive than acetaldehyde.
(ii) Explain why diethyl ketone does not exhibit haloform reaction.
(iii) In what respect, the C = C and C = O bonds resemble each other?
(iv) Arrange HCHO, CH3CHO and CH3COCH3 in order of increasing reactivity

towards HCN.
(v) Explain why the boiling points of aldehydes and ketones are lower than those of
alcohol.
(vi) Explain why the lower members of carbonyl compounds are soluble in water ?
(vii) How is acetaldehyde prepared from ethanol ?
(viii) What is the function of BaSO4 in Rosenmund’s reduction.
(ix) Explain why hydrazones of aldehydes & ketones are not prepared in highly acidic
medium.
(x) Write the structure of Urotropine.
(xi) How will you detect carbonyl group in an organic compound ?
(xii) Explain why trichloroacetaldehyde does not undergo aldol condesation.
(xiii) Explain why benzaldehyde does not undergo aldol condensation whereas
acetaldehyde does.
(xiv) Explain why the bond energy of >C = O is higher than that of >C = C<
(xv) Oximes are more acidic than hydroxylamine. Why ?
(xvi) How does acetaldehyde react with Tollens’ reagent? Give equation.
(xvii) How will you distinguish an aldehyde from a ketone? Give one chemical test.
(xviii) Which type of aldehydes show Cannizzaro reaction?
III. Long Answer type.
1. (a) Give four points of difference between acetaldehyde and acetone
(b) How can you bring out the conversion of ethanol to 2-hydroxy -3-butanoic acid.
2. Explain the action of the following reagents on acetophenone
(a) Hydrogen cyanide
(b) I2, aq.NaOH
(c) Conc.HNO3 in the presence of Conc.H2SO4
(d) Phenylhydrazine.
3. How can you bring out the following conversions ?
(a) Acetaldehyde to acetoxime
(b) Methanal to ethanal
(c) Ethanal to 2-hydroxybutanoic acid
(d) Acetylene to acetone (4 steps)
4. What happens when

(a) Formaldehyde is treated with NH3?
(b) Acetylene is pased through dilute H2SO4 in presence of HgSO4.
(c) Formaldehyde is treated with conc H2SO4.
(d) Acetylchloride is treated with H2 is presence of Pd/BaSO4.
(e) A mixture of calcium formate and calcium acetate undergoes dry distillation.
5. Discuss the reaction used to distinguish between aldehydes and ketones.
(F) Multiple Choice type Questions with answers.

1. The reagent with which both acetaldehyde and acetone react easily is
(a) Fehling solution (b) Grignard reagent
(c) Schiff’s reagent (c) Tollens’ reagent
2. Which of the following compounds is oxidised to prepare methyl ethyl ketone ?
(a) 2-Propanol (b) 1-Butanol
(c) 2-Butanol (d) Formaldehyde
3. Cannizzaro reaction is not given by
(a) Trimethyl acetaldehyde (b) Acetaldehyde
(c) Benzaldehyde (d) Formaldehyde
4. The formation of cyanohydrin from a ketone is an example of
(a) Electrophilic addition (b) Nucleophilic addition
(c) Nucleophilic substitution (d) Electrophilic substitution
5. When acetaldehyde is heated with Fehling’s solution, it gives a precipitates of
(a) Cu (b) CuO
(c) Cu2O (d) Cu + CuO + Cu2O
6. Methyl ketones are usually characterised through
(a) Tollens’ reagent (b) Iodoform test
(c) The Schiff’s test (d) Benedict’s reagent
7. Tollens’ reagent is
(a) Ammoniacal cuprous chloride (b) Ammoniacal cuprous oxide
(c) Ammoniacal silver bromide (d) Ammoniacal silver nitrate
8. Aldehydes can be distinguished from ketones by using

(a) Schiff’s reagent (b) Conc. H2SO4
(c) anhydrous ZnCl2 (d) resorcinol
9. Ethyl alcohol on oxidation with K2Cr2O7 gives
(a) acetic acid (b) acetaldyhyde
(c) formic acid (d) formaldehyde
10. Aldehydes can be oxidised by
(a) Tollens’ reagent (b) Fehling’s solution
(c) Benedict’s solution (d) all
11. Isopropyl alcohol on oxidation forms
(a) Acetone (b) Ether
(c) Formalin (d) Hydrobenzamide
12. Formaldehyde reacts with NH3 to give
(a) Hexamethylenetetramine (b) Formaldehyde ammonia
(c) Formalin (d) Hydrobenzamide
13. At room temperature formaldehyde is
(a) gas (b) liquid
(c) solid (d) all
14. Which of the following can reduce Tollens’ reagent ?
(a) 2-hydroxy propane (b) Acetophenone
(c) Both (d) None
15. RCH = O + H2 RCH2OH
For this reaction the catalyst is
(a) Ni only (b) Pd only
(c) Pt only (d) any of the above
16. Which of the following can reduce Tollens’ reagent ?
(a) CH3 — CH = CH2 (b) CH3COCH3
(c) CH3CHO (d) CH3 — O — CH3
17. Calcium acetate when dry distilled gives

(a) Formaldehyde (b) Acetaldehyde
(c) Acetone (d) Acetic anhydride
18. Formaldehyde when treated with conc. KOH gives
(a) CH3CHO (b) C2H4
(c) CH3OH, HCOOK (d) CH3OH, CH3CHO
19. Which compound undergoes iodoform reaction
(a) HCHO (b) CH3CHO
(c) CH3OH (d) CH3COOH
20. Identify ‘Z’ in the series
HBr Hydrolysis NaOH

CH = CH2 X Y Z
I2excess
(a) C2H5I (b) C2H5OH
(c) CHI3 (d) CH3CHO
21. Formaldehyde when treated with conc. KOH gives methanol and potassium formate.
The reaction is known as
(a) Perkin’s reaction (b) Claisen’s reaction
(c) Cannizzaro’s reaction (d) Knoevenagel’s reaction
22. Formalin is an aqueous solution of
(a) Formic acid (b) Formaldehyde
(c) Fluorescein (d) Furfuraldehyde
23. Hexamethylene tetramine is used as
(a) analgesic (b) antipyretic
(c) Urinary antiseptic (d) all
24. Aldol condensation will not occur in
(a) HCHO (b) CH3CH2CHO
(c) CH3COCH3 (d) CH3CHO
25. Propyne on hydrolysis in presence of HCl and HgSO4 gives
(a) Acetaldehyde (b) Acetone
(c) Formaldehyde (d) None
26. When anhydrous acetaldehyde is brought in contact with a drop of conc. H2SO4 at ordinary
temperature, the following compound is formed.
(a) Aldol (b) Paraldehyde
(c) metaldehyde (d) acetal
27. The reaction between formaldehyde and caustic soda to produce methyl alcohol is known as
(a) Cannizzaro reaction (b) Kolbe’s reaction
(c) Rosenmund’s reduction (d) Friedel Craft reaction
28. Rosaniline hydrochloride decolourised by SO2 is called
(a) Benedict’s solution (b) Tollen’s regent
(c) Schiffs reagent (d) Magenta solution
29. Acetaldehyde reacts with phosphorus pentahalide to produce
(a) acetal (b) ethyledene chloride
(c) alcohol (d) chloral
30. Formaldehyde is a raw malerial for the manufacture of
(a) nylon (b) terylene
(c) bakelite (d) rayon
31. Which of the following reagents helps to distingish an aldehyde from a ketone ?
(a) Phenyl hydrazine (b) NaHSO3
(c) neutral FeCI3 (d) Ammoniacal AgNO3 solution
32. Which of the following does not show aldol condensation ?
(a) CH3CHO (b) CH3CH2CHO
(c) (CH3)3 C — CHO (d) CH3 (CH2)2 CHO
33. In which of the following reactions, both the oxidised and reduced forms of the same
compound are obtained ?
(a) Aldol condensation (b) Cannizzaro reaction
(c) Reimer Tiemann reaction (d) Kolbe’s synthesis
34. In the Cannizzaro reaction given below
2 ArCHO OH Ar CH2OH + ArCOO– , the slowest step is
(a) The attack of OH– at the carbonyl group
(b) The transfer of hydride ion to the carbonyl group
(c) The abstraction of a proton from the carboxylic acid
(d) The deprotonation of Ar – CH2OH.
35. Which of the following statement is not true about benzaldehyde ?

(a) Undergoes Cannizzaro reaction
(b) Forms an addition compound with HCN
(c) Undergoes aldol condensation
(d) Reacts with phenylhydrazine
36. Cannizzaro reaction is given by :
(a) C6H5CHO (b) CH3 CHO
(c) C6H5CH2CHO (d) C6H5CO CH3
37. Cannizzaro reaction is an example of :
(a) Only oxidation (b) Only reduction
(c) Disproportionation (d) None of these
38. Cyanohydrin of benzaldehyde on hydrolysis will give :
(a) an optically active hydroxy acid (b) benzoic acid
(c) benzyl alcohol (d) Acetophenone
39. In the given reaction ‘X’ will be :
H2
C6H5COCl Pd-BaSO ,S ‘X’
4
(a) C6H5 COOH (b) C6H5CH2OH

(c) C6H5CHO (d) C6H5CH3
(G) Fill in the blanks (with answers) (1 mark each)
1. Methanal + Ammonia ————
2. Fehling A consists of an aqueous solution of copper suphate while Fehling ‘B’ consists of
an alkaline solution of ————
3. Ethanol vapour is passed over heated copper and the product is treated with aq NaOH.
The final product is ————
4. 40 % aqueous solution of HCHO is ————
5. Calcium formate on dry distillation gives ————
6. Carbon atom of carbonyl group is ———— hybridised.
7. When acetaldehyde is heated with Fehling solution a ———— precipitate of ————
is formed.
8. IUPAC name of acetaldehyde is ————
9. When vapour of isopropyl alcohol is passed over hot reduced copper ———— is formed.
10. Both aldehydes and ketones react with ———— reagent.
11. Silver mirror test is a test for ————
12. Acetaldehyde on treatement with ———— gives aldol.
13. Sodium potassium tartrate is ———— salt.
14. Magenta is ————

15. Conversion of hexan-1-ol to hexanal is carried out by the reagent ––––––––––.
16. The reagent –––––––––– converts but-2-ene to ethanal.
H. Complete the following with answers (2 marks each)
Hg2+ (CH3CO)2O
1. (A) CH3CHO (B)
dil.H2SO4
Pd / BaSO4, S
2. CH3COCl + H2 (A)
3. CH3CHO dilNaOH (A)

4. 2HCHO + NaOH _______ + ________
5. HCHO + NH3 (A)
CH3 Cu
6. CHOH (A)
CH3 0
300
dry
7. (CH3COO)2 Ca + (HCOO)2 Ca (A)
O distillation
||
8. C2H5 —C—CH3 + I2 + (A) (B) + CHI3 + H2O + NaI
(O) Cl2
9. CH3CH2OH A B CHCl3
10. HCHO + HCN (A)
11. CH3CHO + I2 NaOH (A)
12. CH3COCH3 + H2 NOH (A)
O
Anhydrous
CH3 — C AlCl 3
+ O A
13. CS2
CH3 — C
CH3
(i) CrO 2Cl2

+
A
(ii) H 2O
14.
NO2
15. (C6H5 – CH2) Cd + 2CH3COCl A
CO, HCl
A
16. Anhydrous
AlCl 3
dry, HCl A
O CH2 — OH
17.
CH3 — C — CH 3 + CH2 — OH
18. CH3CHO + [Ag (NH3)2] OH A
CHO
19. LiAlH 4 A
CHO
20. D
+ Conc.NaOH ¾¾® A+B
(i) NaBH 4
21. CH3CO CH2 COO C2H5 A
(ii) H +
Zn/Hg, Conc.HCl
22. C6H5COCH3 A
ANSWERS
Multiple choice type question
1.b 6.b 11.a 16.c 21.c 26.b 31.d 36.a

2.c 7.d 12.a 17.c 22.b 27.a 32.c 37.c
3.b 8.a 13.a 18.c 23.c 28.c 33.b 38.a
4.b 9.b 14.d 19.b 24.a 29.b 34.b 39.c
5.c 10.d 15.d 20.c 25.b 30.c 35.c
Fill in the blanks

1. (CH2)6N4 2. Sodium potassium tartrate 3.Aldol 4.Formalin
5. HCHO 6. sp2 7.red, Cu2O 8.Ethanal
9. CH3COCH3 10.Grignard 11.Aldehyde 12.dil.NaOH
13.Rochelle 14.Rosaniline hydrochloride 15.PCC 16. O3/Zn–H2O
Complete the following
1. CH º CH CH3CH(OCOCH3)2
(A) (B)
2. (A) is CH3CHO
3. (A) is CH3CH(OH) CH2CHO
4. (A) = CH3OH, (B) = HCOONa
5. (A) = (CH2)6N4
CH3
6. (A) = C=O 7. (A) = CH3CHO
CH3
8. (A) = NaOH (B) = C2H5COONa 9. (A) = CH3CHO (B)CCl3CHO
CN
10. (A) = H—CH 11. (A) CHl3
OH CHO
COCH3
CH3
12. (A) = C = N — OH 13. 14.
CH3
CHO NO2
15. C6H5CH2COCH3 16. 17. CH3 O — CH2

C
CH3 O — CH2
CH2OH
18. CH3COONH4 19.
– +
CH2OH COO Na
20. A= B=
21. CH3CHOH CH2 COOC2H5 22. C6H5CH2CH3
qqq
CARBOXYLIC ACIDS 599
CHAPTER - 19
CARBOXYLIC ACIDS
19.1 GENERAL INTRODUCTION :

O
||
Organic compounds having carboxyl group (—C—OH) are called carboxylic acids.
The carboxyl group is a combination of a carbonyl group ( C=O) and a hydroxyl group (—OH)
and hence the name carboxyl (carb from carbonyl and oxyl from hydroxyl).
Carboxylic acids are classified as aliphatic or aromatic depending upon whether —COOH
group is linked to aliphatic alkyl chain or aryl group respectively. For example, formic acid (HCOOH),
acetic acid (CH3COOH), propionic acid (CH3CH2COOH) etc. are aliphatic acids and
COOH COOH
| |
Benzoic acid, ; 2-Amino benzoic acid, —NH2 ; 3-Methyl benzoic acid,
COOH
|
etc. are aromatic acids.
—
CH3
These acids are further classified as mono, di, tri carboxylic acids according to the number
of carboxyl groups present in their molecules.
COOH COOH
For example : | |
Monocarboxylic acids:
NO2
HCOOH CH3COOH Benzoic acid 3-Nitrobenzoic acid
Formic acid Acetic acid
Dicarboxylic acid :
COOH COOH CH2COOH
| H2C |
COOH COOH CH2COOH
Oxalic acid Malonic acid Succinic acid
COOH
—COOH
—COOH
COOH
Phthalic acid Isophthalic acid
(1, 2 - Benzenedicarboxylic acid) (1, 3 - Benzenedicarboxylic acid)
COOH
COOH
Terephthalic acid
(1, 4 - Benzenedicarboxylic acid)
The aliphatic monocarboxylic acids are called fatty acids since many higher acids e.g.
stearic (C17H35 COOH), palmitic (C15H31COOH), oleic (C17H33COOH) etc. are formed by
the hydrolysis of natural fats. The general formula for aliphatic saturated monocarboxylic acids
is CnH2n+1 COOH or CnH2nO or RCOOH where R stands for hydrogen or alkyl group. Lower
members of monocarboxylic acids occur in various plants and animals.
19.2 NOMENCLATURE :
(1) Common System : According to common system, lower members are named after the
source of the individual acids. For example, formic acid was so named because it was
first obtained by the distillation of red ants (Latin: formica meaning ant). Similarly, acetic
acid was so named because it was obtained from vinegar (Latin: acetum meaning vinegar).
In this system, the positions of the substituents are indicated by Greek letters (a, b, g,
d...). Carbon atom adjacent to the carboxyl group is assigned a and the next carbon atom
b and so on.
(2) IUPAC system: (a) Aliphatic carboxylic acids according to IUPAC system are named as
alkanoic acids by replacing the terminal ‘e’ of the corresponding alkane by ‘-oic acid’.
The positions of the substituents are indicated by Arabic numerals according to the
following rules:
(i) The longest carbon chain containing –COOH group is selected.
(ii) The carbon atom of the carboxyl group is assigned the number 1.
Table 19.1: Common and IUPAC names of some aliphatic carboxylic acids
Monocarboxylic acid Common name IUPAC name
HCOOH Formic acid Methanoic acid

CH3COOH Acetic acid Ethanoic acid
CH3CH2COOH Propionic acid Propanoic acid
CH3CH2CH2COOH n-Butyric acid Butanoic acid
Isobutryric acid
CH3CHCOOH or
|
CH3 a-Methyl propionic acid 2-Methylpropanoic acid
CH3
CHCH2COOH b-Methyl butyric acid 3-Methyl butanoic acid
CH3
CH3(CH2)3COOH n-Valeric acid Pentanoic acid

CH3(CH2)4COOH n-Caproic acid Hexanoic acid
HOOC – COOH Oxalic acid Ethanedioic acid
HOOC– (CH2)2 – COOH Succinic acid Butanedioic acid
HOOC – CH2 – CH– CH2 – COOH — Propane-1, 2, 3 –
|
COOH tricarboxylic acid
(b) Aromatic acids are named by common names or as derivatives of parent benzoic
acid,which are also accepted by IUPAC. Examples of this family are :
COOH COOH
OH
Benzenecarboxylic acid 2-Hydroxybenzoic acid

(Benzoic acid) (Salicylic acid)
COOH COOH
NH2
COOH
Benzene - 1, 3 - dicarboxylic acid 2-Aminobenzoic acid
(Isophthalic acid) (Anthranilic acid)
But the compounds where carboxyl group is present on the side chain of aromatic
ring system as in phenyl acetic acid and cinnamic acid are called side-chain aromatic
acids showing similar behaviour as aliphatic carboxylic acids.
—CH2—COOH —CH = CH —COOH
Phenylacetic acid Cinnamic acid
19.3 ISOMERISM :
A. Fatty acids exhibit chain and functional isomerism.
1. Chain isomerism: This type of isomerism occurs due to the difference in the nature of
carbon chain. For example:
CH3
|
CH3CH2CH2COOH and CH3—CH—COOH
Butanoic acid 2-Methyl propanoic acid
CH3
|
CH3CH2CH2CH2COOH and CH3—CH—CH2—COOH
Pentanoic acid 3-Methyl butanoic acid
2. Functional isomerism: This type of isomerism occurs due to the presence of different
functional groups. Carboxylic acids are the functional isomers of esters. For example,
CH3COOH and HCOOCH3
Acetic acid Methyl formate
CH3CH2CH2COOH and CH3CH2COOCH3
Butanoic acid Methyl propanoate
CH3CH2COOH and CH3COOCH3 and HCOOC2H5
Propanoic acid Methyl ethanoate Ethyl methanoate
B. Position Isomerism :
This type of isomerism is exhibited by aromatic acids. For example : Position isomers of
benzene dicarboxylic acids are :
COOH COOH COOH
COOH HOOC
COOH
1, 2 Benzene 1, 3 Benzene 1, 4 Benzene
dicarboxylic acid dicarboxylic acid dicarboxylic acid
(Phthalic acid) (Isophthalic acid) (Terephthalic acid)
19.4 METHODS OF PREPARATION
1. By the oxidation of Alcohols, Aldehydes or Ketones: Primary alcohols and aldehydes

are readily oxidised to carboxylic acids by mild oxidizing agents like potassium
permanganate solution in acid or alkaline medium or acidified potassium dichromate
solution or chromium trioxide (CrO3) in acidic medium.
[O] [O]
R CH2OH RCHO RCOOH
KMnO4/H+
Primary alcohol Aldehyde Acid
[O] [O]
CH3CH2OH CH3CHO CH3COOH
Ethyl alcohol K2Cr2O7/H+ Acetaldehyde Acetic acid
[O] [O]
C6H5CH2OH C6H5 – CHO C6H5–COOH
Benzyl alcohol K2Cr2O7/H+ Benzaldehyde Benzoic acid
Secondary alcohols on oxidation form ketones which on drastic oxidation gives acids,
having less number of carbon atoms.
R [O] R [O]
CHOH C=O RCOOH + R/COOH
R /
K2Cr2O7/H+ R / NaOI
Secondary alcohol ketone Acids
CH3 [O] CH3 [O]

CHOH C=O CH3COOH
CH3 K2Cr2O7/H+ CH3 NaOI
Isopropylalcohol Acetone Acetic acid
2. By the hydrolysis of Alkyl cyanides: Alkyl cyanides are hydrolysed to carboxylic acids
in acidic or alkaline medium.
H+ or OH–
R—C º N + 2H2O RCOOH + NH3
Alkyl cyanide Acid
H+ or OH–
CH3C º N + 2H2O CH3COOH + NH3
Methyl cyanide Acetic acid
H+ or OH–
C6H5 – CN + 2H2O C6H5 – COOH + NH3
Benzonitrile Benzolic acid
3. By the hydrolysis of Esters, Acyl chlorides, Acid amides or Acid anhydrides: Esters,
acyl chlorides or acid anhydrides are easily hydrolysed to carboxylic acids by mineral
acid or alkali.
RCOOR/ + HOH RCOOH + R/OH
H+
Ester Acid Alcohol
CH3COOCH5 + HOH CH3COOH + C2H5OH
H+
Ethyl acetate Acetic acid
COOC2H5 COOH
H3O+
+ C2H5OH
Ethyl benzoate Benzoic acid

RCOCl + HOH RCOOH + HCl
H+
Acid chloride Acid
CH3COCl + HOH CH3COOH + HCl
H+
Acetyl chloride Acetic acid
RCONH2 + HOH R—COOH + NH3
H+
Acid amide Acid
CH3CONH2 + HOH CH3—COOH + NH3
H+
Acetamide Acetic acid
CONH2 COOH
H+
+ H2O + NH3
Benzamide Benzoic acid
RCO H+
O + HOH 2RCOOH
RCO
Acid anhydride Acid
CH3CO H+
O + HOH 2CH3COOH
CH3CO
Acetic anhydride Acetic acid
(C6H5CO)2O + H2O 2C6H5COOH
Benzoicanhydride Benzoic acid
4. By the hydrolysis of Trichloroalkanes:
Trichloroalkanes in which all the three chlorine atoms are linked to the same carbon atom
are hydrolysed by alkali to carboxylic acids.
Cl OH O NaOH O
NaOH –H2O
RC Cl RC OH R—C R—C –
Cl OH OH H+ O
Acid Sodium salt
of acid
Cl OH –H O O NaOH O
HC Cl NaOH HC 2 H—C H—C
OH
Cl OH OH H+ ONa
Formic acid Sodium salt
of Formic acid
5. By Carbonation of Grignard reagent: Alkyl or aryl magnesium halide (Grignard reagent)

reacts with solid carbon dioxide in ether to form addition compound which on acidification
gives carboxylic acid. O
dry ether || H+/H2O OH
O=C=O + RMgX R—C—O MgX RCOOH + Mg
Carbon dioxide Acid X
O
dry ether || H+/H2O OH
O = C = O +CH3Mg Br CH3 —C—O Mg Br CH3COOH + Mg
Br
Acetic acid
O
dry ||
C6H5MgBr + O=C=O C6H5 — C — MgBr
ether
Phenylmagnesium
bromide H+/H 2O
Br
C6H5 – COOH + Mg
Benzoic acid OH
6. Preparation of aromatic (Benzoic acid) by oxidation of alkylbenzenes (arenes) :

Benzoic acid is prepared by the oxidation of alkyl benzenes (irrespective of the length of
the side chain) in the presence of strong oxidizing agent like acidified potassium dichromate
or alkaline / acidic potassium permanganate or dil. HNO 3. Primary and secondary alkyl
groups are oxidized, whereas tertiary group is not at all affected.
CH3 COOK COOH

KMnO4 – KOH H3O+
D
Tolune Benzoic acid
CH2 CH2 CH3 COOK COOH

+
KMnO4 – KOH H 3O
D
1-Propylbenzene Benzoic acid
19.5 GENERAL PROPERTIES :

A. PHYSICAL PROPERTIES:
1. Physical state: The first three members are colourless liquids having pungent odour. The
next six members are oily liquids having faint unpleasant odour. The higher members are
colourless and odourless waxy solids.
2. Solubility: The first four members are soluble in water due to intermolecular hydrogen
bonding with water molecules.
H—O......H—O—C = O......H—O......H—O—C = O ......

| | | |
H R H R
The solubility of carboxylic acids gradually decreases with rise in size of the alkyl group.
This is due to increase in nonpolar part of the molecule.
3. Melting point: For the first ten members of the homologous series, the melting points of
carboxylic acids having even number of carbon atoms are higher than the nearest lower
and next higher acids with odd number of carbon atoms.
CH2 COOH CH2 CH2
CH3 CH2 CH3 CH2 COOH
(Acid with even number (Acid with odd number

of carbon atoms) of carbon atoms)
The acids with odd number of carbon atoms have carboxyl group and terminal methyl
group on the same side of zig-zag carbon chain and such unsymmetrical molecules fit
poorly in the crystal lattice and hence have weaker intermolecular forces. The acids with
even number of carbon atoms have carboxyl group and terminal methyl group on opposite
side of zig-zag carbon chain and hence they fit better in the crystal lattice resulting in
stronger intermolecular forces. This explains why the acids having even number of carbon
atoms have melting points higher than the acids with odd number of carbon atoms.
Melting points of some Alkanoic acids.
Acid Methanoic Ethanoic Propanoic Butanoic Pentanoic Hexanoic
M.P(K) 281 289.6 251 265 238.5 270
4. Boiling points : The carboxylic acids have quite high boiling points due to the presence
of intermolecular hydrogen bonding as shown below.
O......H—O
R—C C—R
O—H......O
(Dimeric structure)
The carboxylic acids have relatively higher boiling points than the corresponding alcohols.
This is because,
(i) O—H bond in carboxylic acid is more polar than O—H bond in alcohol due to
electron withdrawing effect of carbonyl group on O—H bond.
(ii) The molecules of carboxylic acids are held together by two hydrogen bonds forming
cyclic dimers.
Table 19.2 : Boiling points of some Carboxylic acids and Alcohols.

Acids/Alcohols B.P(K)
HCOOH 373
CH3OH 338
CH3COOH 391
C2H5OH 351
C2H5COOH 424
C3H7OH(Propanol) 370
C3H7COOH 437
C4H9OH (Butan-l-ol) 391
B. ACIDIC NATURE OF CARBOXYLIC ACIDS
Carboxylic acids are relatively weaker acids as compared to mineral acids. The strength
of the acid depends upon the extent of ionisation which mainly depends upon the stability of the
carboxylate ion formed.
O O
R—C R—C – + H+
O—H O
(i) A carboxylic acid molecule is a resonance hybrid of the following two resonating
structures (I and II)
.. –
O O
..
..
.. ..
R—C .. R—C +
O—H
.. O—H
..
I II
The structure, II indicates that the oxygen atom of the hydroxyl group carries some positive
charge. As a result, the electron pair of O—H is drifted towards oxygen atom. This
displacement of electron pair causes the formation of a proton and a carboxylate ion.
The carboxylate ion which is formed is also a resonance hybrid of the following two
resonating structures, III and IV.
.. –
O O
..
..
.. ..
R—C .. – R—C
O O
..
..
.. ..
III IV
Thus we observe that (i) carboxylic acid as well as the carboxylate ion both are stabilised
by resonance.
(ii) The contributing structures of carboxylic acid (I & II) are not equivalent and the structure,
II involves charge separation. As a result, the structure II contributes less to the stability
of the carboxylic acid.
(iii) The resonating structures, III and IV are equivalent and contribute to the greater stability
of the carboxylate ion.
Thus, the carboxylate ion being more stable than the undissociated carboxylic acid, the
latter has a tendency to dissociate into proton and the carboxylate ion. Hence, the carboxylic
acids show acidic character.
The strength of a carboxylic acid is expressed in terms of the dissociation constant (K a)as:
RCOOH + H2O RCOO– + H3O+
[RCOO–][H3O+]
Ka = ————————
[RCOOH]
Higher the value of Ka, stronger is the acid and vice versa. As the numerical values of K a
vary by large magnitude, it is more convenient to express the acidic strength in terms of
pKa value, which is defined as
pKa = – log Ka
Smaller the value of pKa, stronger is the acid and vice versa. The Ka and pKa values of
some acids are given below.
Table 19.3: Ka and pKa values of some Carboxylic acids
Acid Ka pKa
HCOOH 17.7 ´ 10–5 3.75
CH3COOH 1.75 ´ 10–5 4.76
FCH2COOH 260 ´ 10–5 2.59
ClCH2COOH 136 ´ 10–5 2.87
BrCH2COOH 125 ´ 10–5 2.90
I CH2COOH 67 ´ 10–5 3.16
Cl2CHCOOH 5530 ´ 10–5 1.26
Cl3CCOOH 23200 ´ 10–5 0.63
Cl3CH2COOH 1.3 ´ 10–5 4.87
C6H5COOH 6.3 ´ 10–5 4.20
1. Effect of substituents on acid strength of aliphatic acids : The substituents affect

appreciably the acid strength of carboxylic acids.
(i) Effect of electron releasing groups (+I effect) : An electron releasing group attached to
carboxyl group tends to release electrons towards the carbon atom to which it is attached
and this effect is transmitted throughout the carbon chain. This increases the electron
density on the oxygen atom of the – O – H group and as a result the release of H + becomes
difficult. This explains why formic acid is a stronger than acetic acid.
O O
H—C CH3 C
O—H O—H
Release of H becomes easy Release of H becomes
due to absence of electron difficult due to presence of
releasing group an electron releasing group
(– CH3)
Acid strength decreases with increase in electron releasing nature (+I effect) of the
substituents. The +I effect of alkyl groups increases in the following order:
CH3– < C2H5 – < (CH3)2 CH – < (CH3)3 C –
Therefore, the acid strength of carboxylic acids decreases in the following order:
HCOOH > CH3COOH > CH3CH2COOH > (CH3)2CHCOOH
Formic acid Acetic acid Propionic acid Isobutyric acid.
(ii) Effect of electron withdrawing groups (–I effect):
An electron withdrawing group attached to carboxyl group tends to withdraw electrons

from the carbon atom to which it is attached and their effect is transmitted throughout the
chain. As a result, the electron pair forming the O – H bond is displaced more towards
oxygen of O – H group and the release of H+ becomes more easier. Therefore, chloroacetic
acid is a stronger acid than acetic acid.
H H
| O | O
H —C C < Cl C C
| O—H | O H
H H
Acetic acid Chloroacetic acid
(a) Effect of number of halogen atoms: –I effect increases with increase in number of electron
withdrawing atoms and hence acid strength increases.
For example,
H Cl Cl
| O O O
CI C C < Cl C C < Cl C C
| O H | O H O H
H H Cl
(Monochloroacetic acid) (Dichloroacetic acid) (Trichloroacetic acid)
(b) Effect of nature of halogen atoms: The strength of carboxylic acid depends upon nature
of electron withdrawing substituent. Greater the electron withdrawing power of the
substituent stronger is the acid. The electron withdrawing effect (– I effect) of halogen
decreases in the order:
F > CI > Br > I.
Hence the acid strength of halogen substituted monocarboxylic acids decreases in the
order.
FCH2COOH > CICH2COOH > Br CH2COOH > I CH2COOH.

(c) Effect of position of halogen atoms: The electron withdrawing effect of halogen atom
decreases as its distance from the – COOH group increases. The electron withdrawing
effect of halogen is maximum when the halogen atom is linked to a - carbon atom of the
carboxylic acid. Thus, a- chloropropionic acid is a stronger acid than b- chloropropionic
acid.
2. Comparison of Relative Acid Strength of Monocarboxylic acid and Alcohol
Both carboxylic acid and carboxylate ion are stabilised by resonance and the carboxylate
is more stabilised by resonance as compared to carboxylic acid. Hence the carboxylic acids have
tendency to release H+ ions with the formation of stable carboxylate ions. However, resonance is
not possible for alcohols and also alkoxide ions. Therefore, carboxylic acids are stronger acids
than monohydric alcohols.
O O
|| || – –
R – C – O – H + H2O R – C – O + H3O
Conjugate base
.. –
O O
..
..
.. ..
R—C .. R—C +
O—H
.. O—H
..
Less stable
.. –
O O
..
..
.. ..
R—C .. – R—C
O O
..
..
.. ..
– +
R – OH + H2O R – O + H3O
Not resonance
stabilized
3. Acidity of Benzoic acid
Aromatic acids are slightly stronger acids than aliphatic acids because of greater value of
Ka. For example, benzoic acid is a stronger acid than acetic acid, because benzoate ion is more
resonance stabilized than acetate ion.
–
COOH COO
+ H+
Benzoic acid Benzoate ion

–
COO
|
H+
Ka = = 6.3 x 10—5
COOH
|
–
O O
|| ||
CH3 —C—OH CH3 —C—O + H+
Ka = 1.75 x 10—5
Effect of substitutents on acid strength:

Acidity of carboxylic acids is determined by both inductive effect and the resonance effect.
(i) Electron releasing substitutents (ortho-para directing groups) tend to decrease the
strength of the acid. This is due to intensification of -ve charge on the carboxylate
ion making it unstable. Thus with –OH group at the ortho or para position the
benzene ring is incapable of delocalising the negative charge on the carboxylate
anion.
.. +O—H +O—H +O—H
O—H O—H
..
| || || || ||
| | | | |
C C C C C
– – – – –
||
||
||
||
||
|
O O O O O O O O O O
p — Hydroxy benzoate
..
||
||
||
.. |
| O—H | O—H | O—H | O—H | O—H
C – C – C – C – C –
||
||
||
||
||
|
|
O O O O O O O O O O
o — Hydroxy benzoate
On the other hand electron withdrawing groups like —NO2, –CN etc. tend to increase the
strength of the acid. This is due to dispersal of the –ve charge on carboxylate ion making it more
stable. In otherwords due to delocalisation of –ve charge on the carboxylate anion it gets stabilised.
Thus, p-nitrobenzoic acid (Ka=40 x10—5)is a stronger acid than benzoic acid.
(ii) The + I or –I effect of the substituents is more pronounced if the substituents are present
at the para positions rather than at meta positions.
(iii) Irrespective of the nature of the substituents (+I or -- I), ortho substituted benzoic acids are
found to be stronger than benzoic acid. This is called ortho effect. This is probably due
to resultant of steric and electronic factor. However, amino benzoic acids are exceptions.
All of them are weaker than benzoic acid. Acidity of amino benzoic acids is in the order.
m— > o — > p —.
From the above discussion it can be concluded that the effect of substituents on acidity
depends not only on the nature of the group but also on its position with respect to the position of
the —COOH group.
Some important observations
(i) Strength of o —, m — & p — hydroxy benzoic acids relative to benzoic acid
follows the order,
COOH COOH COOH COOH
| OH | | |
|
> > >

OH |
OH
o-Hydroxy m-Hydroxy Benzoic acid p-Hydroxy
benzoic acid benzoic acid benzoic acid
(ii) Strength of o —, m — & p — nitrobenzoic acids relative to benzoic acid follows

the order.
COOH COOH COOH COOH

| NO2 | | |
|
> > >
| NO2
NO2
o-Nitrobenzoic p-Nitrobenzoic m-Nitrobenzoic Benzoic acid

acid acid acid
(iii) Strength of o —, m — & p — toluic acids relative to benzoic acid follows the
order,
COOH COOH COOH COOH

| CH3 | | |
|
> > >

CH3 |
CH3
o-Toluic Benzoic m-Toluic p-Toluic
acid acid acid acid
(iv) Strength of o —, m — & p — chlorobenzoic acid reative to benzoic acid follows

the order,
COOH COOH COOH COOH

| Cl | | |
|
> > >

Cl |
Cl
o-Chloro benzoic m-Chloro benzoic p-Chloro benzoic Benzoic acid
acid acid acid
4. Comparison of acid strength of aliphatic and aromatic acids (unsubstituted)
It is a fact that electron releasing groups tend to decrease the acid strength. Let us compare
the acid strength of HCOOH, CH3 COOH & C6H5 COOH. CH3 —group is electron releasing.
When it is attached to —COOH group the release of H+ becomes comparatively difficult. So it is
a weaker acid than HCOOH, where —COOH group is attached to a H atom. In case of benzoic
acid the phenyl group (C6H5—) is attached to —COOH group, phenyl group has an over all
electron donating effect when it is attached to a —COOH group. But this effect is weaker than +I
effect of alkyl group. Thus, benzoic acid is a stronger acid than acetic acid. The acid strength
follows the order,
HCOOH > C6H5COOH > CH3COOH
But when the phenyl group is attached to —COOH group through one or more CH2—
groups, it causes a slight electron withdrawing (—I) effect. Therefore phenyl acetic acid (C 6H5CH2
COOH) is slightly stronger than benzoic acid i.e. C6H5CH2COOH > C6H5COOH.
5. Comparison of acid strength of Carboxylic acids and Phenols
Though phenols are acidic due to the resonance stabilized conjugate base phenoxide ion,
they are less acidic than the carboxylic acids.
O O
R — C — OH + H2O R — C — O + H 3O
OH O
+ H2O + H 3O
The higher strength of carboxylic acid in comparision to phenols can be explained on the
basis of higher stability of its conjugate base carboxylate ion which is having two equivalent
resonating structures because of the presence of two electronegative oxygen atoms.
O O
R—C R—C
O O
(Two equivalent resonating structures of carboxylate ion making it highly stable)
O O
So on
(Not equivalent though resonance stabilized.)

C. Chemical properties
The chemical properties of carboxylic acids may be discussed under the following heads:
(a) Reaction due to H atom of – COOH group.
(b) Reaction due to – OH part of – COOH group.
(c) Reaction due to – CO – part of – COOH group.
(d) Reaction due to – COOH group as a whole.
(e) Reactions due to alkyl group.
(a) Reaction due to H atom of – COOH group (acidic property)
1. Reaction with metals: Carboxylic acids react with strong electropositive metals like Na,
Zn, Mg etc. to liberate hydrogen gas with the formation of salts.
2RCOOH + 2Na 2 RCOONa + H2
Acid Sodium of acid
2HCOOH + 2Na 2 HCOONa + H2
Formic acid Sodium formate
2CH3COOH + Zn (CH3COO)2 Zn + H2
Acetic acid Zinc acetate.
2. Reaction with alkali: Carboxylic acids react with alkali (NaOH or KOH) to form salts
and water.
RCOOH + OHNa RCOONa + H2O
HCOOH + OHNa HCOONa + H2O
Foomic acid Sodium formate
CH3COOH + OHNa CH3COONa + H2O
CH3COOH + NH4OH CH3COONH4 + H2O
3. Reactions with carbonates and bicarbonates:
Carboxylic acids react with carbonates or bicarbonates to liberate carbondioxide.
2RCOOH + Na2CO3 2RCOONa +CO2 + H2O
2HCOOH + Na2CO3 2HCOONa +CO2 + H2O
CH3COOH+NaHCO3 CH3COONa +CO2 + H2O
Acitic acid Sodium acetate

This reaction is used to distinguish between carboxylic acids and phenols because phenols
do not produce effervescence (evolution of CO2) with aqueous solution of NaHCO3 or
Na2CO3.
(b) Reaction due to – OH part of – COOH group.
1. Formation of amides - Carboxylic acids react with ammonia to form ammonium salts
which when heated decompose to give amides.
RCOOH + NH3 RCOONH4 RCONH2 + H2O

Acid Ammonium salt Acid amide
HCOOH + NH3 HCOONH4 HCONH2 + H2O

Formic acid Ammonium Formamide
formate
CH3COOH + NH3 CH3COONH4 CH3CONH2 + H2O

Acetic acid Ammonium Acetamide
acetate
COOH COONH4 CONH2
+ NH3 + H2O
Benzoic acid Ammonium benzoate Benzamide
2. Formation of esters (Esterification) - Carboxylic acids react with alcohols in presence

of a dehydrating agent like anhydrous zinc chloride or concentrated sulphuric acid to
form esters.
RCO OH + H OR/ H+ RCOOR/ + H2O

Acid Alcohol Ester
HCO OH + H OH5C2 H+ HCOOC2H5 + H2O

Formic acid Ethyl alcohol Ethyl formate
CH3CO OH + H OCH3 H+ CH3COOCH3 + H2O

Acetic acid Methyl alcohol Methyl acetate
COOH C–OC2H5
H+
+ HOH5 C2 + H2 O
Benzoic acid Ethyl alcohol Ethyl benzoate
This reaction is reversible and is known as esterification. In order to shift the equilibrium
in forward direction water formed has to be removed immediately. The dehydrating agent takes
away water.
Mecanism :
The esterification of carboxylic acid with alcohol is one type of nucleophilic acyl
substitution. It involves the following steps.
Step-1 : Protonation of the carboxyl oxygen.
+
O O — OH
R — C — OH + H+ R — C — OH
Step-2 : Nucleophilic attack by the alcohol molecule
+
O — OH OH
R — C — OH + H — O — R¢ R — C — OH
+ O — R¢
Step-3 : Loss of a molecule of water and a proton resulting with an ester.
OH OH
+ H
R — C — OH H+ transfer R—C—O
H
+ O — R¢ O — R¢
H — H 2O
+
O O —H
R — C — OR¢ R — C — OR¢
Ester — H+
3. Formation of acid chlorides : Carboxylic acids react with phosphorus halides (PCl 5,
PCl3) and thionyl chloride (SOCl2) to form acid halides.
3RCOOH + PCl3 3RCOCl + H3PO3
Acid chloride
RCOOH + PCl5 RCOCl + POCl3 + HCl
RCOOH + SOCl2 RCOCl + SO2 + HCl
3CH3COOH + PCl3 3CH3COCl + H3PO3
Acetic acid Acetyl chloride
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
4. Formation of anhydrides : Carboxylic acids on heating with a dehydrating agent like

phosphorus pentoxide form acid anhydrides.
R COO H RCO
O + H2O
R CO OH P2O5 RCO
Acid anhydride
CH3COO H CH3CO
O + H 2O
CH3CO OH P2O5 CH3CO
Acetic acid Acetic anhydride
(c) Reaction due to – CO – part of – COOH group:

Reduction of carboxylic acids: These are reduced to primary alcohols when heated with
lithium aluminium hydride (LiAlH4) or with hydrogen and copper chromite (CuCr2O4)
(in case of higher fatty acids).
LiAlH4
R-COOH RCH2OH
or CuCr2O4
Primary alcohol
+H2
LiAlH4
CH3COOH + 4H CH3CH2OH +H2O
Ethyl alcohol
(d) Reaction due to – COOH group as a whole:
1. Reduction :
(a) Reaction with HI and red phosphorus (Reduction to alkanes) :
Carboxylic acids when heated with red phosphorus and hydrogen iodide at 500K are
reduced to alkanes. In this reaction – COOH group is reduced to – CH3 group
red P
RCOOH + 6 HI RCH3 + 2H2O + 3I2
at 500K
Alkane
red P
CH3COOH +6HI CH3CH3 + 2H2O + 3I2
at 500K
Acetic acid Ethane
(b) Reduction to alcohols :
Carboxylic acids can be reduced to alcohols on reaction with lithium aluminium hydride
(LiAlH4) or with diborane (B2H6).
(i) LiAlH4/ether
RCOOH RCH2OH
(ii) H3O+ Primary alcohol
(i) LiAlH4/ether
CH3COOH CH3CH2OH
(ii) H3O+ Ethanol
Ethanoic acid
COOH CH2OH
(i) LiAlH 4/ether

(ii) H 3O +
Benzoic acid Benzyl alchol
2. Decarboxylation on Reaction with soda lime: Sodium or potassium salt of a carboxylic

acid when heated with dry sodalime (NaOH + CaO) forms alkane with one carbon atom
less than the parent acid. NaOH takes part in the reaction and calcium oxide helps in
fusion of NaOH.
CaO/D
R COONa + H ONa RH + Na2CO3
Alkane
CaO/D
CH3COONa + HONa CH4 + Na2CO3
Sodium acetate Methane
3. Kolbe’s Electrolytic reaction (Electrolytic decarboxylation) : Aqueous solution of

sodium or potassium salt of a fatty acid on electrolysis gives alkane.
2RCOONa 2RCOO– + 2Na+
H2O 2OH– + 2H+
At anode: 2RCOO– R – R + 2CO2+ 2e
At cathode: 2H+ + 2e H2
At cathode both Na+ and H+ are present, but H+ ions are discharged preferentially due to
their lower discharge potential thant Na + ions. Hence hydrogen gas is evolved at the
cathode.
For examples :
2CH3COONa 2CH3COO– + 2Na+
Sod.acetate
2H2O 2OH– + 2H+
At cathode: 2H+ + 2e H2
At anode: 2CH3COO– – 2e CH3 – CH3 + 2CO2

Ethane.
4. Decomposition of Calcium salts of carboxylic acids : Dry distillation of calicum salts

of fatty acids results in the formation of carbonyl compounds.
Calcium formate when distilled gives formaldehyde.
HCOO
Ca CaCO3 + HCHO
HCOO
Formaldehyde.
Calcium formate
Calcium formate when distilled with calcium acetate gives acetaldehyde.
HCOO OOCCH3
Ca + Ca 2CaCO3 + 2CH3CHO
HCOO OOCCH3
Calcium acetate when distilled alone forms acetone.
OOCCH3 CH3
Ca C = O + CaCO3
OOCCH3 CH3
Acetone.
(e) Reactions due to alkyl or aryl group.
1. Reaction with halogens : Carboxylic acids having an a-hydrogen atom react with
chlorine or bromine in the presence of small amount of red phosphorus to form a-
halocarboxylic acids.
(i) X2 / Red phosphorus

R — CH2—COOH R — CH — COOH X = Cl, Br
—
a-halocaroxylic acid
X
When more than one mole of Cl2 or Br2 is used, the second and third hydrogen atoms are
replaced.
Red P Cl2/Red P
CH3COOH + Cl2 ClCH2 COOH Cl2CHCOOH
– HCl Monochloroacetic – HCl Dichloroacetic acid
Acetic acid
acid Cl2 Red P –HCl
Cl3CCOOH
Trichloroacetic acid
Br
Br2 /Red P Br2 /Red P |
CH3CH2COOH CH3CHCOOH CH3—C—COOH
–HBr | –HBr |
Br Br
Propionic acid a- Bromo propionic acid a, a-Dibromo propionic acid
This reaction is known as Hell - Volhard - Zelinsky (HVZ) reaction
2. Reaction with mild oxidising agent such as H2O2

Carboxylic acids when heated with mild oxidising agent like hydrogen peroxide the alkyl
group gets oxidised at the b- position. For example,
OH
b a [O] |b a
CH3CH2 CH2 COOH CH3CH CH2 COOH
H2O2
n- Butyric acid b - Hydroxy butyric acid.
Carboxylic acids can also be oxidised at a - carbon by using oxidising agent such as
selenium dioxide, SeO2. Keto acids are obtained in this reaction.
O
||
RCH2COOH + SeO2 R—C—COOH + H2O + Se.
a - keto acid
3. Electrophilic substitution reaction
In benzoic acid, the carboxylic functional group is directly linked to the benzene ring and
behaves as an electron withdrawing group. Due to the electron-withdrawing character (–
R effect), the functional group behaves as a ring deactivator and makes the ortho and
para- positions electron deficient.
Hence, the carboxylic acid group behaves as a ring deactivator and meta - director towards
electrophilic substitution reactions, like, nitration, sulphonation and halogenation. But
benzoic acid does not undergo Friedel crafts reation due to deactivations of the benzene
ring by electron withdrawing effect of — COOH
(a) Nitration :
Benzoic acid reacts with concentrated nitric acid in the presence of concentrated sulphuric
acid to form m-nitro benzoic acid.
COOH COOH
conc.
H2SO4 + H2O
+ HNO3
conc. NO2
Benzoic acid m- Nitrobenzoic acid
(b) Sulphonation :
Benzoic acid on heating with conc. H2SO4 forms meta sulphobenzoic acid.
COOH COOH
D
+ conc. H 2SO4 + H 2O
SO3H
Benzoic acid m-sulphobenzoic acid
(c) Halogenation :
Benzoic acid reacts with a molecule of halogen in ther presence of FeCl 3 or Anhy. AlCl3
to form m-halobenzoic acid.
COOH COOH
Anhy. AlCl3
+ X2 + HX
X
Benzoic acid m - Halobenzoic acid
(for X = Cl / Br)
COOH COOH
Anhy. AlCl3
+ Cl2 + HCl
Cl
Benzoic acid m - Chlorobenzoic acid
+ HBr
(f) Unique characteristic reactions of Formic acid:

Reducing nature - Formic acid acts as a strong reducing agent since it gets readily oxidised.
It reduces ammoniacal solution of silver nitrate (Tollens’ regent), Fehling’s solution and
mercuric chloride to metallic silver, red cuprous oxide and mercurous chloride respectively.
Acidified potassium permanganate solution is also decolourised by formic acid. This is
due to reducing nature of formic acid, which distinguishes it from other carboxylic acid.
[O]
HCOOH CO2 + H2O
Formic acid
HCOOH + Ag2O 2Ag + CO2 + H2O
(From Tollens’ reagent)

HCOOH + 2CuO Cu2O + CO2 + H2O
(From Fehling’s solution)Cuprous oxide (red)
HCOOH + 2HgCl2 2HgCl + CO2 + 2HCl
Mercurous chloride
Reaction of formic acid with acidified KMnO4 solution is represented as :
[MnO–4 + 8H+ + 5e Mn2+ + 4H2O] ´ 2
[HCOOH CO2 + 2H+ + 2e] ´ 5
2MnO–4 + 6H+ + 5HCOOH 2Mn2+ + 8H2O + 5CO2
19.6 TESTS :
1. Carboxylic acids react with aqueous sodium bicarbonate to liberate CO 2 with

effervescence, which turns lime water milky.
2. Carboxylic acids react with alcohol in presence of a little conc. H 2SO4 to form ester
having fruity smell.
19.7 USES OF CARBOXYLIC ACIDS :
(a) Methanoic acid is used :

(i) as an antiseptic
(ii) in medicine for teatment of gout
(iii) in coagulating rubber latex
(iv) in leather industry
(v) in textile indusry for dyeing and finishing
(vi) in the preservation of fuits
(vii) as a rducing agent
(b) Ethanoic acid used :

(i) as a coagulent for latex in rubber industry
(ii) as vinegar in cooling and in the preparation pickles
(iii) as a laboratory reagent
(iv) in curing meat and fish
(v) in the manufacture of plastics (polyvinyl acetate), rayon (cellulose acetate) and
silk.
(c) Benzoic acid is used :
(i) in medicine as urinary antiseptic.
(ii) for making aniline blue in dye industry.
(iii) as a preservative. Sodium benzoate is the most useful for this purpose specially
for preserving food products like tomato sauce, fruit jams and juices.
(iv) in ferfumes in the form of its esters.
(d) Higher fatty acids are mainly used for the manufacture of soaps and detergents.
SOME IMPORTANT CONVERSIONS
1. Formic acid to Acetic acid:

Ca(OH)2 HCOO 2H
HCOOH Ca HCHO CH3OH
Formic acid HCOO – CaCO3 Formaldehyde Na–Hg/H2O Methyl alcohol
PCl5
Hydrolysis KCN
CH3COOH CH3CN CH3Cl
Acetic acid H+ Methyl cyanide Methyl chloride
2. Acetic acid to Formic acid :
NaOH (Na OH + CaO) Cl2

CH3COOH CH3COONa CH4 CH3Cl
hu Methyl cyanide
Acetic acid Sod.acetate Methane
KOH(aq)
[O] [O]
HCOOH HCHO CH3OH
Formic acid Formaldehyde K2Cr2O7+H2SO4 Methyl alcohol
3. Propanoic acid to Propanol :

LiAlH4
CH3CH2COOH + 4H CH3CH2CH2OH + H2O
Propanoic acid Propanol.
4. Acetic acid to Acetone :
Ca(OH)2 CH3COO D CH3

CH3COOH Ca C=O
CH3COO – CaCO3 CH3
Acetic acid
Ca-acetate Acetone
5. Acetic acid to tertiary butyl alcohol.
Ca(OH)2 CH3COO CH3

CH3COOH Ca D
C=O
Acetic acid
CH3MgBr
Ca-acetate
CH3 CH3
| H+ |
CH3— C — OH CH3— C — OMgBr
| H2O |
CH3 CH3
6. Acetic acid to Acetic anhydride :
D
2CH3COOH (CH3CO)2O + H2O
P2O5
Acetic acid Acetic anhydride
7. Acetic acid to Isopropyl alcohol :
Ca(OH)2 CH3COO D CH3

CH3COOH Ca C=O
Acetic acid
H
+2H |
CH3— C — OH
LiAlH4 |
CH3
Isopropyl alcohol
8. Acetic acid to Acetaldehyde
PCl5 +2H
CH3COOH CH3COCl CH3CHO
Pd – BaSO4,S
Acetic acid Acetyl chloride Acetaldehyde
9. Acetic acid to Ethylene
LiAlH4 D
CH3COOH CH3CH2 OH CH2= CH2
+4H conc.H2SO4
Acetic acid Ethyl alcohol Ethylene
at1600C
10. Acetic acid to Acetylene.
LiAIH4 D
CH3COOH CH3CH2 OH CH2= CH2
conc.H2SO4
Acetic acid Ethyl alcohol Ethylene
at443K
Br2
KOH(alc) CH2 Br
CH º CH |
D CH2 Br
Acetylene
Ethylene dibromide
11. Acetic acid to Ethane.
NaOH Electrolysis
CH3COOH CH3COONa CH3 – CH3
Acetic acid Sod. acetate Ethane
12. Acetic acid to Methane.
NaOH Sodalime D
CH3COOH CH3COONa CH4
Acetic acid Sod. acetate Methane
13. Formic acid to Formaldehyde.

Ca(OH)2 HCOO D
HCOOH Ca HCHO
HCOO – CaCO3
Formic acid Formaldehyde
Ca-formate
14. Acetic acid to Acetamide.

NH3 D
CH3COOH CH3COONH4 CH3CONH2
–H2O
Acetic acid Ammonium acetate Acetamide
15. Acetic acid to Diethyl ether.
LiAlH4 conc.H2SO4
CH3COOH CH3CH2OH C2H5–O–C2H5
+4H at 413K
Acetic acid Excess Diethyl ether
16. Propanoic acid to Ethyl bromide.
NaOH D Br2
CH3CH2COOH CH3CH2COONa CH3–CH3 CH3CH2Br
Sodalime hv
Propanoicacid Sod. propanoate Ethane Ethyl bromide
17. Acetic acid to Methyl amine.

NH3 D Br2+KOH
CH3COOH CH3COONH4 CH3 CO NH2 CH3NH2
–H2O
Acetic acid Ammonium acetate Acetamide Methyl amine
18. Acetic acid to Methyl alcohol
NH3 D
CH3COOH CH3COONH4 CH3 CO NH2
–H2O
Acetic acid Ammonium acetate Acetamide
Br2 / KOH
NaNO2+HCl
CH3OH CH3NH2
Methyl alcohol Methyl amine
19. Acetic acid to Butane.

LiAlH4 P + I2 Na
CH3COOH CH3CH2OH CH3CH2I CH3CH2CH2CH3
Ether
Acetic acid Ethyl alcohol (dry) Butane
20. Propionic acid to n – Butyl amine
LiAlH4 P/I2
CH3CH2COOH CH3 CH2 CH2OH CH3 CH2 CH2 I
Propionic acid n – propyl alcohol n – propyl iodide
KCN(alc)
Zn–Hg/HCl
CH3 CH2 CH2 CH2 NH2 CH3CH2CH2CN
reduction
n-Butylamine n-Propyl cyanide
21. Benzene to m-Nitrobenzoic acid.

Br MgBr
Br2 Mg/dry Ether

Anh.AlBr3
Benene Bromobenzene Phenylmagnesium

bromide
COOH COOH
(i) CO 2 conc.HNO3
(ii) H 3 O conc.H 2SO4
NO2
Benzoic acid m-Nitrobenzoic acid
22. Benzene to p-Nitrobenzoic acid.

CH 3 CH 3
CH 3Cl/Anh.AlCl 3 conc.HNO 3
F.C. Alkylation conc.H 2SO 4
Benene Toluene NO 2
p-Nitrotoluene
(i) KMnO4 (ii) H3O+
KOH, D
COOH
NO 2
p-Nitrobenzoic acid
23. Benzene to phenylacetic acid
MONOCARBOXYLIC ACIDS
General formula : R – COOH.
1. Oxidation of alcohols, aldehydes and Ketones (by K2Cr2O7 and conc. H2SO4)
[O] [O]
R – CH2OH R – CHO R – COOH
[O]
R – CH2 – CH – CH2 – R/ R – CH2 – CO – CH2 – R/
|
OH
R – CH2 – COOH + R/COOH

[O]
or
R – COOH + R/CH2COOH
2. Hydrolysis of alkyl cyanides (by acid or alkali) :
H+ +
> RCOOH + NH4
R–Cº N – –
OH
> RCOO + NH3
3. Hydrolysis of acid chlorides, acid amides, esters and acid anhydrides(by acid or alkali):
+
H
> RCOOH
R – CO – X – –
+
OH H
> RCOO RCOOH
(X = Cl,NH2, OR/, O.OC.R)
4. Hydrolysis of trichloroalkanes (by alkali) :
O
CI OH O ||
NaOH – H2O H+
R–C CI R–C OH R–C – R – C – OH
CI OH O
5. Carbonation of Grignard reagent :
O H2O/H+ O
O = C = O + R – Mg – X R–C R–C (X = Cl, Br, I)
OMgx OH
6. Decarboxylation of dicarboxylic acids :
COOH heat
R – CH R – CH2 – COOH
COOH – CO2
COOH Glycerol
| HCOOH + CO2 (Lab method for formic acid)
COOH 380K
7. Heating sodium alkoxide and carbon monoxide :
heat dil.H2SO4
R – ONa + CO R – COONa R – COOH + Na2SO4
high press.
+
High temp. H
When R = H, HONa + CO HCOONa HCOOH + Na2SO4
High press.
REACTIONS:
1. Reaction due to H atom of – COOH Group :
(i) Salt formation (with metals like Na, K, Mg, Zn etc. and with alkali)
R – COOH + M/ 1
RCOOM + —H
I I
(M = monovalent metal)
2 2
II II
R – COOH + M// (RCOO)2M + H2 (M = divalent metal)
2R – COOH + Na2CO3 2RCOONa + CO2 + H2O
R – COOH + NaHCO3 2RCOONa + CO2 + H2O
R – COOH + NaOH RCOONa + H2O
2. Reaction due to –OH part of –COOH group:
(i) With NH3 : R – COOH + NH3 R – COONH4

Salt
R – COONH4 D R – CO – NH2 + H2O
(acid amide)
Conc.H2SO4
(ii) Esterification : R – CO OH + H O – R/ R – COOR/ + H2O
(acid) (alcohol) (ester)
(ii) With PCl3, PCl5 or SOCl2 : 3R – COOH + PCl3 3RCOCI +H3PO3
R – COOH + PCl5 RCOCl + POCl3 + HCl
R – COOH + SOCl2 R – COCl + SO2 + HCl
P2O5
(iii) Dehydration : 2RCOOH RCO – O – CO – R + H2O
D
3. Reaction due to –COOH group:
(i) Formation of alkanes :

Red P / HI
R – COOH R – CH3 + I2 + H2O
500K
NaOH + CaO
R – COONa R – H + Na2CO3
Electrolysis
2RCOONa R – R + 2CO2 (Kolbe’s reaction).
+ 2H2O + 2H2+ NaOH
(at the anode)
(ii) Action of heat on the salts of acid :

D
(RCOO)2 Ca R – CO – R + CaCO3
(Ketone)
D
(RCOO)2 Ca + (HCOO)2Ca RCHO + 2CaCO3
(Aldehyde)
D
(HCOO)2Ca HCHO + CaCO3
(formaldehyde)
D
RCOONH4 RCONH2 + H2O
(amide)
heat
RCOONH4 R – C º N + 2H2O
P4O10
(alkyl cyanide)
RCOOAg + Br2 R – Br + CO2 +AgBr (Hunsdiecker reaction)
RCOOAg + R/ – X RCOOR/ + AgX
(ester)
4. Reaction due to alkyl group :
(i) Reaction with halogens : Hell – Volhard – Zelinsky reaction

Cl
Re d P / Cl 2 a Cl2
/Red P |
RCH 2 - COOH ¾ ¾¾¾¾ ® R - CH - COOH ¾¾® R - C - COOH
| |
Cl Cl
(a-chloroacid) (a, a-Dichloroacid)
(ii) Reaction with H 2 O 2 :

OH
|H 2O2
R - CH 2 - CH 2 COOH ¾ ¾¾
¾® R - CH - CH 2 - COOH
b
(b-hydroxy acid)
(iii) Reaction with SeO 2 :
2 SeO
R - CH 2 - COOH ¾ ¾¾ ® R - CO - COOH
(Keto acid)
5. Special reactions of Formic Acid :
Reducing properties:
HCOOH + Tollens’ reagent ¾

¾® Silver mirror (Ag)
HCOOH + Fehling’s solution ¾

¾® Red precipitate (Cu2O)
HCOOH + KMnO4 solution ¾

¾® Decolourisation (Mn2+)
HCOOH + HgCl2 solution ¾

¾® White precipitate (HgCl)
QUESTIONS
A. Very short answer type [1 mark each]
1. Methyl cyanide on hydrolysis yields ——
2. What happens when acetic acid is treated with sodium carbonate solution.
3. How will you prepare acetamide from acetic acid ?
4. Give any two uses of formic acid.
5. C6H5COOH is formed by carbonation of ——
6. Write the structural formula of 3 –Hydroxy Butanoic acid.
7. Write the IUPAC name of the following compound CH2(Br) – CH2 – COOH.
8. Write the IUPAC name of the following compounds :
(i) CH3 – CH2 – COOC2H5
(ii) HOOC – CH2– CH2– CH2– COOH
9. Write one reaction to distinguish between formic acid and acetic acid. Give equation.
10. Benzoyl chloride is formed by the action of PCl 5 on ––––– .
B. Short answer type [2 marks each]

1. What is the reaction of formic acid with Tollen’s reagent and also with sodium ?
2. Explain why formic acid has two different C – O bond lengths i.e. 1.23A° and 1.36A°,
where in sodium formate two C – O bond are same having bond length 1.27A°
3. Give two tests to distinguish between formic acid and acetic acid.
4. How can you convert toluene into m-nitrobenzoic acid ?
5. How formic acid can be converted to acetic acid ?
6. What happens when acetic acid is treated with NH4OH and the product is then heated ?
7. Why m-nitorbenzoic acid is a stronger acid than benzoic acid?
8. Adentify A and B
conc. HNO3 NaOH/CaO
C6H5COOH A B
conc. H2SO4 D
9. What happens when acetamide is boiled with NaOH solution ?
10. Adentify A and B

SOCl2 H2
C6H5COOH A B
Pd/BaSO4, S
11. Distinguish between acetic acid and ethanol
12. Explain why the bond length of C – O in carboxylic acid is slightly larger than that in
aldehydes and ketones.
13. What happens when sodium propionate is heated with sodalime.
14. What happens when acetic acid reacts with ethyl alcohol in presence of conc. H 2SO4 ?
15. How acetic acid is prepared from methyl cyanide ?
16. What happens when sodium acetate is heated with sodalime ?
17. What happens when formic acid reacts with acidified KMnO 4 solution ?
18. Explain : acetic acid is stronger acid than ethanol.
19. What is the reaction of acetic acid with lime water ?
20. How can you get acetone form acetic acid ?
21. What happens when formic acid reacts with meruric chloride?
22. Arrange the following in the increasing order of acidic strength.
(i) ClCH2COOH (ii) ClCH2CH2COOH
(iii) FCH2COOH (iv) CH3COOH [Ans: (iv) < (ii) < (i) < (iii)]
23. How can you distinguish acetic acid from acetone ?
24. How would you convert acetic acid to methylamine ?
25. Explain the reaction of formic acid with Fehling’s solution.
26. Complete the following equation by writing the structures of A,B and C.
Cl / P NaCN H O
CH 3 COOH ¾ ¾¾
2
¾® A ¾¾¾
¾® B ¾ ¾¾
2
®C
H+
27. How can a carboxylic acid be converted to an aldehyde in two steps?
C. Short answer type (3 marks each)
1. Convert methyl iodide to acetic acid.

2. What happens when CH3COONa is electrolysed ? Explain with mechanism.
3. Explain: Benzoic acid is more acidic than aliphatic acids.
PCl5
4. Identify A, B and C from the following, C2H5OH
KCN H3O+
(A) (B) (C)
5. Acetic acid is weaker than formic acid, but chloroacetic acid is stronger than formic acid.
Explain.
6. How will you distinguish between benzoic acid and phenol ?
7. How do you prepare 2 - hydroxy propionic acid from acetaldehyde ?
8. Complete the equation
? Excess
CH3COOH ClCH2COOH ?
of NH3
9. Give the IUPAC name of (i) CH3COCH2COOH.

(ii) CH3CH = CHCOOH.
(iii) HO — CH2CH2CH — COOH
—
CH3
10. What are the following reagents ? Give one use of each reagent.
(a) Tollens’ reagent (b) Schiff’s base (c) Fehling’s solution.
11. What is esterification? Explain with mechanism taking the example of benzoic acid.
12. CH3COOH gives HVZ reaction, where as HCOOH does not. Explain.
D. Long answer type (7 marks each)

1. Give any two methods of preparation of monocarboxylic acids. How formic acid reacts
with Tollens’ reagent ? How can you obtain acetamide from acetic acid ?
2. Explain with equation how monocarboxylic acid is obtained from alkyl cyanide. How
does acetic acid react with the following ?
(a) C2H5OH (b) PCl5 (c) Sodamide
3. How do you prepare the followings from acetic acid ?
(a) Acetaldehyde (b) Methyl amine
(c) Methyl cyanide (d) Acetone
4. Describe any two general methods of preparation of monocarboxylic acid. How does
formic acid react with.
(a) Tollens’ reagent (b) alcohol (c) Sodium

5. Discuss any two methods for preparing benzoic acid. How benzoic acid is converted to
benzoyl chloride?
6. How is acetic acid prepared ? Give any two methods. Give its reaction with Cl 2 in the
presence of Red P, P2O5 and ethyl alcohol in presence of sulphuric acid.
7. Give any one method of preparation of acetic acid. Write its reaction with
(a) chlorine (b) alkali (c) phosphorus pentachloride.
8. (a) Synthesize benzoic acid from toluene
(b) How does it react with (i) conc. HNO3 and conc.H2SO4
(ii) Cl2 in the presence of anhydrous AlCl3
9. Give any two general methods of preparation of monocarboxylic acids. What is the reaction
of formic acid with.
(a) ammonia (b) Tollens’ reagent ?
10. Compare the acid characters of formic acid and acetic acid.
11. How acetic acid is prepared by using Grignard’s reagent ? Give one method to distinguish
acetic acid from formic acid. Mention two uses of acetic acid.
12. Write notes on — (5marks each)
(i) Halogenation of benzoic acid
(ii) HVZ reaction
13. Explain why carboxylic acids behave as acids ? Discuss bfiefly the effect of electron -
donating and electron withdrawing substitueents on the acidity of aliphatic carboxylic
acids.
MULTIPLE CHOICE TYPE

E. Select the correct answer :
1. The oils from which soaps are prepared belong to a class of compound known as :
(a) Amine (b) Acid
(c) Hydrocarbon (d) Ester
2. Formic acid and acetic acid may be distinguished by reaction with
(a) Sodium (b) Dilute acidified KMnO4
(c) 2, 4 dinitrophenyl hydrazine (d) Sodium ethoxide
3. The end product in the sequence of reaction.

KCN NaOH
R–X A B is :
(a) an alkane (b) A carboxylic acid
(c) sodium salt of carboxylic acid (d) Saponification
4. Which of the following reduces HgCl2 to Hg2Cl2 ?
(a) Formic acid (b) Ammonia
(c) Acetic acid (d) CCl4
5. Acetic acid can be halogenated in presence of red P and halogen, but formic acid cannot
be halogenated in the same way due to
(a) Presence of a - hydrogen atom in acetic acid
(b) Presence of – COOH group in formic acid
(C) Presence of carbonyl group in acetic acid
(d) None of the above
6. Among acetic acid, phenol and n-hexanol, which of the compounds reacts with NaHCO 3
solution to give sodium salt and carbon dioxide ?
(a) Acetic acid (b) n - Hexanol
(c) Acetic acid and phenol (d) Phenol
7. Vinegar contains
(a) 10 to 20% acetic acid (b) 10% acetic acid
(c) 6 to 10% acetic acid (d) 100% acetic acid
8. Which acid is strongest ?
(a) CCl3 COOH (b) Cl2CHCOOH
(c) ClCH2COOH (d) CH3COOH
9. The acid which does not contain – COOH group is
(a) Ethanoic acid (b) Picric acid
(c) Lactic acid (d) Palmitic acid
10. Which of the following cannot reduce Fehling’s solution ?
(a) Formic acid (b) Acetic acid
(c) Formaldehyde (d) Acetaldehyde
11. When benzoic acid is reacted with LiAlH4, it forms
(a) Benzene (b) Benzaldehyde
(c) Toluene (d) Benzylalcohol
12. Electrolysis of sodium salt of maleic acid to ethyne is known as

(a) Wurtz’s reaction (b) Clemmensen’s reduction
(c) Kolbe’s reaction (d) Sabatier Senderen’s reaction.
13. Which of the following reactions is expected to readily give a hydrocarbon product in
good yield.
electrolysis I
(a) RCOOK (b) RCOOAg 2
oxidation
Cl2 C2H5OH
(c) CH3CH3 (d) (CH3)3 C Cl
hu
14. Monocarboxylic acids show functional isomerism with
(a) esters (b) alcohols
(c) ethers (d) aldehydes
15. The boiling point of acetic acid is higher than expected from its molecular weight,
because of
(a) solubility in water (b) non-polar character
(c) strong oxidising character (d) association through hydrogen bonding
16. Acids are obtained as a result of reaction between a Grignard reagent and
(a) Oxygen (b) CO2
(c) CH3COCl (d) CH3CHO
17. Which acid is weaker than benzoic acid?
(a) p-Methyl benzoic acid (b) p-chlorobenzoic acid
(d) p-Nitrobenzoic acid (d) o-Chlorobenzoic acid
18. Carboxylic acids are more soluble in
(a) Ether (b) C6H6
(c) Na2CO3 solution (d) CHCl3
19. Stinges of bees and wasps contain
(a) formalin (b) formaldehyde
(c) acetic acid (d) formic acid
20. Formic acid is obtained by the hydrolysis of
(a) HCN (b) CH3CN
(c) (COONa)2 (d) CO + CO2
21. What is the main reason for the fact that carboxylic acids can undergo ionisation?
(a) Absence of a-hydrogen (b) Resonance stabilisation of the
carboxylate ion
(c) High reactivity of (d) Hydrogen bonding.
a-hydrogen
22. RCOOH RCH2OH. This mode of reduction of an acid to alcohol can be affected
by
(a) Zn/HCl
(b) Na/Alcohol
(c) Aluminium isopropoxide and isopropyl alcohol.
(d) LiAlH4
23. Calcium acetate on heating yields
(a) CaO, CO2 and H2O (b) CaCO3 and H2O
(c) Acetaldehyde and CaCO3 (d) CaCO3 and acetone
24. n-Butyl benzene on oxidation will give
(a) Benzyl alchohol (b) Butanoic acid
(c) Benzoic acid (d) Benzaldehyde
25. Benzoic acid may be converted into ethyl benzoate by reaction with
(a) Ethyl chloride (b) DryHCl – C2H5OH
(c) Ethyl alcohol (d) Sodium ethoxide
(i) CO2
26. C6H5MgBr P
+
(ii) H 3O
In the above equation, Product ‘P’ is
(a) Benzaldehyde (b) Benzoic acid
(c) Phenol (d) Benzophenone
27. Which of the following does not give benzoic acid on hydrolysis ?
(a) Phenyl cyanide (b) Benzoyl chloride
(c) Benzyl chloride (d) Methyl benzoate
28. Which of the followings is the strongest acid ?
(a) o-Nitrobenzoic acid (b) p-Nitrobenzoic acid
(c) p-Chlorobenzoic acid (d) Benzoic acid
Zn CH 3Cl Alk
29. Phenol dust X Anhyd.AlCl Y KMnO Z, the product ‘Z’ is
3 4
(a) Benzaldehyde (b) Benzoic acid

(c) Benzene (d) Toluene
30. Which has the highest pKa value ?
(a) Benzoic acid (b) p-Nitrobenzoic acid
(c) m-Nitrobenzoic acid (d) o-Nitrobenzoic acid
31. Which of the following compounds will have the smallest pK a value ?
(a) Benzoic acid (b) Formic acid
(c) Acetic acid (d) Phenylacetic acid
32. Among the following compounds, most acidic is :
(a) p-Nitrophenol (b) p-Hydroxybenzoic acid
(c) o-Hydroxybenzoic acid (d) p-Toluic acid
ANSWERS
A. 1. Acetic acid,
2. 2CH3COOH + Na2CO3 2CH3COONa + CO 2+ H2O
sodium acetate
3. CH3COOH + NH3 CH3COONH4 CH3CONH2 + H2O
Amm.acetate Acetamide
4. Formic acid is used in leather industry in tanning for removing lime, from the hides. It is
also used for preparing certain medicines and antiseptics.
5. Phenyl magnesiumbromide
6. CH3 – CH – CH2 –COOH
|
OH
7. 3 Bromo propanoic acid.
8. (i) Ethylpropanoate (ii) Pentanedioic acid
9. Formic acid reduces Tollen’s reagent or Fehling solution.
10. Benzoic acid
E. 1. (d) 2. (b) 3. (c) 4. (a) 5. (a) 6. (a) 7. (c) 8. (a) 9. (b) 10. (b)
11.(b) 12.(c) 13.(a) 14.(a) 15.(d) 16.(b) 17. (a) 18. (c) 19. (d) 20.(a)
21.(b) 22.(d) 23.(d) 24.(c) 25.(b) 26.(b) 27.(c) 28.(a) 29. (b) 30.(a)
31. (b) 32.(c)
qqq
AMINES 643
UNIT - XIII
ORGANIC COMPOUNDS CONTAINING NITROGEN
CHAPTER - 20
AMINES
20.1 INTRODUCTION :
The amines are considered as alkyl / aryl derivatives of ammonia in which one or more
hydrogen atoms in an ammonia molecule have been replaced by alkyl and / or aryl groups.
20.2 TYPES OF AMINES :
20.2.1 ALIPHATIC AMINES :
Aliphatic amines are the derivatives of ammonia in which one or more hydrogen atoms in
ammonia molecule are replaced by alkyl groups. These are classified as primary, secondary and
tertiary amines depending on whether one, two or three hydrogen atoms of ammonia molecule
are replaced by alkyl groups.
H H R R
| | | |
H—N—H R—N—H R—N—H R—N—R
or or or or
NH3 RNH2 R2NH R3N
Ammonia Primary amine Secondary amine Tertiary amine
Primary, Secondary and Tertiary amines :
(i) Primary or 10 amines : The primary amines have the general formula, RNH 2 and are
characterised by — NH2 group linked to an alkyl group. The —NH2 group in primary
amine is called the amino group.
(ii) Secondary or 20 amines : The secondary amines have the general formula, R 2NH and
are characterised by NH group linked to two same or different alkyl groups. The NH
group in secondary amine is called the imino group.
(iii) Tertiary or 30 amines : The tertiary amines have the general formula, R 3N and are
characterised by — N group linked to three same or different alkyl groups.
Quaternary ammonium salts : If all the four hydrogen atoms of an ammonium salt are
replaced by same or different alkyl groups, the compound is called quaternary ammonium
salt or tetraalkyl ammonium salt.
+ +
H R
| |
H — N — H Br— R — N — R Br—
| |
H R
NH4Br R4NBr
Ammonium bromide Tetra-alkyl ammonium bromide
20.2.2 ARYL AMINES :
Arylamines are those having the amino group (one or more) directly attached to an aromatic
NH2 NH-CH3
nucleus. For example : aniline methylaniline O-phenylenediamine
NH2
etc. Like aliphatic amines, arylamines may be primary (1 0), secondary (20) or tertiary (30)
NH2
according as one, two or all the hydrogen atoms of ammonia are replaced by phenyl or aryl radicals. In
case of secondary and tertiary amino compounds, all the hydrogen atoms may not be replaced by aryl
groups. There may be both alkyl and aryl groups. Such amines are of mixed aliphatic – aromatic type
secondary and tertiary amines. A few examples of both pure and mixed amines are given below.
NH2 NH2 NH2
Primary :
CH3
Aniline NH2
m- toluidine p-phenylenediamine
NHCH3
Secondary : NH
Diphenylamine N- Methylaniline
(mixed)
N CH3
Tertiary : N
CH3
N, N -Dimethylaniline
Triphenylamine (mixed)
AMINES 645
Aromatic compounds with amino groups present in the side chain are called arylalkyl amines.
CH2–NH2 CH2– CH2– NH2
For example, benzylamine , b - phenylethylamine etc. These are
aryl substituted aliphatic amines and behave very much like aliphatic amines.
NH2
Aminobenzene or Benzenamine or C6H5 – NH2
Aniline [C6H5NH2] is the simplest primary arylamine.
20.3 NOMENCLATURE :
1. Common system : The common names of aliphatic amines are derived by listing the
alkyl groups on the nitrogen in order of increasing size ending with amine. If same type
of alkyl group occurs twice or thrice on the nitrogen atom, the prefix di- or tri- is placed
before the name of the alkyl group.
CH3
|
CH3NH2 CH3NHCH3 CH3 — N — CH3 CH3NHCH2CH3
Methylamine Dimethylamine Trimethylamine Methyl ethylamine
2. IUPAC system : In IUPAC system primary amines are called alkanamines; secondary
amines, alkyl alkanamines and tertiary amines, dialkyl alkanamines. The longest alkyl
group is considered as the parent chain.
CH3NH2 CH3CH2NH2 CH3CH2CH2NH2
Methanamine Ethanamine Propanamine
CH3
CH3CH2NH2CH3 CH3 — CH2 — CH2 — N
CH3
N – Methyl ethanamine N, N – dimethyl propanamine
In the higher and more complex compounds the amino group is treated as a substituent
and is assigned the locant keeping in view the lower number rules and the order of priority of
different functional groups. Names of a few amines are given below.
NH2 NH2
| |
CH3 — CH — CH2 — CH3 CH3CH2CH2CH2CH2NH2 CH3— CH—CH3
2-Butanamine 1-Pentanamine 2-Propanamine

NH2 CH3
| |
CH3 — C — CH3 CH3 — CH — CH — CH2— CH3
| |
CH3 NH2
2 – Methyl – 2 –propanamine 3–Methyl –2– pentanamine
3. Nomenclature of some common aryl amines are given below :
Structure Common name IUPAC name

NH 2
Aniline Aniline or Benzenamine
NH 2
CH3
o-Toluidine 2-Methylanine
NH 2
p-Cloroaniline 4-Chlorobenzenamine
or
4-Chloroaniline
Cl
N(CH 3) 2
N, N-Dimethylaniline N, N – Dimethyl - benzenamine
20.4 ISOMERISM :
Amines exhibit (i) Chain isomerism (ii) Position isomerism (iii) Functional isomerism
(iv) Metamerism.
(i) Chain isomerism : CH3
|
CH3 — CH2 — CH2 — NH2 CH3 — CH — NH2
n-Propylamine (common name) Isopropylamine (common name)
(ii) Position isomerism : NH2
|
CH3 — CH2 — CH2 —CH2 — NH2 CH3 — CH — CH2 — CH3
n-Butylamine sec-Butylamine
NH 2
NH 2 NH 2
CH3
CH3 CH3
1-Methylaniline 2-Methylaniline 3-Methylaniline

AMINES 647
(iii) Functional isomerism :
CH3 — CH2 — NH2 CH3 — NH — CH3

Ethylamine Dimethylamine
C6H5CH2NH2 C6H5 — NH — CH3

Benzylamine N-Methylaniline
(iv) Metamerism :
C2H5 CH3 CH3
NH NH CH3 — NH — CH
C2H5 C3H7 CH3
Diethylamine Methyl Methyl
propylamine isopropylamine
C6H5 C6H5CH2
NH NH
C2H5 CH3
N-Ethylaniline N-Methylbenzylamine
20.5 GENERAL METHODS OF PREPARATION :
1. Ammonolysis of Alkyl halides (Hofmann’s method)
Primary amines may be prepared by heating an alkyl halide with excess of alcoholic
solution of ammonia in a sealed tube.
R– X + H – NH2 RNH2 + HX
Alkyl halide Ammonia 10 amine
CH3 – I + H – NH2 CH3NH2 + HI

Methyl iodide Methylamine
The primary amine reacts with another molecule of alkyl halide to form secondary amine.
R – X + H HN R R2NH + HX
20 amine
The secondary amine can combine with another molecule of alkyl halide of form a tertiary
amine which in turn can combine with another molecule of alkyl halide to form quaternary
ammonium salt.
R X + H N R2 R3N + HX
30 amine
R X + R3 N R4NX
Tetra - alkyl ammonium halide
Commercially, the amines are separated by fractional distillation.
Simple aryl halides i.e. when the halogen atom (X) is directly attached to the aromatic
ring are ordinarily inert towards ammonia. This is because, in aryl halide the C – X bond
is stronger than C – X bond in alkyl or benzyl halides. However, aryl halides react with
ammonia in presence of catalyst (copper salts) at high temperature and under high pressure
to form the corresponding amino compounds.
Cu2 O
Ar – X + NH3 Ar – NH2 + HX
D, pressure
Aryl halide 1°-Amine
Cu2 O
C6H5 – X + NH3 C6H5NH2 + HX
D, pressure
Halobenzene Aniline
Like aliphatic primary amines, aniline react with alkyl halides (RX) giving successively
secondary, tertiary amines and quaternary ammonium salts.
RX RX RX + –
C6H5NH2 C6H5NHR C6H5Nr2 C6H5N R3X
2° Amine 3° Amine Quaternary
ammonium salt
2. Ammonolysis of alcohols and phenol : When vapours of an alcohol and ammonia are
passed over a dehydrating catalyst such as thoria or alumina at 300 0C, a mixture of primary,
secondary and tertiary amines is formed.
ThO2
R – OH + H – NH2 RNH2 + H2O
3000C
R – OH + H – H NR R2NH + H2O
R – OH + H – NR2 R3N + H2O

Phenols react with ammonia in the presence of zinc chloride at about 300°C to form the
corresponding amines.
ZnCl 2
Ar – OH + HNH2 Ar – NH2 + H2O
300°C
ZnCl 2
C6H5 – OH + NH3 C6H5 – NH2 + H2O
300°C
Phenol Aniline
AMINES 649
3. Reduction of nitroalkanes and nitroarenes : When a nitro group is reduced it is easily

converted to amino group. The reduction can be brought about by tin and hydrochloric acid
or iron and hydrochloric acid or hydrogen in presence of nickel or platinum or lithium
aluminium hydride.
Sn + HCl
R NO2 + 6H R NH2 + 2H2O
or Fe + HCl
Nitroalkane
CH3NO2 + 6H CH3NH2 + 2H2O
Nitromethane Methylamine
C6H5NO2 + 6H C6H5NH2 + 2H2O
Nitrobenzene Aniline
Catalytic reduction :
Nitrobenzene can also be catalytically reduced by hydrogen under pressure in presence of
Platinum or Raney nickel.
Raney Ni or
C6H5NO2 + 3H2 C6H5NH2 + 2H2O
Pt or Pd
Nitrobenzene Aniline
4. Hofmann bromamide reaction : The action of bromine on acid amides in an alkaline

(NaOH or KOH) solution produces an amine containing one carbon atom less than the
number present in the amide. This reaction was developed by Hofmann and used in
degradation of carbon chain.
RCONH 2 + Br2 + 4 KOH ® R - NH 2 + 2 KBr + K 2 CO 3 + 2 H 2 O
CH 3CONH 2 + Br2 + 4 KOH ® CH 3NH 2 + 2 KBr + K 2 CO 3 + 2 H 2 O

Acetamide Methylamine
C6H5CONH2 + Br2 + 4KOH ® C6H5NH2 + 2KBr + K2CO3 + 2H2O

Benzamide Aniline
5. Reduction of alkyl and aryl cyanides :
When alkyl cyanides are reduced by sodium and alcohol (Mendius reaction) or lithium
aluminium hydride, 10amines are formed
Na+ Alcohol
RCN + 4H RCH2NH2
or LiAlH4
CH3CN + 4H CH3CH2NH2
C6H5CN + 4H C6H5CH2NH2
6. From Grignard reagent : Alkyl magnesium halides react with chloramine to form primary
amines.
X
RMgX + ClNH2 RNH2 + Mg
Cl
Grignard reagent
7. From isocyanates : Acyl azides on heating produce isocyanates. When alkyl isocyanates
are boiled with alkali, they undergo hydrolysis to form primary amines. This is known as
Curtius reaction.
RCOCl + NaN3 RCON3 + NaCl
RCON3 heat R—N=C=O

Acyl azide Alkyl isocyanate
H2O
R—N=C=O RNH2 + CO2
Carboxylic acids react with hydrazoic acid to form primary amines. This is called Schmidt
reaction.
H2SO4
RCOOH + HN3 RNH2 + N2 + CO2
heat
8. Gabriel’s phthalimide synthesis : Phthalimide reacts with alcoholic potash to form

potassium phthalimide which reacts with alkyl halide to give N - alkyl phthalimide. This
on hydrolysis with 20% HCl gives primary amine
CO CO CO 2H2O
NH KOH NK RI NR
CO CO CO
Phthalimide Potassium phthalimide N — alkyl phthalimide
COOH
+ RNH2
COOH
Phthalic acid 10Amine
Phthalic acid can be utilised for preparing phthalimide.
Aromatic primary amines cannot be prepared by this method because aryl halides will
not react with potasium phtholimide to form N – aryl phthalimide.
AMINES 651
20.6 GENERAL PROPERTIES :
Basicity of aliphatic amines : Amines are derivatives of ammonia and hence like ammonia
these are basic in character. The basicity of amines and ammonia is due to the presence of unshared
electron pair on nitrogen atom which accepts a proton. The readiness with which the lone pair of
electrons is available for coordination with a proton determines the relative basicity of amines.
.. .. .. ..
H—N—H R—N—H R—N—R R—N—R
| | | |
H H H R
Ammonia Primary amine Secondary amine Tertiary amine
Alkyl groups are electron releasing groups. As a result the nitrogen atoms become electron
rich. The lone pair of electrons is more readily available than ammonia. Thus amines are
stronger bases than ammonia. Accordingly the basicity should increase with number of
alkyl groups. However, the basicity follows the order, [in case of methylamine (1 0),
dimithelamins (20) and trimethyl amine (30)]
Secondary > Primary > Tertiary > Ammonia
The reason for this is the steric factor. In tertiary amines three alkyl groups prevent the
proton for coordination with lone pair. Hence tertiary amines are less basic than even
primary amine. Ethyl amine is more basic than methyl amine since the +I effect of ethyl
group is more than that of methyl group. Since chlorine is electron withdrawing group,
chloramine is less basic than ammonia.
C2H5NH2 > CH3NH2
NH3 > ClNH2
Basic Character of aromatic amines : Aniline is weakly basic and forms crystalline
salts with acids. It also forms double salt with PtCl 4 and AuCl3
+ –
C6 H5 – NH2 + HCl [C6H5 – NH3 ] Cl
Aniline hydrochloride
C6H5 NH2 + H2SO4 [C6H5 – NH3] HSO4
Aniline hydrogensulfate
2 C6H5 NH2 + 2HCl + PtCl4 [C6H5 NH3Cl]2 PtCl4
Aniline chloroplatinate
+
Basicity of a compound is its ability to accept a proton (H ). We have seen that the
amines behave as bases due to the capacity of the lone pair of electron on nitrogen to form a
coordinate bond with the proton. Thus aliphatic amines are basic and more basic than ammonia,
because the alkyl group pushes the electron towards nitrogen (+I effect). Hence, electron density
on nitrogen increases. Aniline is a resonance hybrid of the following canonical structures:
Due to the resonance interaction between the p – electron of the benzene ring and the
lone pair of electron on nitrogen atom of the amino group, the lone pair of electron on the nitro-
gen atom responsible for the basicity of aniline is less available to be donated to a proton. Fur-
ther, a small amount of positive charge on nitrogen atom tends to repel proton. Hence, aniline is
a weak base.
Aniline may accept a proton to form a small amount of anilinium ion.
.. +
NH2 NH3
+ H+
(Anilinium ion)
But anilinium ion less stable since there is no resonance in this ion. Therefore, the
equilibrium shifts to the other side ie. towards aniline which is more stable. The low basicity of
aniline is, therefore, due to the fact that aniline is stabilized by resonance to a greater extent than
anilinium ion.
Electron releasing substituents, like – CH3 increase the basicity of aniline whereas elec-
tron withdrawing substituents, like Cl, Br, I, NO2 decrease the basicity. This is due to the fact that
electron release stabilizes the anilinium ion relative to aniline by dispersing the positive charge
of the anilinium ion. Thus, monomethyl and dimethylanilines are stronger bases than aniline,
CH3 CH3
NH2
Again, o-toluidine and p –toluidine would be more basic than aniline. It
NH2
is observed that o-toluidine has a Kb= 2.5 x 10-10 and p-toluidine, Kb = 12 x 10-10 in comparison
to the Kb of aniline (4.2 x 10-10). The anomalous behaviour of o-substituted anilines is, however,
possibly due to ortho effect. Thus o-substituted anilines tend to have Kb lower than that of
AMINES 653
aniline irrespective of the nature (electron – releasing or electron withdrawing) of the substitu-
ent. The base –weakening effect of electron –withdrawing substituents is most marked when
present in ortho position of the amino group.
Physical Properties :
(1) State : The lower members of amines are gases. Those of three to eleven carbon atoms
(except trimethyl amine) are liquids at ordinary temperature. Higher members are solids.
(2) Odour : Amines of lower molecular mass possess odour similar to that of ammonia. As
the molecular mass increases these have characteristic unpleasant odour of a decaying
fish. In general it can be stated that aliphatic amines possess fishy or fish -like odour.
(3) Density : These are lighter than water.
(4) Solubility : The lower members (less then six carbon atoms) of the family are highly
soluble in water as all amines including tertiary amines are capable of forming hydrogen
bonds with water.
(5) Boiling point : The boiling points are higher than those of the corresponding alkanes.
This is due to the polar nature and intermolecular hydrogen bonding in amines. The
boiling points of amines are lower compared to alcohols and carboxylic acids of comparable
molecular mass. It is due to weaker hydrogen bonding as oxygen is more electronegative
than nitrogen.
(6) Physical properties of Aniline : Freshly distilled aniline is a colourless liquid with
0
unpleasant odour, b.p. 184 C. On exposure to light and air, it undergoes oxidation and
turns brown. It is heavier than water and is slightly soluble in it, but it is highly soluble in
alcohol, ether and benzene. Aniline is a polar molecule and its dipole moment is 1.48D.
Chemical Properties :
1. Reaction with water : Amines combine with water to form alkyl ammonium hydroxides
which ionise to give protonated amines and hydroxide ion.
RNH2 + H2O RNH3OH RNH3+ + OH—
Amine Alkyl ammonium hydroxide Protonated amine
2. Reaction with acids : Amines react with strong acids to form ammonium salts. Methyl
amine combines with hydrochloric acid to form methylammonium chloride.
+
CH3NH2 + HCl CH3NH3 Cl–
Methylammonium chloride
RNH2 + HCl RNH3Cl

1° Amine Alkylammonium chloride
2C2H5NH2 + H2SO4 (C2H5NH3)2SO4
+ –
C6H5NH2 + HCl [C6H5 – N H3] Cl (Crystalline salt)
Aniline Aniline hydrocloride
R2NH + HCl R2NH2Cl
20Amine Dialkyl ammonium chloride
R3N + HCl R3NHCl
30Amine Trialkyl ammonium chloride.
3. Reaction with alkyl halides : Primary amines take up three molecules of alkyl halide to
form secondary and tertiary amines and quaternary ammonium salts.
CH3NH2 + CH3I (CH3)2NH + HI

Methyl amine Dimethyl amine
(CH3)2NH + CH3I (CH3)3N + HI

Trimethyl amine
(CH3)3N + CH3I (CH3)4NI

Tetramethyl ammonium iodide.
Like aliphatic primary amines, aniline can react with alkyl halides giving successively
secondary, tertiary amine and quaternary ammonium salts. These are all typical nucleophilic
substitution reactions.
.. heat OH
C6H5– NH2 + R–X C6H5– NH2R X C6H5 – NHR
Aniline alkyl halide N-alkylaniline
(Sec. amine)
.. heat OH
C6H5– NH – R + R – X C6H5– NHR2 X C6H5 NR2
N,N-dialkylaniline
(tertiary amine)
.. heat
C6H5– NR2 + R–X C6H5– NR3 X
Quaternary ammonium salt
This process of introducing alkyl group in the molecule is called alkylation. N-arylation
is usually more difficult and purely aromatic quaternary ammonium salt of the type
+
[(C6H5)4N)] X is unknown.
AMINES 655
4. Reaction with acid chloride and acid anhydride (Acylation) : Primary and secondary
amines react with acid chlorides and anhydrides to form alkyl derivatives of amides
(substituted amides).
O O
|| ||
RNH – H + Cl — C — R/ R — NH — C — R/
10 Amine N - Alkylamide
O
R/CO ||
R2NH + O R2N — C — R/ + R/ COOH
R/CO
20 Amine Acid anhydride N, N - dialkylamide
Aniline reacts with acetyl chloride in presence of a base like pyridine or sodium hydroxide
to neutalise the acid formed. The product is a substituted acid amide.
O O
|| ||
CH3 – C – Cl + H2N — base CH3– C – NH –
– HCl
(Acetyl chloride) (aniline) (Acetanilide or
N-phenylethanamide)
Substituted acid amides like acetanilide can also be considered as acyl derivatives of
0
amines. Thus, acetanilide is acetyl derivative of aniline. It is to be noted that only 1 and
0
2 amines containing hydrogen atom attached to nitrogen can undergo acylation reaction.
O
=
Acylation is a process of introducing R – C – group into the molecule. Introduction of
CH3 –CO – group is called acetylation. Similarly, introduction of benzoyl group

O
=
(C6H5– C –) is called benzoylation. Benzoylation of aniline is carried out by treating

aniline with benzoyl chloride in presence of NaOH.
NaOH
C6H5– NH2 + Cl – CO – C6H5 C6H5– CONHC6H5
(Aniline) (Benzoyl chlonde) (Benzanilide)
In this reaction, H atom of – NH2 group is substituted by benzoyl group. (C6H5 – CO –).
This reaction is known as Schotten- Baumann reaction.
5. Reaction with nitrous acid : (Distinction): Amines are distinguished by this reaction.
Nitrous acid is formed by the reaction by sodium nitrite with dilute mineral acids.
(a) Primary amines react with nitrous acid to form primary alcohol with the liberation
of nitrogen.
NaNO2 + HCl NaCl + HNO2

CH3CH2NH2 + HONO CH3CH2OH + N2 +H2O
Ethyl amine Ethyl alcohol
Important : Methylamine does not give methyl alcohol with NaNO2 & dil. HCl. Instead
it gives methyl nitrite and dimethyl ether.
CH3NH2 + 2HONO CH3 — O — N = O + N2 + H2O
2CH3NH2 + 2HONO CH3 — O — CH3 + 2N2 + 3H2O
(b) Secondary amines react with nitrous acid to form nitrosoamine (yellow oil).
(CH3)2NH + HONO (CH3)2N — N = O + H2O
Dimethylamine Nitrosodimethylamine
(c) Tertiary amines dissolve in nitrous acid to form addition product which decomposes
to form nitrosoamine and alcohol.
HNO2 heat
(CH3)3N (CH3)3 NHNO2 (CH3)2NNO + CH3OH
Nitrosodimethylamine
Aryl primary, secondary and tertiary amines react differently with nitrous acid. Since
nitrous acid is unstable, it is prepared in the reaction medium by the action of dilute
hydrochloric acid on sodium nitrite at low temperature.
(a) Primary amines :
Aromatic primary amines react with nitrous acid at 273 – 278 K (0 – 5 0C) to form
arenediazonium salts. Thus,
NaNO2 + HCl HNO2 + NaCl

+
NH2 N NCl
+ HNO2 + HCl 273-278K + 2H2O
Benzenediazonium chloride
This reaction of converting primary aromatic amines into diazonium salts by treatment
with a cold (273 - 278K) solution of nitrous acid is called diazotisation.
(b) Secondary amines :
Secondary amines (both aromatic and aliphatic) react with nitrous acid to give N-
nitrosoamine which being insoluble in dilute mineral acids separate out as yellow oily
compounds.
AMINES 657
CH3 CH3
NH + HONO N – N = O + H2O
N-Methylaniline N-Nitroso-N-methylaniline
(Yellow oil)
These N-nitrosoamines on warming with a crystal of phenol and a few drops of conc.H 2SO4
form a green solution which when made alkaline with aqueous NaOH, turns deep blue
and then red on dilution. This reaction is called Liebermann nitroso reaction and is
used as a test for secondary amines.
(c) Tertiary amines :
Aromatic tertiary amines undergo electrophilic substitution with nitrosonium ion at p-

position of the phenyl ring to form green-coloured p-nitrosoamines.
CH3 CH3
N + HONO N N = O + H2O
CH3 CH3
N, N-Dimethylaniline p-Nitroso-N, N-dimethylaniline (green)
Thus, the reaction with nitrous acid can be used for the distinction of 1 0, 20 and 30 amines.
Uses : Aniline is largely used for preparation of dyes and drugs. It is also used in the manufacture
of accelerators used in rubber industry. Aniline also finds its use in calico printing.
6. Carbylamine reaction : This reaction is responded only by primary amines. Primary
amines on heating with chloroform and alcoholic caustic potash give isocyanides
(carbylamines) with very unpleasant odour.
RNH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O
Alkylisocyanide
(Carbylamine)
CH3NH2 + CHCl3 + 3KOH CH3NC + 3KCl + 3H2O
Primary arylamines like aliphatic primary amines undergo carbylamine reaction. When
heated with chloroform and alcoholic KOH, aniline give obnoxious smelling carbylamine
or phenyl isocyanide.
C6H5NH2 + CHCl3 + 3KOH C6H5NC + 3KCl + 3H2O
(Aniline) (Phenyl isocyanide)
In general,
Ar NH2 + CHCl3+ 3KOH Ar NC + 3KCl + 3H2O
(Arylamine) Aryl isocyanide
or carbylamine
7. Reaction with benzene sulphonyl chloride (Distinction): Primary amines react with
benzene sulphonyl chloride to form alkyl benzene sulphonamides, soluble in caustic alkali.
Secondary amines form dialkyl benzene suphonamides insoluble in caustic alkali. Tertiary
amines do not react.
RNH– H + Cl – SO2 C6H5 RNHSO2C6H5 + HCl
R2N – H + Cl – SO2 C6H5 R2NSO2C6H5 + HCl

8. Reaction with Grignard reagent : Primary amines react with Grignard reagent to form
hydrocarbons.
RNH2 + R/MgX R/H + RNHMgX
9. Formation of Schiff’s bases : Primary amines react with aldehydes to form imine or
Schiff’s bases. This is catalysed by acids.
H+
RN H2 + O HCR/ R — N = CH — R/ + H2O
Schiff’s base
10. Electrophilic Substitution reaction of Aryl amines : We have seen that due to resonance,
the ortho – and para – positions with respect to – NH2 group in aniline become electron
rich. Therefore, electrophilic substitution in aniline becomes easier, and the substituents
enter the ortho – or / and para-positions in the ring with respect to – NH2 group.
(a) Halogenation : The presence of – NH2 group in aniline activates the nucleus so
much that all the H – atoms of o – and p – positions are readily replaced by bromine
or chlorine atoms. Thus, aniline reacts with bromine – water to form 2, 4, 6 –
tribromoaniline. Bromine enters para and both the ortho positions.
NH2 NH2
Br Br
H2O
+ 3Br
2
(Aniline) Br
(2, 4, 6 tribromoaniline)
Chlorine, however, reacts with aniline in presence of water – free solvent like
chloroform to form 2 , 4, 6 – trichloroaniline.
NH2 NH2
Cl Cl
Chloroform
+ Cl
2
(Aniline) Cl
(2, 4, 6
trichloroaniline)
AMINES 659
For the preparation of a monobromo compound, aniline is first acetylated before

bromination. Finally, the acetyl group is removed through hydrolysis.
NH2 NHCOCH3 NHCOCH3 NH2

| | | |
base Br2 Hydrolysis
+ CH3COCl +CH3COOH
CH3COOH H2O,H
(acetyl chloride) | |
(aniline) (Acetanilide) Br Br
(p- bromoacetanilide)
(p- bromoaniline)
Major product
The reactivity of the nucleus is decreased by acetylating – NH 2 group, since acti-

vating influence of – NHCOCH3 group is much less than that of – NH2 group. In
that case, only mono substituted product is formed.
(b) Sulphonation : When aniline is heated with excess of conc. H2SO4 or fuming
sulphuric acid at about 1800 – 2000C for 3 – 4 hours, p – amino benzene sulphonic
acid or sulphanilic acid is formed as the main product. Aniline hydrogen sulphate,
formed loses a molecule of water to form phenyl sulphamic acid which rearranges
to sulphanilic acid.
– NH.SO3H NH3
NH2 NH3HSO4 NH2
| | | | |
H2SO4 heat
1800 – 2000
| |
(Aniline) (aniline hydrogen (Phenyl Sulphamic SO3H SO3
sulphate) acid) (Sulphanilic acid) (Zwitter ion)
Sulphanilic acid contains one acidic group (SO3H) and one basic group (-NH2).
The H ion of – SO3H group combines with – NH2 group forming –NH3. This is a
special type of salt in which an acid group and a basic group of the same molecule
+ –
neutralize each other. Thus, sulphanilic acid molecule contains both N H3 and SO3
ions. So, it is a dipolar ion or Zwitterion. Sulphanilic acid does not show basic
character. The acidic property predominates in the molecule.
(c) Nitration : Aniline can not be nitrated directly by the nitrating mixture (conc.
H2SO4 + Conc. HNO3), because the amino group is oxidized to form various tarry
products. To prevent this oxidation, - NH2 group is first protected by acetylating the
group with acetyl chloride or acetic anhydride and acetanilide formed is then ni-
trated. – NHCOCH3 group is o–, p– directing. So, o–nitro and p–nitroacetanilides
are formed. The two isomers are separated and hydrolysed separately with dilute
acid, when o–nitroaniline and p–nitroaniline are formed.
NH2 NHCOCH3 NHCOCH3 NHCOCH3

| | | |
(CH3CO)2O HNO3 NO2
or +
H2SO4
(aniline) (CH3COCl |
(Acetanilide)
(o-nitroacetanilide) NO2
(p- nitroacetanilide)
H2O HCl H2O HCl
NH2 NH2
| |
NO2
|
(o-nitroaniline) NO2
(p- nitroaniline)
20.7 TESTS :
(1) The aqueous solution of water soluble amines turn red litmus blue. All three classes of
amines (1°, 2°. 3°) being basic dissolve in mineral acids like HCl, H 2SO4 etc. to form salt.
(2) On addition of a concentrated aqueous solution of sodium nitrite to a solution of amine in
dil HCl, primary amines give alcohols with rapid effervescence of nitrogen, secondary
amines form water-insoluble yellow oil and tertiary amines form nitrite addition salts.
Aromatic primary amines, however, react with HNO2 at O – 5°C to from arenediazonium
salts which couple with an alkaline solution of b-naphthol to form orange or red coloured
azo dyes. (distinction form primary alkyl amines).
(3) Carbylamine test (For primary amines) : When a primary amine (aliphaticor aromatic)
is heated with chloroform and alcoholic KOH, an alkyl isocyanide is formed which has a
foul smell.
(4) Liebermann nitroso reaction (For secondary amines) :
R2NH + (NaNO2 + HCl) R2N — N = O + H2O
(Nitrosoamine)
Insoluble yellow oil
AMINES 661
Nitrosoamines on warming with phenol and conc. H2SO4 give a brown or red colour and
when the mixture is poured into alkaline solution, a blue or violet colour is observed.
This is known as Liebermann’s nitroso reaction and often used to detect a secondary
amino group.
20.8 SEPARATION OF PRIMARY, SECONDARY AND TERTIARY AMINES :
Hinsberg’s method — The mixture of amines is treated with Hinsberg’s reagent (Benzene
sulphonyl chloride). Primary and secondary amines react and tertiary amines do not react.
R — NH + C H SO Cl — HCl R.NH.SO C H
2 6 5 2 2 6 5
0
1 amine N– alkyl benzene sulphonamide
R2NH + C6H5SO2Cl — HCl R2N.SO2C6H5
20 amine N, N– dialkyl benzene sulphonamide
To the above mixture some NaOH solution and ether are added. Sulphonamide from
primary amine forms its sodium salt.
RNHSO2 .C2H5 + NaOH R.N (Na)SO2C6H5
Sodium salt (in aqueous layer)
Sulphonamide from secondary and unreacted tertiary amine dissolves in ether and forms
the upper layer. The two layers are separated.
(1) The aqueous layer is acidified with dilute hydrochloric acid and then hydrolysed with
conc. HCl. It is then distilled over NaOH when primary amine passes over.
R.N(Na)SO2.C6H5 + HCl R.NH SO2C6H5 + NaCl
R.NHSO2.C6H5 + HCl+H2O R.NH2HCl + C6H5SO2OH
R.NH2HCl + NaOH R.NH2 + NaCl + H2O
Primary amine
(2) Ether layer is subjected to fractional distillation when tertiary amine distils over. The
remaining sulphomamide of secondary amine is treated with conc. HCl
R2NSO2C6H5 + HCl + H2O C6H5SO2OH + R2NH.HCl
Dialkylamine hydrochloride is then distilled over NaOH when secondary amine is
produced.
R2NH.HCl + NaOH R2NH + NaCl + H2O
20.9 USES :
1. Methyl and ethylamines are used in leather industries for dehairing of hides .
2. Methylamine is used as a refrigerant.
3. Methylamine and ethylamine are used in preparing dyes and medicines.
4. Amines are used in organic synthesis as condensing agents and catalysts.
5. Aromatic amines such as aniline are widely used in the manufacture of dyes and
drugs. Used as additives (antioxidants) and vulcanization accelerators in rubber
industry. It is used for the preparation of phenyl isocyanate needed for the
manufacture of polyurethane plastics. It is also used for the preparation of
arenediazonium salts which in turn is used in the synthesis of wide variety of
aromatic compound.
20.10 CONVERSIONS :
1. Methyl amine to ethyl amine
HNO2 P + I2
CH3NH2 CH3OH CH3I
KCN Reduction
CH3CN CH3CH2NH2
4H
2. Ethyl amine to Methyl amine :
HNO2 [O] Acidified
CH3CH2NH2 CH3CH2OH CH3CHO
K2Cr2O7
[O] NH3 heat Br2+KOH
CH3COOH CH3COONH4 CH3CONH2 CH3NH2
20.11 DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY AMINES :

Reaction Primary Secondary Tertiary
1. Action of nitrous acid Alcohol and N2are formed Nitrosoamine is No reaction
RNH2 + HONO formed. R2NH+ (Only salt is
ROH + N2 + H2O HNO2 formed.)
(Aromatic primary amines R2N—N=O+H2O
undergo diazotisation) at
0 to 5°
2. Action of CH3I Three molecules CH3I Two molecules of One molecule
react to form quaternary CH3I react to form of CH3I reacts
salt quaternary salt to form
quaternary salt.
3. Action of CH3COCl Forms N– alkyl amide Forms N,N– No reaction.
dialkyl amide
4. Carbylamine reaction Forms isocyanide having No reaction No reaction.
a foul smell
5. Action of Hinsberg’s Forms N-alkyl benzene Forms N,N– dialkyl No reaction.
reagent(C6H5SO2Cl) sulphonamide soluble in benzene sulphonamide
aqueous NaOH insoluble in aqueous
NaOH
20.12 CYANIDES AND ISOCYNIDES :

These classes of organic compounds are not dealt separately. Their methods of preparation
and chemical reactions have been discussed at relevant places in the text.
AMINES 663

R
R / //
General formula: R–NH2(10), NH (20) R/ N (30) (R, R , R may be same or
R/ R// different alkyl groups)
Methods of Preparation :
1. Hofmann’s method:
alc.soln.
NH3 + RX RNH2 + HX
1000C
(10amine)
R NH2 + RX R2NH + HX
(20amine)
R2NH + RX R3N + HX
(30amine)
+ –
R3N + RX R4 N X
Quaternary ammonium salt
2. Ammonolysis of Alcohols:
ThO2 orAl2O3
R — OH + H NH2 R–NH2 + H2O
3000C (10amine)
R — OH + H NHR R2NH + H2O

(20amine)
R — OH + H NR2 R3N + H2O
(30amine)
3. Reduction of nitroalkanes :
Sn/conc.HCl
R – NO2 + 6H R–NH2 + 2H2O
(10amine)
4. Hofmann bromamide reaction:
RCONH2 + Br2 + 4KOH RNH2 + 2KBr + K2CO3 + 2H2O
(10amine)
5. Reduction of alkyl cyanides : Mendius reaction

Na/C2H5OH
R – CN + 4H R – CH2 – NH2
or LiAlH4
(10amine)
6. From Grignard reagent :
RMgX + ClNH2 R – NH2 + Mg(X)Cl.

(10amine)
7. From Acids and Acid derivatives :
Curtius reaction : RCOCl + NaN3 RCON3 + NaCl
heat NaOH
RCON3 RNCO R–NH2
boil
(Acid azide) (alkyl isocyanate) (10amine)
Schmidt reaction : RCOOH + HN3 RNH2 + N2 + CO2
(Acid) (Hydrazoic acid) (10amine)
8. Gabriel’s Phthalimide synthesis :
CO KOH CO
NH NK
CO CO
(Phthalimide)
RI CO HCl COOH
NR RNH2+
CO COOH
(10amine)
(Phthalic acid)
General Properties :
1. Basicity : Amines are more baisc than ammonia due to the alkyl group(s) attached to
nitrogen. Aromatic amines are less basic than aliphatic amines.
2. Boiling points : Amines have higher boiling points than the corresponding alkanes due to
intermolecular hydrogen bonding.
AMINES 665
3. Chmical reactions :
(i) Basic nature :

+ –
RNH2 + H2O RNH3 OH
+ –
RNH2 + HX RNH3 X
Free bases (amines) can be
+ –
R2NH + HX R2NH2 X obtained from the salts by
+ – adding dilute base solution.
R3N + HX R3NHX
(ii) Alkylation :
RX(heat) RX RX
RNH2 R2NH R3N R4NX
Pressure –HX
(10amine) (–HX) (20amine) (30amine) Quarternary salt
(iii) Acylation : By acid chloride and acid anhydride.
RNH2 + R/COCl RNHCOR/ + HCl

(N–Alkyl amide)
R2NH + R/COCl R2NCOR/ + HCl
(N, N–Dialkylamide)
No – NH group
R3N No acylation.
Acid anlydrides react in a similar way as above.
(iv) With HNO2 (NaNO2 and cold dilute mineral acid)
R – NH2 + HONO R – OH + N2 + H2O

(10amine) (alcohol)
R2NH + HONO R2N– N = O + H2O

(20amine) (Nitrosoamine)
(Insoluble yellow oil)
heat NaOH
R2N–N=O + phenol + conc.H2SO4 Brown or Blue or Violet
red colour colour
(Liebermann’s nitroso reaction)
+ –
R3N + HNO2 R3NHNO2
Aryl primary amines, however, react with HNO2 to form arenediazonium salts.
(v) Carbylamine reaction : For 10 amines only.

heat
R–NH2 + CHCl3 + 3KOH RNC + 3KCl +3H2O
(alcoholic) (Carbylamine)
unpleasant odour
R2NH and R3N do not respond to this reaction.
(vi) With benzene sulphonyl chloride :
KOH Excess
R–NH2 + C6H5SO2Cl C6H5SO2NHR soluble
KOH
(10amine) (benzene sulphonamide)
KOH KOH
R2NH + C6H5SO2Cl C6H5SO2NR2 Insoluble
(20amine)
No reaction with 30amine
(vii) With aldehydes : Formation of Schiffs base.
+
H
R – NH2 + R/– CHO R – N = CH – R/ + H2O
(1 amine) (Schiff’s base)
(viii) Aryl amines undergo electrophlic substitution reactions.
NH2 NH2
X X
3X2
(a)
[X = Cl or Br]
X
2,4,6 - trihaloaniline
NH2 NH2
(b) Sulphonation
SO3H
NH2 NH2 NH2

NO2
(c) Nitration and
NO2
(d) C6H5NH2 Diazotisation [ C6H5 N N ]+X
(e) 10, 20, 30 Amines HNO 2 React differently

AMINES 667
4. Distinction between 10, 20 and 30 amines :
(i) By the action of nitrous acid :

10 amine alcohol + N2 gas. (except methylamine)
20 amine nitrosoamine responds to Liebermann nitroso reaction.
30 amine salt formation (dissolves in HNO2 solution).
Aryl primary amines form arenediazonium salts which couple with alkaline solution of
b- naphthol to red or orange colour azo dyes.
(ii) Alkylation :
10 amine takes up 3 moles of CH3I for quaternisation.

+ –
RNH2 + 3RI R4 N I

+ –
R2NH + 2RI R4 N I

+ –
R3N + RI R4 N I
(iii) Acylation:
10 amine RCOCl N–alkyl acid amide
20 amine RCOCl N, N–dialkyl acid amide
30 amine RCOCl No reaction.
(iv) Carbylamine reaction :

CHCl3
10 amine Isocyanide (unpleasant odour)
alc.KOH
20 amine No reaction
30 amine No reaction
(v) Hinsberg’s reagent (C6H5SO2Cl)
10 amine N–alkyl benzene sulphonamide. (soluble in alkali)
20 amine N, N–dialkyl benzene sulphonamide. (insoluble in alkali)
30 amine No reaction.
5. Separation :
A mixture of 10, 20 and 30 amines can be conveniently separated by Hinsberg’s method.
QUESTIONS
A. Short questions (one mark each)

1. Which of the following is basic ?
(a) CH3 CH2 OH (b) CH3 COOH
(c) CH3 NH2 (d) CH3 OCH3
2. Complete the following reaction and give the names of the products ?
CH3CH2NH2 + HNO2 ——— + —— ?
What happens when an alkyl cyanide is reduced by sodium metal in ethanol ?
3. Why aniline is soluble in aqueous HCl.
4. Write the IUPAC name for C6H5N (CH3)2
5. Identify the products in the following
(i) C6H5NO2 Sn/HCl
Raney Ni or Pt or Pd
(ii) C6H5NO2
H2
(iii) C6H5NH2 RX A RX B RX C (identify A, B & C)
(iv) C6H5NH2 Br2 water
(v) C6H5NH2 Sulphonation
(vi) C6H5NH2 Nitration

(vii) C6H5NH2 Diazotsation
(viii) C6H5NHCH3 HNO 2
(ix) C6H5N(CH3)2 HNO2
6. Fill in the Blanks :

(i) Benzyl amine is basic than aniline
(ii) Among the isomeric o- m- and p- anisidine is the weakest base.
(iii) The reaction of aniline with NaNO2 and HCl at 00 C to from benzenediazonium
chloride is called
(iv) Aniline on treatment with bromine water gives
(v) Tetra-alkyl ammonium salts are called
Answer : 1. (more), 2. (m-Anisidine), 3. (diazotisation), 4. (2,4,6 - tribromoaniline),
5. (quaternary ammonium salts)
AMINES 669
B. Short questions (Two marks each)

1. How will you prepare ethyl amine from methyl iodide ?
2. Give a method of preparation of primary amine.
3. Why methylamine is more basic than aniline ?
4. What is carbylamine reaction ? Give equation.
5. How will you obtain methanol from methyl amine ?
6. How can you get methylamine from ethylamine?
7. Give the IUPAC name of the following compounds:
(a) CH3CH2CH2NH2
(b) CH3NHCH2CH3
(c) (CH3)2CHNH2
(d) (CH3)3 C.NH2
(e) (CH3)2 NCH2CH2CH3
(f) CH3CH2CH (NH2) CH2CH3
8. Give the structural isomers of C3H9N and C4H11N and give their names. Classify each
as primary, secondary and tertiary amines.
9. Name the functional groups in the following compounds :- CH3CH2NH2 and CH3CONH2
10. What happens when nitromethane is reduced ?
11. Give a chemical test and reagents used to distinguish between ethylamine and diethylamine.
12. A compound molecular formula CH5N on treatment with HNO2 liberates a colourless
and odourless gas. What is the name of the compound and the gas liberated ? Write the
equation.
13. How you will distingush C2H5NH2 for C6H5NH2
14. What is carbylamine test?
15. Why aniline is less basic than ammonia?
16. Why ethyl amine is more basic than ammonia?
17. How will you carry out the conversion of benzene to p-nitroaniline ?
18. Direct nitration of aniline is not carried out at all. Explain why ?
19. Give an example of a Zwitterion.
+
[Ans. H3 N SO3– Sulphanilic acid]
C. Short questions (Three marks each) :

1. Arrange the following compounds in decreasing order of basicity, Give reason.
Methyl amine, dimethylamine, aniline, N-methyl aniline
2. How will you prove that amines are basic compounds ?
3. Distinguish between primary and secondary amines Give one test only with equation.
4. Complete the following equation and balance.
PCl5 KCN H3O+ NH3

C2H5OH A B C D
5. How will you prepare ethylamine from
(a) Methyl cyanide (b) Propanamide
6. Name a tertiary amine in IUPAC system which is isomeric with
CH3
|
CH3—C—NH2 and C2H5 – CH2 – CH2 – NH2
|
CH3
7. Describe a test to distinguish between aniline, N-methylaniline and N-ethyl-N-

methylaniline
8. How will you convert the following
(i) Benzene to aniline and (ii) Aniline to N,N-dimethylaniline ?
9. Write reactions of the final alkylation product of aniline with excess of methyl iodide in
the presence of sodium carbonate solution.
10. Write the chemical reaction of aniline with benzoyl chloride and mention the name of the
product.
11. Convert aniline to 1,3,5 – tribromobenzene.
12. Account for the following.
(i) Aniline is less basic than methylamine
(ii) p-Nitroaniline is less basic than aniline
(iii) p-Toluidine is more basic than aniline.
13. Describe a method for the identification of primary, secondary and tertiary amines.
14. Accomplish the conversion of aniline to p-bromoaniline.
15. Write the reactions of aromatic and aliphatic primary amines with nitrous acid.
16. How you will prepare benzonediazonium chloride?
17. How you will obtain 2,4,6-trichloroaniline from aniline ?
18. How will you convert nitrobenzene to (i) acetanilide and (ii) benzamide ?
AMINES 671
D. Long questions :
1. Give any two methods for the preparation of a primary amine. How does it react with
(a) HNO2 (b) CH3CHO (c) CH3COCl
2. Give any two methods for the preparation of a an aromatic primary amine. How does it
react with
(a) CH3COCl (b) HNO2
3. Write notes on :
(a) Hofmann reaction
(b) Hofmann bromamide reaction
(c) Hinsberg’s method for distriction of 1 0, 20 & 30 amines ?
4. What are amines ? Explain three types of aliphalic amines giving one example from each.
Write with equations how amines react with
(a) alkyl halide and (b) acid chloride
5. Give any two methods of preparation of primary amine. How does it react with CHCl 3
presence of alcoholic KOH?
6. What are different types of amines ? Give two methods for the preparation of primary
amine. How does it react with methyl iodide? C2H5NH2 is more basic than CH3NH2;
Explain.
7. What are different types of amines ? How primary amines are prepared from
(a) nitroparaffins (b) cyanides (c) alkyl halides ?
What happens when methylamine reacts with methyl iodide ?
8. What are different types of aliphatic amines? How aliphatic primary amines are prepared
from (i) acid amides, (ii) alkyl cyanides. What happens when methylamine reacts with
nitrous acid?
9. Describe the methods of preparation of aromatic monoamines, taking example of aniline.
Discuss the relative basic character of aniline and methyl amine Explain the weak basic
character of aniline.
10. Give the general chemical reactions of aryl amines.
11. How is aniline prepared on a laboratory scale ? Summarise its chemical reactions.
12. How is basicity of aniline affected by substituents on the benzene ring ? How do you
explain the ortho and para directive influence of –NH2 group ?
13. Explain the action of nitrous acid on primary, secondary and tertiary amines. How aniline
differs from methyl amine in its reaction with nitrous acid ?
14. How does aniline react with the following reagents ?
(i) Acetic anhydride, (ii) benzoylchloride (iii) Sodium nitrite / HCl.
15. How will you distinguish between aniline and benzylamine ?
How N, N-dimethylaniline is prepared ? How will you distinguish it from aniline ?
E. Multiple Choice Questions :

1. Most basic among the following is C6H5NH2, (C2H5)2 NH (C2H5)3 N, C2H5NH2
I II III IV
(a) I (b) II (c) III (d) IV
2. Which of the following compounds gives dye test ?
(a) Aniline (b) Methylamine (c) Diphenylamine (d) Ethylamine
3. In the following reaction, X is
Boiling
X Bromination Y NaNO2/HCl Z Tribromobenzene
C2H5OH
(a) Benzoic acid (b) Salicylic acid (c) Phenol (d) Aniline
4. The correct increasing order of basic strength for aniline (I), p-nitroaniline (II), and p-
toluidine (III) is.....
(a) II < III < I (b) III < I < II (c) III < II < I (d) II < I < III
5. In the nitration of benzene using a mixture of conc. H 2SO4 and conc. HNO3, the species
which initiate the reaction is.....
(a) NO2 (b) NO+ (c) NO2+ (d) NO2–
6. Reduction of nitrobenzene by which of following reagent gives aniline ?
(a) Sn/HCl (b) LiAlH4 (c) Zn/NH4OH (d) SnCl2
7. C6H5NO2 Sn/HCl C6H5X
In the above reaction ‘X’ is
+
(a) Cl (b) NH2 (c) NH3+Cl– (d) N2 Cl
8. Which of the following is the weakest Bronsted base ?
(a) NH2 (b) N– H (c) CH3 NH2 (d) CH2 – NH2
9. Which of the following will react with CH3COCl ?

(a) Trimethylamine (c) Dimethylethylamine
(b) Dimethylamine (d) Trimethylamine
10. Acetamide is treated separately with the following reagents. Which of these would give
methylamine?
(a) PCl5 (c) NaOH + Br2
(b) Sodalime (d) Hot Conc. H2SO4
11. Which of the following shows optical activity?
(a) Butanamine - 1 (c) Isopropylamine
(b) Butanamine - 2 (d) Ethylmethylamine
AMINES 673
12. Number of saturated isomeric primary amines possible for the molecular fomula C 3H5N is
(a) Zero (c) 2
(b) 3 (d) 4
13. Primary amines on reaction with alcoholic KOH yields :
(a) Isocyanide (c) Cyanide
(b) Aldehyde (d) Alcohol
14. The compound on reaction with aqueous HNO 2 at low temperature produces oily
nitrosoamine is
(a) Methylamine (c) Diethylamine
(b) Ethylamine (d) Triethylamine
Answer : 1. (b), 2. (a), 3. (d), 4. (d), 5. (c), 6. (a), 7. (c), 8. (a), 9. (b), 10. (c), 11. (b), 12. (a),
13. (a), 14. (c).
qqq
CHAPTER - 21
ARYL DIAZONIUM SALTS
When primary arylamines or their salts react with nitrous acid in ice-cold solution, an
important class of compounds called the diazonium salts are formed. They are so called, because
they contain diazo group –N N (Di means two, azo from French word azote, meaning nitrogen).
+ –
These salts have the general formula Ar N 2 X where Ar is an aryl group ( e.g. benzene ring)
– – – –
and X is any anion like Cl , Br , HSO 4 etc. Structurally, they may be represented as
[Ar – N N:] X
and are named by adding diazonium to the parent aromatic compound to which they are related,
followed by the name of the anion. For example –
+
–
N N Cl is benzenediazonium chloride,
|
+
–
H3C N N Br is p-toluenediazonium bromide etc.,
|
21.1 PREPARATION OF BENZENEDIAZONIUM CHLORIDE :

Aniline is dissolved in dil. hydrochloric acid and the solution is cooled to 0 0 – 50C.
Aqueous solution of sodium nitrite is added to the cooled solution in small portions with stirring.
The temperature is maintained at 0 0 – 50C. Addition of sodium nitrite solution is discontinued
when a drop of the solution turns starch-iodide paper blue indicating the presence of slight excess
of nitrous acid. Benzenediazonium chloride is formed in the solution.
0 0
0 –5 C
NaNO2 + HCl NaCl + HNO2
0 0
+ –
C6H5 – NH2 + HNO2 + HCl 0 – 5 C C6H5 N2 Cl + 2H2O
(Aniline) (Benzenediazonium chloride)
This reaction between a primary arylamine and nitrous acid in presence of a mineral
acid to produce aryldiazonium salt is called diazotisation. Nitrous acid is unstable and it is
always generated in situ from NaNO2 and mineral acid like HCl or H2SO4. The reaction is carried
0 0
out at a low temperature (0 – 5 C), because both nitrous acid and diazonium salt would decompose
at higher temperature.
ARYL DIAZONIUM SALTS 675
21.2 PROPERTIES :
Physical : Dry aryldiazonium salts are unstable crystalline solids and readily explode when in
dry state liberating nitrogen gas. Therefore, they are not isolated and are used in the
solution in which they are prepared.
Chemical : Aryldiazonium salts are very reactive and undergo a large numbers of substitution
reactions in which the diazo group is replaced by different univalent atoms or groups.
These are all unimolecular nucleophilic substitution reactions. (SAr N1)
H2O
Ar OH
slow + fast X Ar X
Ar N2X Ar – N2 + X Ar
– N2
CN
Ar CN
i. Replacement by hydrogen : Synthesis of benzene :
When benzene diazonium salt solution is treated with hypophosphorus acid, the diazo
group is replaced by hydrogen and benzene is formed.
+ _
C6H5N2 Cl + H3PO2 + H2O C6H6 + H3PO3 + HCl + N2
(Benzenediazonium chloride) (Benzene)
The reaction is carred out simply by dissolving the amine in hypophosphorus acid and
cold NaNO2 solution is added. The reaction takes place immediately. The net result is removal of
NH2 group from the aromatic ring and hence the process is known as de-amination. Nitro group
can also be removed after converting it to – NH 2 group.
ii. Replacement by halogens : Synthesis of chlorobenzene, bromobenzene and

iodobenzene
Sandmeyer’s Reaction : When benzenediazonium chloride solution is added to a solution of

cuprous chloride dissolved in HCl or cuprous bromide dissolved in HBr, the diazo group is
replaced by chlorine or bromine respectively resulting in the formation of chlorobenzene or
bromobenzene.
+ _ CuCl, HCl
C6H5 N2 Cl C6 H5 Cl + N2
(Chlorobenzene)
_ CuBr, HBr
C6H5 N+
2
Cl C6 H5 Br + N2
(Bromobenzene)
The reaction is known as Sandmeyer’s reaction. Gatterman used a modified method in

which cuprous halides were replaced by copper powder to prepare chlorobenzene and
bromobenzene. The reaction is known as Gattermann reaction.
+ – Cu-powder
C6H5 N2 Cl C6 H5– Cl + N2
HCl
(Chlorobenzene)
+ Cu-powder
C6H5 N2 Br– C6 H5– Br + N2
HBr
(Bromobenzene)
The best method for introducing iodine atom in benzene nucleus is to add a saturated
solution of potassium iodide to benzene diazonium chloride solution. It is not necessary to add
copper salt.
+ –
C6H5 N2 Cl + KI C6 H5– I + N2 + KCl
(Iodobenzene)
iii. Replacement by cyano group:Synthesis of cyanobenzene or benzonitrile or phenyl

cyanide
When diozonium salt solution is treated with cuprous cyanide dissolved in aqueous
potassium cyanide, the diazo group is replaced by –CN group and aryl cyanide is formed. This is
also called Sandmeyer’s reaction. Benzene diazonium chloride with cuprous cyanide in aqueous
KCN yields phenyl cyanide or cyanobenzene.
+ _ CuCN, KCN
C6H5 N2 Cl C6 H5 – CN + N2
(Phenyl cyanide or
cyanobenzene)
This is a method for introducing – CN group and hence – CH2 – NH2 and – COOH
groups in the benzene nucleus (how?)
H2 / Ni H2 O/ H+
C6H5 CH2 NH2 C6 H5–CN C6H5–COOH
Benzylamine Phenyl cyanide Benzoic acid
SnCl2 / Conc. HCl
C6H5–CHO
(Benzaldehyde)
iv. Replacement by hydroxyl group : Synthesis of phenol

When benzenediazonium salt solution is boiled with water containing dil H 2SO4, it
undergoes hydrolysis and diazo group is replaced by – OH group. Phenol is formed.
+ [H+]
C6H5 N2 Cl + H2O C6 H5 — OH + N2 + HCl
boil
(Phenol)
v. Replacement by fluorine : Synthesis of fluorobenzene
When an aqueous solution of a diazonium salt is treated with fluoroboric acid (HBF 4),
diazonium fluoroborate gets precipitated. It is filtered and dried. Unlike other diazonium salts,
diazonium fluoroborates are fairly stable. When dry diazonium fluoroborate is heated, it composes
to aryl fluoride and boron trifluoride.
ArN2+Cl– + HBF4 ArN2+ BF4– + HCl
Diazonium fluoroborate
+ D Ar – F + N2 + BF3
Ar N NBF4
Aryl fluoride
This reaction is known as Balz - Schiemann reaction.
vi. Replacement by nitro (–NO2) group : Synthesis of nitrobenzene.
Nitro compounds are generally prepared by treating an arenediazonium fluoroborate with
an aqueous solution of sodium nitrite in presence of copper powder.
+ +
N NCl N NBF4 NO2
+ HBF4 NaNO2 / Cu + N2 + NaBF4

HCl
D
Benzenediazonium Benzenediazonium Nitrobenzene
chloride fluoroborate
vii. Coupling reactions :

Arene diazonium salts react with electron rich (highly reactive) aromatic compounds such
as phenols and amines to form brightly coloured azo compounds, Ar – N = N – Ar. This reaction
is known as Coupling reaction. Azo compounds are used as dyes.
Coupling takes place almost exclusively at the para position if it is unoccupied. If it is not,
then coupling takes place at ortho position. Coupling with phenols occurs in basic medium (pH
9-10) whereas with amines it occurs in faintly acidic medium (pH 4 – 5) at 273 – 278 K.
+ Base
N NCl + H – OH N=N OH + HCl
273-278K
Benzenediazonium Phenol p-Hydroxyazobenzene
chloride
OH OH
+ Base N=N
N NCl + 273-278K + HCl
CH3 CH3
p-cresol 2-phenylazo-4-methylphenol
(Para position occupied)
+ CH3 CH3
C6H5 – N NCl + H N C6H5 – N = N N
CH3 CH3
(Butter yellow) + HCl
p-N,N-Dimethylazobenzene
Azo dyes almost always contain one or more than one SO3– Na+ groups so that they are soluble in
water.
+ + CH3
NaO3S N NCl + H N
CH3
+ CH3
NaO3S N=N N
CH3
Methyl orange
21.3 SOME IMPORTANT CONVERSIONS :
1. Toluene to m- nitrotoluene
CH3 CH3 CH3 CH3
Nitration Reduction CH3COCl

–
Sn / HCl OH
(Toluene) NH2 NHCOCH3
NO2
CH3 CH3 CH3
Nitration hydrolysis NaNO2 / HCl

NO2 NO2 O0C NO2
_
NHCOCH3 NH2 N2Cl
CH3
H3PO2
NO2
H2O
m- nitrotoluene
2. Benzene to 1, 3, 5 - tribromobenzene
NO2 NH2 NH2

Br Br
Nitration Sn / HCl Br2/H2O
(Benzene) (Nitroben- (Aniline) Br

zene)
+ _
N2Cl
Br Br Br Br
NaNO2/HCl H3PO2
00C H2O
Br Br
(1, 3, 5 - tribromobenzene)
3. Toluene to p-hydroxybenzoic acid
CH3 CH3 COOH COOH

Nitration oxdn Sn
Na2 Cr2O7 / H2SO4 HCl
(Benzene) NO2 NO2 NH2
COOH COOH
NaNO2/HCl H2O/H
0
0C boil
N2Cl OH
(p- hydroxybenzoic acid)
4. Benzene to m-bromophenol
NO2 NO2 NH2
Nitration Br2/Fe Sn/HCl NaNO2/ HCl

Br Br 00C
(Benzene) (nitrobenzene)
_
N+2Cl OH
H2O / H+
Br
Br
(m-bromophenol)
5. Aniline to p-toluidine
NH2 NHCH3 NH.CH3HCl NH2
CH3Cl HCl heat
(Aniline)
CH3
(p-toludine)
6. p - Toluidine to m - bromotoluene
CH3 CH3 CH3
Acetylation Br2
Br
NH2 NHCOCH3 NHCOCH3

(p- toluidine)
CH3
i. H3+O
ii. NaNO2 / H+ Br
iii. H3 PO2 (m- bromotoluene)

Methods of Preparation
NaNO2/HCl +
C6H5 NH2 C6H5 N NCl
273-278K
Synthetic applications (Properties)
H3PO2+H2O
ArH
CuCl, HCl or
Ar – Cl or Ar – Br Sandmeyer’s reaction
CuCl, HBr
+ HX Ar – X [X = Cl or Br]
Ar N Cu
Gattermann reaction
KI Ar – I
CuCN, KCN Ar – CN
H2O, D
Ar – OH
HBF4 /D
Ar – F Schiemann reaction
(i) HBF4
Ar – NO2
(ii) NaNO2, Cu
Phenol
Ar – N = N OH
Coupling (Basic)
Aniline
Ar – N = N NH2
(Acidic)
QUESTIONS
A. Short Answer questions : (1 mark)
1. Write the structure of benzenediazonium chloride.
2. Why benzenediazonium salts are soluble in water ?
3. What should be the nature of medium (neutral/acidic/basic) for diazotisation of arylamines.
4. Give only the equations for the synthesis of the following from benzenediazonium chloride.
(i) Benzene (ii) Phenol (iii) Chlorobenzene (iv) Fluorobenzene (v) Phenyl cyanide
(vi) p-Hydroxyazobenzene
B. Short Answer Questions (2 marks)
1. Suggest reasons why excess mineral acid is used in diazo reaction.
2. Complete the following equations
(i) C6H5N2Cl + H3PO2+H2O
(ii) C6H5N2Cl (i) HBF4

(ii) NaNO2/Cu, D
(iii) C6H5N2Cl + H2O D

CuCl
(iv) C6H5N2Cl
HCl
(v) C6H5OH ArN+2Cl
OH
ice cold
(vi) C6H5N2Cl + ArNH2
pH 4-5
3. Give the chemical equation for the following.
(i) Diazotisation reaction
(ii) Coupling reaction
(iii) Sandmeyer reaction
4. How will you convert ?
(a) Aniline to nitrobenzene, (b) Aniline to iodobenzene
C. Short Answer Questions (3 marks)
1. Why the diazonium salts of aromatic amines are more stable than those of aliphatic amines ?
2. How you will obtain p-hydroxyazobenzene from aniline ?
3. What is coupling reaction ? give two examples.
4. How will you carry out the conversion of aniline to m-bromonitrobenzene ?
5. Give the structure of A, B and C in the following reactions.
CuCN H2O/H
+
NH3
(i) C6H5N2Cl A B C
Fe/HCl HNO2 C6H5OH
(ii) C6H5NO2 A B C
273-278K
D. Long Answer Questions
1. Discuss in detail the preparation of benzenediazonium chloride from aniline. Why it is not
separated in solid state and used as soon as produced in solution ? How can you convert
benzenediazonium chloride to fluoro and iodobenzene.
2. Describe the synthetic applications of aryl diazonium salts.
3. How will you obtain
(a) Iodobenzine from nitrobenzine
(b) m-Dichlorobenzene from benzene
4. How will you synthesise the following ?
(a) Azobenzene from benzene
(b) Benzene from azobenzene
(c) Azobenzene from nitrobenzene
(d) Nitrobenzene from azobenzene
5. Write notes on :
(a) Sandmeyer reaction
(b) Coupling reaction
6. How can benzene diazonium chloride be prepared from nitrobenzene ? Starting from a
diazonium salt how can you prepare (a) iodobenzene (b) benzoic acid ?
E. Multiple Choice Questions

1. The diazonium salts are the reaction products of the reaction of nitrous acid with
(a) primary aliphatic amines (b) primary aromatic amines
(c) secondary aliphatic amines (d) secondary aromatic amines
2. Preparation of a diazonium salt from a primary aromatic amine is known as :
(a) Coupling reaction (b) Sandmeyer reaction
(c) Diazotisation (d) Corey-House synthesis
3. Which of the following reagents is used to prepare benzenediazonium chloride from aniline ?
(a) NaN02 + HC1 (b) LiAlH4
(c) NH2NH2 + KOH (d) NaOH
4. Which of the following are optimum temperature conditions for making benzonediazonium
chloride from aniline ?
(a) 0°C to 10°C (b) 20°C to 25°C
(c) 30°C to 40°C (d) 45°C to 50°C
5. Benzenediazonium chloride reacts with warm water to give

(a) Aniline (b) Phenol
(c) Benzene (d) Chlorobenzene
6. Bromobenzenes can be prepared by treating aniline with
(a) Conc. HBr (b) Br2/FeBr3
(c) CuBr (d) Nitrous acid then CuBr
7. Chlorobenzene can be prepared by treatment of aniline with
(a) Cuprous chloride
(b) Chlorine in the presence of UV light
(c) Nitrous acid followed by treatment with CuCl
(d) Chlorine in the presence of FeCl3.
8. lodobenzene can be prepared by
(a) treating chlorobenzene with I2 using FeCl3 catalyst.
(b) treating phenol with I2 in NaOH solution.
(c) treating benzenediazonium chloride with KI
(d) treating benzene with CH3I using A1C13 catalyst.
9. Benzene diazonium chloride reacts with Kl to form :
(a) Benzene diazonium iodide (b) m-Diiodobenzene
(c) lodobenzene (d) o-, plus p-Diiodobenzene
10. What is the major product of the following reaction ?
NH2
NaNO2 CuCN
HC1, 0°C
(a) Benzonitrile (b) Benzoic acid

(c) Nitrobenzene (d) Benzene diazonium chloride
11. Benzene diazonium chloride reacts with hypophosphorus acid to form :
(a) Phenol (b) Benzaldehyde
(c) Aniline (d) Benzene
12. Benzene diazonium chloride reacts with phenol to form :
(a) p-chlorophenol (b) Chlorobenzene
(c) p-Hydroxyazobenzene (d) DDT
ANSWERS
1. (b) 2. (c) 3. (a) 4. (a) 5. (b) 6. (d) 7. (c) 8. (c) 9. (c) 10. (a) 11. (d) 12. (c)
qqq
BIOMOLECULES 685
UNIT - XIV
CHAPTER - 22
BIOMOLECULES
22.1 INTRODUCTION :
The branch of Chemistry dealing with the structure, composition and the chemical changes
which take place in the living system is called biochemistry. Living cells, the fundamental unit
of life are composed of some complex biologically important organic molecules otherwise termed
as biomolecules. Important biomolecules constituting the ultimate structure of living cells are
carbohydrates, fats, proteins, lipids, nucleic acids etc. In this chapter elementary ideas on such
biomolecules are described in brief which are related to the living organism in the following
sequence.
Living organisms ® Organs ® Tissues ® Cells ® Organelles ® Biomolecules.
22.2 CARBOHYDRATES :
Introduction : The glucose, cellulose, starch and glycogen, all belong to the class of
organic compounds known as carbohydrates. Carbohydrates are the main source of energy for
our body in the form of food. The carbohydrates provide us with three necessities of life, that is
food, clothing and shelter.
The term “carbohydrate” was originally given to the compounds with general formula,
Cx(H2O)y where x and y may be same or different and they were considered to be hydrates of
carbon. However, this definition could not hold ground for long due to following reasons:
(i) Compounds like formaldehyde (HCHO), acetic acid (CH3COOH) etc. have the general
formula Cx(H2O)y, but they do not show the characteristic properties of carbohydrates.
(ii) Some carbohydrates, such as deoxyribose (C5H10O4) do not have the required ratio of
hydrogen to oxygen.
To accommodate wide variety of compounds, the carbohydrates are now-a-days broadly
defined as polyhydroxy aldehydes or ketones and their derivatives or as substances that yield one
of these compounds on hydrolysis.
A. CLASSIFICATION OF CARBOHYDRATES :
I. CLASSIFICATION ON THE BASIS OF HYDROLYSIS PRODUCTS :
Carbohydrates are classified into following classes depending upon their behaviour towards
hydrolysis.
(i) Monosaccharides
(ii) Oligosaccharides
and (iii) Polysaccharides.
(i) Monosaccharides : (Greek: Mono = one; Sakcharon= sugar):
Monosaccharides are simple sugars and can not be hydrolysed to still simpler compounds.
Monosaccharides contain 3 to 7 carbon atoms each. Monosaccharides are generally sweet to
taste, soluble in water and crystalline.
Monosaccharides may be further subdivided into trioses, tetroses, pentoses, hexoses,
heptoses etc. depending upon the number of carbon atoms they possess.
Monosaccharides which contain an aldehyde (–CHO) group are called aldoses. Since the
aldehyde group is monovalent, it is present at one end of the carbon chain. Similarly,
monosaccharides which contain a keto group are called ketoses. As keto group is divalent, it is
present anywhere along the chain. In all, the naturally occurring ketoses, keto group is present at
the carbon atom next to the terminal carbon, that is, at C–2.
Some important examples of monosaccharides are :
Name Formula Aldoses Ketoses

(Aldo Sugars) (Keto Sugars)
Trioses C3H6O3 Glycerose Dihydroxyacetone
Tetroses C4H8O4 Erythrose Erythrulose
Pentoses C5H10O5 Ribose Ribulose
Hexoses C6H12O6 Glucose Fructose
Heptoses C7H14O7 Glucoheptose Sodoheptulose
Both these characters, that is, number of carbon atom and the nature of functional group
may also be combined into one. For example, glucose is an aldohexose and fructose is a ketohexose
BIOMOLECULES 687
CHO CH2OH
| |
H—C—OH C=O
| |
HO—C—H
| HO—C—H
H—C—OH |
| H—C—OH
H—C—OH
| |
CH2OH H—C—OH
|
Glucose (Aldohexose) CH2OH
Fructose (Ketohexose)
(ii) Oligosaccharides : (Greek : Oligos = a few):

There are carbohydrates which on hydrolysis give two to ten molecules of the same or
different monosaccharides on hydrolysis.
Depending upon the number of monosaccharide molecules obtained on hydrolysis, they
are further classified as di, tri, tetrasaccharides etc.
(a) Disaccharides : These carbohydrates on hydrolysis give two molecules of
monosaccharides. The general formula of disaccharides is C n(H2O)n–1
The exmaples of disaccharides are sucrose, lactose, maltose, cellobiose etc.
(b) Trisaccharides : These carbohydrates on hydrolysis give three molecules of
monosaccharides.
For example, raffinose, C18H32O16.
(c) Tetrasaccharides : These carbohydrates on hydrolysis give four molecules of
monosaccharides. Example : Stachyose, C24H42O21.
(iii) Polysaccharides : (Poly = many) :
These are carbohydrates which on hydrolysis give a large number of monosaccharide
molecules. The most commonly occurring polysaccharides are starch, glycogen, cellulose
and gums. Their general formula is (C6H10O5)n where n = 100 to 3000.
II. Sugars and Non-sugars :
Carbohydrates can be classified on the basis of their taste as follows :
(a) Sugars :
All the monosaccharides and oligosaccharides are crystalline solids, soluble in water and
sweet in taste and hence are termed as sugars.
(b) Non-sugars :
Polysaccharides are amorphous in nature, insoluble in water and tasteless and hence are
called non-sugars.
III. Reducing and Non-reducing sugars :
On the basis of the reducing character of carbohydrates, they can be classified into two
types.
(a) Reducing sugars :
All those carbohydrates which contain free aldehydic or ketonic group, thus reducing
Tollen’s reagent and Fehling’s solution are called reducing carbohydrates or sugars.
Examples are glucose, fructose, maltose, lactose.
(b) Non-reducing sugars :
Those carbohydrates which are incapable of reducing Tollens’ reagent or Fehling’s solution
are called non-reducing sugars. Examples : sucrose.
B. FUNCTIONS OF CARBOHYDRATES :
Carbohydrates have a number of diverse functions in the living organisms. These are,
(i) Structural material : The chief structural material in the cell walls of all plants are cellulose,
which is a polysaccharide. We make furnitures from cellulose in the form wood and
clothe ourselves with cellulose in the form of cotton fibre. Cellulose is the raw material
for industries like textiles, paper etc.
(ii) Reserve food materials: Some polysaccharides act as reserve food materials for plants
and animals. For example, starch is a major food reserve in plants. In seeds, starch acts as
a reserve food material for the tiny plant till it is capable of preparing its own food by the
process of photosynthesis. Similarly, in animals glycogen acts as a reserve food material,
which is present in liver cells. Glycogen is a source of glucose for the blood.
(iii) As a biofuel : Carbohydrates, such as glucose, fructose, starch, glycogen etc. provide
energy for the functioning of living organisms and act as a biofuel. In the living systems,
polysaccharides such as starch and glycogen present are hydrolysed by enzymes to glucose.
Glucose is then transported to the various cells, where it is oxidised to CO 2 and H2O by
a series of enzyme catalysed reactions. The energy thus released during oxidation, provides
energy for the functioning of cells.
C6H12O6 + O2 6CO2 + 6H2O + energy.
(glucose)
(iv) In nucleic acids : Monosaccharides like ribose and 2-deoxyribose are the essential
components of RNA and DNA respectively. Nucleic acids play an essential role in the
biosynthesis of proteins.
BIOMOLECULES 689
C. MONOSACCHARIDES
1. GLUCOSE
Glucose, the most common monosaccharide is also known as Dextrose because it occurs
in nature as the optically active dextrorotatory isomer. Glucose is found in most of the sweet
fruits especially grapes and honey.
(a) Preparation :
(i) From starch :
Glucose is produced commonly by the hydrolysis of starch with dilute hydrochloric
acid at high temperature under pressure. atm
HCl
(C6H10O5)n + n H2O n C6H12O6
393K, 2 - 3 atm
Starch Glucose
(ii) From sucrose :
Sucrose i.e. cane sugar on acid hydrolysis produces an equal amounts of glucose
and fructose.
H+
C12H22O11 + H2O C6H12O6 + C6H12O6
D
Sucrose Glucose Fructose
(a) Structure of Glucose :
The structure of glucose can be elucidated basing on its following characteristics
I. Open Chain Structure of Glucose :
(i) Molecular formula : Elemental analysis and molecular weight determination have
established the molecular formula of glucose to be C 6H12O6
(ii) Presence of 6-carbon unbranched chain : The complete reduction of glucose
with concentrated hydrogen iodide and red phosphorus gives n-hexane proving
that glucose molecule is made of an unbranched i.e. a straight chain of six carbon
atoms.
Conc. HI/Red P
C6H12O6 CH3 – CH2 – CH2 – CH2 – CH2 – CH3
D
Gluclose n-Hexane
(iii) Presence of 5-OH groups : Glucose forms a pentacetyl derivative when refluxed
with acetic anhydride showing the presence of five hydroxyl groups. Since it is a
stable compound, no two - OH groups are attached to the same carbon and hence
the five -OH groups are on different carbons.
Reflux
C6H12O6 + 5 (CH3CO)2O ¾¾ ¾¾® C6H7O (OCOCH3)5 + 5 CH3COOH
Glucose Glucose penta-acetate
(iv) Presence of C = O Group : Presence of a carbonyl group in glucose is proved by

the following observations.
(1) With HCN, it forms an addition product, called glucose cyanohydrin.
C6H12O6 + HCN C5H111O5CH (OH) CN
Glucose Glucose cyanohydrin
(2) It forms an oxime with hydroxylamine.
H+
C6H12O6 + NH2OH C5H111O5CH = NOH + H2O
Glucose Glucoxime
(v) Presence of – CHO (aldehyde) group : On mild oxidation with bromine water,
glucose is converted to gluconic acid which when reduced with excess of HI yields
n-hexanoic acid.
(O) HI
C5H11O5 × CHO C5H111O5 × COOH CH3 (CH2)4 COOH
Br2(aq)
Glucose n-Hexanoic acid
This shows that glucose contains a straight chain of six carbon atoms with – CHO
at one end, which has been oxidised to – COOH
(vi) Presence of a primary alcoholic group (–CH2OH) : On heating with nitric acid,
glucose forms dicarboxylic acid (glucaric acid) with the same number of carbon
atoms confirming the presence of a terminal primary alcohol group.
HNO3
OHC – (CHOH)4 – CH2OH ¾¾ ¾¾ ® HOOC – (CHOH)4 – COOH
Glucose Glucaric acid
(vii) Open chain structure of glucose : Basing on the above observations the open
chain structure of glucose can be represented as :
CHO
|
*CH (OH)
|
*CH (OH)
|
*CH (OH)
|
CH2OH
The above structure having four chiral carbon atoms correspond to 16 ( = 2 4) optically
active isomers, out of which one isomer is Glucose.
II. Configuration of Glucose :
Basing on its preparation from lower aldose and its properties Fischer put forth the exact
arrangement of different –OH groups in space around the chiral centres and the open chain structure
of glucose with correct canfiguration can be reprsented as :
BIOMOLECULES 691
CHO
|
H — C — OH
|
HO — C — H
|
H — C — OH
|
H — C — OH
|
CH2OH
D (+) Glucose
Here D stands for configuration, where as (+) represents the dextrorotatory nature of
glucose. This open chain structure is able to explain all the above reaction.
CH3–CH2–CH2–CH2–CH2–CH3
n–Hexane
,D
CHO
dP | O
/ Re (CH–O–C–CH3)4
HI O
|
CHO O CH2O–C–CH3
AC 2
| Glucose penta acetate
H — C — OH
|
HO — C — H CN
| HCN |
H — C — OH CH–OH
| |
H — C — OH (CHOH)4
| |
CH2OH NH CH2OH
2 OH Glucose cyanohydrine
D (+) Glucose
CH=N–OH
|
Br 2
(CHOH)4
(a
q)
|
HN
CH2OH
O3
Glucoxime
COOH
|
(CHOH)4
|
CH2OH
COOH Gluconic acid
|
(CHOH)4
|
COOH
Glucaric acid
III. Evidence against open chain structure :

The open chain structure of glucose explains most of the properties, but unable to explain
the followings
(i) It does not react with NaHSO3 and also with ammonia, although it contains a free–CHO
group.
(ii) Penta acetyl derivative of glucose is not oxidized by Tollen’s reagent or Fehling’s solution,
indicating the absence of free –CHO group.
(iii) Two stereo isomeric forms (a- and b-) are found to exist with different value of specific
rotation. Crystallization from alcohol produces a- Glucose (+110°) whereas from pyridine
results with b- Glucose (+19°). This behaviour could not be explained by open structure.
(iv) Mutarotation : The phenomenon involving spontaneous change in specific rotation of
the aqueous soluton of an optically active compound without any change in other properties
is known as muta-rotation.
Muta rotation is observed in glucose. The optical rotation of the aqueous solution of a-
Glucose (+110°) and b- Glucose (+19°) change gradually with time till finally a constant
value of +53° is reached, which represents the state of equilibrium between a-D-glucose
and b-D-glucose.
a-D (+) Glucose Equilibrium mixture b-D (+) Glucose
[a]D = + 110° [a]D = + 53° [a]D = + 90°
IV. Cyclic structure of D-Glucose :
Failure of open chain structure to explain some of the important characeristics of glucose
suggests that the –CHO gr is not free, rather it combines with one of the –OH grs to form a cyclic
hemiacetal structure. The stable cyclic structure expected is either a six-membered ring (pyranose
structure) or a five-membered ring (furanose structure), out of which the pyranose structure for
glucose is confirmed explaining the existence of two cyclic forms in equilibrium with open chain
structure.
1*CHOH
|
H—2C—OH
|
HO—3C—H O
|
H—4C—OH
|
Furan Pyran H—5C
|
6 CH2OH
Pyranose structure of glucose

BIOMOLECULES 693
During hemiacetal formation C1 - aldehydic group combines with C5 – OH group resulting

with a chiral centre at C1 and thus it has two possible arrangements of H and OH groups around
it. Hence D-glucose exists in two stereoisomeric forms i.e. a-D-glucose and b-D-glucose. Such
pair of stereoisomers which differ in configuration only around C 1 are called anomers and C1
carbon is called anomeric carbon.
O
||
H—1C—OH H—C HO—1C—H
| | |
H—2C—OH O H—C—OH H—2C—OH O
| | |
HO—3C—H HO—C—H HO—3C—H
| | |
H—4C—OH H—C—OH H—4C—OH
| | .. |
H—5C H—C—OH.. H—5C
| | |
6CH OH CH2OH 6CH OH
2 2
a-D- (+) Glucose D (+) Glucose b-D- (+) Glucose

(Open chain form)
The cyclic pyranose structure of glucose can be more correctly represented by Haworth
structures as shown below.
CH2OH 6CH OH CH2OH

2
O 5 OH O
..
H H H H H H H H OH
1 4 C=O 1
OH OH H OH OH OH H 1 OH OH H H
3 2
H OH H OH H OH
a-D- (+) Glucose D (+) Glucose b-D- (+) Glucose

(Open chain form)
2. FRUCTOSE
Fructose, the important ketohexose is otherwise termed as levulose bcause the naturally
occurring form of fructose is laevorotatory. It is found along with glucose in the juices of ripe
fruits and in honey. In the combined state it occurs in sucrose.
(a) Preparation
Fructose is obtained from sucrose (cane sugar by warming with dilute sulphuric acid or
with enzymes inverstase.
H2SO4
C12H22O11 + H2O C6H12O6 + C6H12O6
or invertase
Sucrose Fructose Glucose
(a) Structure of fructose :
I. Open Chain Structure of fructose :
(i) Molecular formula : As per elemental analysis and molecular weight determination,
the molecular formula of fructose is C 6H12O6.
(ii) Presence of a straight chain of six carbon atoms : On complete reduction with
HI and red P, it forms n-Hexane thus proving the presence of a straight chain of six
carbon atoms.
(iii) Presence of 5 –OH groups : It gives pentaacetyl derivative on reaction with acetic
anhydride indicating the presence of five hydroxy groups, each being attached to a
separate carbon as fructose is a stable compound.
(iv) Presence of carbonyl ( C = O) group : On oxidation with nitric acid fructose
forms a mixture of trihydroxy glutaric aicd, tartaric acid and glycollic acid, all
containing fewer carbon atoms than six. Thus, the carbonyl group is fructose must
be ketonic.
(vi) Carbonyl is on C-2 : Fructose forms cyanohydrin which upon hydrolysis and
subsequent reduction with HI and red P yields 2-methylhexanoicacid. Since the
COOH has appeared in place of CN, it is bonded to C-2 in the cyanohydrin
confirming the position of carbonyl group at position 2 on the six carbon chain.
1CH OH 1CH OH CH2OH CH3
2 2
| | | |
2C = O 2C CN C
COOH 2 CHCOOH
¾HCN
¾¾¾® HO
¾¾2¾® | OH
[H]
¾¾¾® |
| | OH
(CHOH)3 (CHOH)3 (CHOH)3 (CH2)3
| | | |
6CH OH 6CH OH 6CH OH 6CH
2 2 2 3
Fructose Cyanohydrin 2-Methylhexanoic acid

(vii) Open-chain structure : From the above observations, the open chain structure of
fructose can be represented as :
1CH OH
2
|
2C = O
|
3*CHOH
|
4*CHOH
|
5*CHOH
|
6*CH OH
2
This structure has three chiral centres with 8 ( = 2 3) optically active forms out of
which one is D (–) fructose.
BIOMOLECULES 695
II. Configuration of Fructose :

In the presence of excess phenyl hydrazine fructose forms the osazone which is identical
with that obtained from glucose. This shows that the configuration of asymmetic carbon atoms
C–3, C–4 and C–5 in D-fructose is the same as in D-glucose. Thus,
CHO CH = NNHC6H5 CH2OH

| | |
H—C—OH C = NNHC6H5 C=O
| Excess | Excess |
HO—C—H C H NHNH2 HO—C—H C H NHNH 2 HO—C—H
| ¾¾6 ¾5 ¾ ¾ ¾
¾® | ¬¾6¾5¾ ¾ ¾ ¾¾ |
H—C—OH H—C—OH H—C—OH
| | |
H—C—OH H—C—OH H—C—OH
| | |
CH2OH CH2OH CH2OH
D - Glucose Osazone D-fructose

Open chain structure
with correct
III. Evidence against open chain structure : configuration
Open chain structure of fructose fails to explain the following :
(i) It does not form addition product with NaHSO3, although it contains a ketonic
group.
(ii) Since an aqueous solution of fructose shows the properties of mutarotation, it shows
the existence of two stereo-isomers of fructose (a and b varieties)
(iii) The a - and b - isomers of fructose are also confirmed as it forms two stereo-
isomeric methyl fructosides.
IV. Ring or cyclic structure of fructose :
To explain the objection led against open chain structure, a five membered cyclic structure
i.e. furanose structure was proposed for fructose which is confirmed.
HOH2C—C—OH CH2OH HO—C—CH2OH

| | |
HO—C—H O C=O HO—C—H O
| | |
H—C—OH HO—C—H H—C—OH
| | |
H—C H—C—OH H—C
| | .. |
CH2OH H—C—OH .. CH2OH
|
CH2OH
a-D- (–) Fructofuranose Open chain structure b-D- (–) Fructofuranose
of D (–) Fructose
The furanose structures can be better represented by Haworth structures.
..
O OH
.. O
HOH2C CH2OH HOH2C
C
CH2OH
H H HO OH H H HO
OH H OH H
a-D- (–) Fructofuranose Open chain structure

of D (–) Fructose
O
HOH2C OH
H H HO CH2OH
OH H
b-D- (–) Fructofuranose
D. DISACCHARIDES
Disaccharides (C12H22O11) are carbohydrates that produce two monosaccharides on acid
hydrolysis.
H O/H+
Sucrose ¾¾2¾ ¾¾® Glucose + Fructose
H O/H+
Maltose ¾¾2¾ ¾¾® 2 Glucose
H O/H+
Lactose ¾¾2¾ ¾¾® Glucose + Galactose
Disaccharides are composed of two units of monosaccharides joined by a glycosidic linkage
with the elimination of a water molecule.
I. SUCROSE :
Sucrose is ordinary table sugar obtained from cane sugar.
(i) Sucrose is composed of a-D-glucose and b-D-fructose unit being joined by a, b - glycosidic
linkage between C–1 of the glucose unit and C–2 of the fructose unit.
BIOMOLECULES 697
6 CH OH CH2OH
2
5 O O
H H H H H H
4 1 1
OH OH H
OH OH OH H
3 2
H OH – H2O H OH a, b - linkage
a-D- Glucose
O
6
HOCH2 O OH HOCH2 O
5 2 2
H H HO CH2OH H H HO CH2OH
1
4 3
OH H OH H
b-D- Fructose Sucrose
(ii) The structure of sucrose explains the following characteristics.

(a) Sucrose does not form an osazone with phenyl hydrazine.
(b) It does not reduce Tollens’ reagent or Fehling’s solution.
(c) It does not exhibit mutarotation.
(iii) Sucrose is dextrorotary but after hydrolysis gives dextrorotary glucose (+52.5°) and
laevorotatory fructose (– 92.4°) and hence the mixture is laevorotatory. Thus hydrolysis
of sucrose is associated with change in the sign of rotation, for which the product is
termed as invert sugar.
+
C H O
12 22 11 + H O ¾H ¾¾®
2 CH O 6 12 6 + CH O 6 12 6
Sucrose D (+) Glucose D (–) Fructose
[a]D = 66.5° + 52.5° – 92.4°
Equimolar mixture [a]D = –19.85°
2. MALTOSE :
Maltose is obtained from starch, being composed of two a-D-Glucose units joined by an
a-glycosidic linkage between C–1 of one unit and C–4 of the other unit.
CH 2OH CH 2OH CH2 OH CH2 OH
O O O O
H H H H H H H H
H H H H
1 +4 1 1 4
OH H OH H – H 2O OH H OH H
OH OH OH O
OH HO OH
H OH H OH H OH H OH
Two a-D-Glucose units a-Linkage

Maltose
(i) C–1 of the second Glucose unit in the maltose structure is a hemiacetal carbon and hence
can exist in a - and b forms.
(ii) Since it has a potential aldehyde group, it shows mutarotation.
(iii) It forms osazone.
(iv) It reduces Fehling’s solution and Tollen’s reagent. Thus maltose in a reducing sugar.
3. LACTOSE :
Lactose is found in the milk of all animals, and hence commonly known as milk sugar.
Lactose is composed of b-D-Galactose unit and a-D-Glucose unit joined by b-D-Glycosidic
linkage beween C–1 of the galactose and C–4 of the glucose unit.
CH 2OH CH 2OH CH2 OH CH2 OH
O O O O
OH OH H H OH H H
H H H H
1 4 1 O
OH H + OH H – H 2O OH H OH H
H H HO OH OH H OH
H OH H OH H OH H OH
b-D-Galactose a-D-Glucose b-Linkage

Lactose
(i) Because of potential aldehyde group present lactose exists in both a - and b - forms.
(ii) It is a reducing sugar reducing Tollen’s reagent and Fehling’s solution.
(iii) It shows mutarotation.
E. POLYSACCHARIDES :
Polysaccharides are made of a large number of monosaccharide units joined together by
glycosidic linkages. The most common naturally occurring polysaccharides mainly acting as the
food storage or structural materials are :
BIOMOLECULES 699
(a) STARCH :
Starch is the main contributor of carbohydrates in our diet. It exists exclusively in plants,
stored in seeds, roots and fibres as food reserve. The chief sources of starch are cereals, potatoes,
corn and rice.
Structure :
Starch is a polymer of a-glucose and consists of two components.
(i) Amylose : The water soluble component of starch is amylose. The amylose molecule is
made up of D-glucose units joined by a - glycosidic linkages between C-1 of one glucose
unit and C–4 of the next glucose unit.
CH 2OH CH 2OH CH 2OH
O O O
H H H H H H
H H H
4 1 4 1 4 1
OH H OH H OH H
O O O O
H OH H OH H OH
a- link a - link
Amylose
(ii) Amylopectin : Amylopectin has a branched chain structure and insoluble in water
constituting about 80-85% of starch. It is composed of chains of 25 to 30 D-glucose unit
joined by a-glycosidic linkages between C-1 of one glucose unit and C-4 of the next
glucose unit. These chains are in turn connected to each other by 1, 6 - linkages.
CH 2OH CH 2OH
O O
H H H H
H H
4 1 4 1
OH H OH H
O O a - link
O
H OH H OH
Branch at C6
CH 2OH 6 CH 2
O 5 O
H H H H
H H
4 1 4 1
OH H OH H
O O O
H OH H OH
Amylopectin
(b) CELLULOSE :
Cellulose is the main structural material of trees and other plants. Wood is 50% cellulose,
while cotton wool is almost pure cellulose. Other sources of cellulose are straw, corncobs, bagasse
and other agricultural wastes.
(i) Structure : Cellulose is a straight-chain polysaccharide composed of D-glucose units
being joined by b - glycosidic linkages between C–1 of one glucose unit and C–4 of the
next glucose unit. The number of D-glucose units in cellulose ranges from 300 – 2500.
H
CH2 OH
O
H O
CH 2OH H
OH H
O
H O H
CH2 OH H
OH H H OH
O
H O H
H
OH H H OH
O H
b - links
H OH
Cellulose
(ii) The grazing animals like, cow, deer etc. can digest cellulose of grass and plants as the
enzyme cellulase is present in their stomach, whereas the humans can not digest cellulose
because of the absence of cellulase.
(C) GLYCOGEN :
Glycogen is present in liver and muscles and is known as the reserve carbohydrate of
animals or animal starch. When energy i.e. glucose is needed for any work by the body, glycogen
is broken down to glucose by enzymes.
The structure of glycogen is similar to that of amylopectin and it has 1,6 as well as 1,4
glycosidic linkages, but it is much more branched than amylopectin.
22.3 AMINO ACIDS :

Proteins are linear polymers of a-amino acids. Therefore amino acids are regarded as
“building blocks of proteins.” The general structure of a-amino acid is represented as,
NH2
|
a
R—C—COOH
|
H
BIOMOLECULES 701
Here amino group is present at a-carbon atom, R may be a hydrogen atom or any alkyl
group or an aromatic ring or a heterocyclic ring. Hence each amino acid is a nitrogeneous compound
containing both an acidic carboxyl and a basic amino group. Except in glycine, a-carbon atom in
all the amino acids is asymmetric in nature.
About 20 commonly occurring a-amino acids are known, which are obtained by the
hydrolysis of proteins. These amino acids differ from one another due to the different nature of
their side chain group, R. The properties of side chain present in the amino acid determine the
properties of proteins they constitute.
A. Structure of amino acids :
According to the general formula, amino acids contains both an acidic (—COOH) group
and a basic (-NH2) group. In fact, these two groups interact resulting in the transfer of a proton
from acidic carboxylic acid group to basic amino group, thereby resulting in the formation of an
internal salt as shown below.
NH3
NH2 -
a| R - CH - COO
R—CH—COOH
The dipolar structure of internal salt is known as zwitter ion.
The a- carbon atom of all amino acids (except glycine) is asymmetric. Hence, except
glycine all amino acids are optically active. They give two stereoisomers, which are mirror images
of each other. However, all the naturally occurring amino acids have L-configuration having–
NH2 group on the left as –OH group in L-glyceraldehyde.
COOH CHO
H 2N H HO H
R CH2OH
L-aminoacid L-glyceraldehyde
COOH COOH
| |
H2N—C—H H—C—NH2
| |
R R
Mirror
L (–) a - Amino acid D (+) a - Amino acid
B. Classification of Amino acids :

Amino acids can be classified mainly in two ways;
(a) Neutral, acidic and basic amino acids.
(b) Essential and non-essential amino acids.
(a) Neutral, acidic and basic amino acids :
Amino acids are classified as neutral, acidic and basic according to the relative number of
amino and carboxyl groups in the molecule.
(i) Neutral amino acids contain one amino group and one carboxyl group. (ii) Acidic
amino acids contain one amino group and two carboxyl groups. (iii) Basic amino acids
contain two amino groups and one carboxyl group. Examples of each type are given in
Table 22.1
Table 22.1 Amino acids derived from proteins
Common name Abbreviated name Structure
NEUTRAL
AMINO ACIDS:
Glycine Gly H2N – CH2 – COOH
NH2
|
Alanine Ala CH3 — CH — COOH
CH3 NH2
| |
Valine Val CH3 — CH — CH — COOH
NH2
|
Tyrosine Tyr HO — — CH2 — CH — COOH
Proline Pro
CH - COOH
N
H
ACIDIC AMINO ACIDS : NH2

|
Aspartic acid Asp HOOC — CH2 —CH COOH
NH2
|
Glutamic acid Glu HOOC—CH2—CH2—CH—COOH
BIOMOLECULES 703
Common name Abbreviated name Structure
BASIC AMINO ACIDS :

Arginine Arg HN = C —NH —(CH2)3— CH — COOH
| |
NH2 NH2
NH2
|
Histidine His HC===C — CH2 — CH — COOH
| |
N NH
C
H
NH2
|
Lysine Lys H2N — (CH2)4 — CH — COOH
(b) Essential and non-essential amino acids :

Amino acids can also be classified as essential and non-essential amino acids.
(i) Those amino acids that can not be synthesised by the body and must be supplied in
the diet are called essential amino acids. For example; valine, leucine, isoleucine
etc.
(ii) But the amino acids that can be synthesised by the human body are called non-
essential amino acids. Examples are glycine, alanine, tyrosine etc.
C. PEPTIDES & POLYPEPTIDES
Peptides are the condensation products of two or more a-amino acids. The bond between
two adjacent amino acids is a special type of amide bond, known as the peptide bond and the
chain thus formed, is called a peptide chain.
Peptides can be classified as dipeptides, tripeptides and polypeptides depending upon the
number of amino acid molecules taking part in the condensation.
When two amino acids condense together, the resulting product is called a dipeptide.
Similarly, when theree amino acids combine, the product is called a tripeptide. When four or
more amino acids combine in this way, the product is called a polypeptide. Proteins are
polypeptides containing atleast 100 or more amino acids, but there is no clear demarcation
between polypeptides and proteins.
As for example, when glycine and alanine condense together, a dipeptide results.
O H O
|| | ||
H2N — CH2— C — OH + H — N — CH — C — OH
|
(glycine) CH3
(Alanine)
A peptide linkage
– H2O
O H O
|| | ||
H2N — CH2 — C — N —CH— C — OH
|
CH3
Glycil - alanine
(A dipeptide)
22.4 PROTEINS :
Proteins are essential compounds for living cells. The name protein (Greek : Proteios =
pre-eminent or first) was suggested by Berzelius. According to him, proteins are complex organic
nitrogeneous substances found in the cells of the living beings and essential to cell structure and
cell function. Thus, proteins are vital chemical substances essential for the growth and maintenance
of life. Proteins are present in almost all living cells of plants and animals.
Chemically, proteins are linear unbranched polymers of a-amino acids. In a protein
molecule, a-amino acids are linked together by peptide bonds formed between amino and
carboxylic groups of successive amino acids. Hence, proteins are polypeptides with more than
100 amino acids.
1. CLASSIFICATION OF PROTEINS :
(a) On the basis of structures, the proteins are classified into three main groups namely
simple, conjugated and derived proteins.
(i) Simple proteins give aminoacids on hydrolysis, carried out by acid, alkali or enzyme.
Examples are globulins, collagens, elastins etc.
(ii) Conjugated proteins are simple proteins which are bonded with non-proteinous prosthetic
groups. Examples are nuclein, nucleohistone, haemoglobin, chlorophyll, cytochrome,
albumin, casein, serum proteins etc. Albumin contains glycoprotein as protein and
carbohydrates as prosthetic group. Casein has phosphoprotein and phosphoric acid other
than nucleic acid. Serum protein has lipoprotein and lipid as prosthetic group.
(iii) Derived proteins are obtained from simple proteins by regulated hydrolytic process.
(b) According to solubility, proteins are classified as fibrous proteins and globular proteins.
BIOMOLECULES 705
(i) Fibrous proteins are insoluble in water and possess long threadlike structures. They are
found in nails, horn, hair (keratin), wool, silk and feathers.
(ii) Globular proteins are soluble in water, acid and alkali. These are highly branched and
cross-linked. These proteins perform various functions related to maintenance and
regulation of life process. They include all enzymes, many hormones (insulin), albumin
in egg, haemoglobin, antibodies responsible for allergies and for defence against foreign
organisms.
2. STRUCTURE OF PROTEINS :
The complete structure of a protein is quite complex. Therefore, their structures are usually
discussed in four different levels such as primary, secondary, tertiary and quaternary structures of
the protein.
(i) Primary structure : The primary structure of proteins refers to the sequence in which
various amino acids are linked together by peptide linkages. The primary structure of a
protein is determined by its successive hydrolysis with acids, alkalies or enzymes.
Successive hydrolysis of proteins yield different products having decreasing molecular
masses as shown below.
Proteins Proteoses Peptones Polypeptides Simple Peptides a - amino acids
In primary structure, the peptide bonds form the backbone and the side chains of amino
acids project outside the peptide backbone.
H O H
H R
1.24A°
N ° C 1 .3 C N
3A 2A
1. 5 ° °
7A
C N 1. 4 C
H R
O O
Fig : 22.1 Primary structure of protein
The amino acid sequence of a protein determines its function and is critical to its biological
activity. The amino acid sequence in proteins can be determined by taking the following
generalisations. They are (a) Proteins are made up of L-amino acids only; (b) Sequence of amino
acids along the protein chain is random; and (c) Even a change of just one amino acid can drastically
alter the properties of the entire protein molecule. For example a disease called sickle cell anaemia
is caused when one a-amino acid is replaced in haemoglobin.
(ii) Secondary structure : The secondary structure of proteins refers to the conformation which
the polypeptide chains assume as a result of hydrogen bonding between the carboxylic
acid and amino groups. Two different secondary structures are possible depending on the
size of the side chain (R-)
(a) a-Helix structure : When the size of the R- group is very large, intermolecular hydrogen
bonding occurs between C = O group of one amino acid unit with N — H group of
the fourth amino acid unit present in the chain. As a result, the polypeptide chain coils up
into a spiral structure, called right handed a- helix structure. a- Helix structure are seen
in most of fibrous proteins like a-keratin in hair, nail and myosin in muscles.
R H
O H R H
H || |
| C C N C
H C N
| C N C C N
|| || | || |
N O O H R H O H
C
||
O C
||
O
H H C H O
| C R H
| || | ||
N || N O C N C
H O N
H C C C
| | ||
N C | R H H R H
C N O
|| ||
O O
Fig : 22.3 b-Pleated sheet structure
Fig : 22.2 a-Helix structure
(b) b-pleated sheet structure: When the size of R-group is small, the polypeptide chains lie
side by side in a zig-zag manner with alternate R- groups on the same side situated at
fixed distances. As a result of which intermolecular hydrogen bonding occurs between
two neighbouring chains. This results in the formation of a flat sheet structure.
(iii) Tertiary structure : An a- helix may be considered to be a piece of a rope which is free
to bend, twist and fold. The tertiary structure of a protein refers to the final three -
dimensional shape that results from the twisting, bending and folding of the protein helix
with main forces operating are hydrogen bonding, disulphide linkage, and van der Waal’s
forces of attraction. Tertiary structures of proteins results with fibrous and globular
molecular shapes.
(iv) Quaternary structure : Complex proteins are formed by the combination of two or more
polypeptide chains. Each chain is a complete protein with a characteristic primary,
secondary and tertiary structure. The quaternary structure refers to the way in which these
polypeptide chains of a complex protein are associated with each other.
BIOMOLECULES 707
3. BIOLOGICAL ROLES OF PROTEINS :

Proteins are of great importance to biological systems. These are most essential to life
and perform various functions. Some of their important roles are given below:
(i) Many proteins act as catalysts, which enhance the rate of chemical reactions to an
appriciable extent as required by the living cells and are known as enzymes.
(ii) The fibrous proteins act as “components of the tissues” holding together the skeletal
elements. For example, collagen is a structural unit of connective tissues.
(iii) Protein hormones regulate the growth of plants and animals, besides controlling
many other physiological functions.
(iv) Interferon is a cellular protein, which is naturally produced by the body in response
to virus infections.
(v) Blood plasma, which is a solution of proteins in water is used for the treatment of
shock produced by serious injuries and operations.
4. DENATURATION OF PROTEINS :
The process after which proteins lose their physiological activity and certain other
properties is called denaturation which is caused by
(i) action of bacteria
(ii) action of heat
(iii) by shaking with alcohol and
(iv) by treatment with acids.
(a) Examples of denaturation :
(i) Boiling of an egg : Coagulation of the white of an egg by the action of heat is a
very common example of denaturation.
(ii) Formation of cheese : The coagulation of milk in the presence of an acid (lemon
juice) to form cheese is an example of denaturation.
(b) Cause of denaturation :
Denaturation is due to the disruption of the secondary and tertiary structure due to the
breaking of hydrogen bonding and salt bridges in proteins causing uncoiling of the protein
molecules from an ordered and specific confirmation into a more random conformation resulting
into its coagulation from solution.
Denaturing Agent
Natural protein Denatured protein

(c) Renaturation :
The reversible process by which the original form of the denatured protein can be regained
is known as renaturation. Protein denaturation may or may not be reversible. Coagulation of
white of an egg on heating is an irreversible process. But in case of reversible denaturation, the
protein can be coagulated from their colloidal solution by saturating the solution with soluble
salts like ammonium sulphate, or by the addition of water or alcohol thus rejoining the original
form.
22.5 ENZYMES :
Enzymes are defined as the complex nitrogenous organic compounds produced by living
plants and animals. They are polypeptides i.e. proteins of high molecular mass responsible for
catalyzing natural processes prevailing in the bodies of animals and plants, for which the enzymes
are also termed as biochemical catalysts and the phenomenon is termed as biochemical catalysis.
Some examples of enzyme catalysis are :
(a) Inversion of cane sugar : The enzyme invertase converts cane sugar into glucose and
fructose.
C12H22O11(aq) + H2O(l) ¾Invertase
¾ ¾ ¾¾® C6H12O6(aq) + C6H12O6(aq)
Glucose Fructose
(b) Conversion of milk into curd : The enzyme lacto bacilli is responsible for the conversion
of milk into curd.
(c) Conversion of glucose into ethyl alcohol : The zymase enzyme converts glucose into
ethyl alcohol and carbon dioxide.
C6H12O6(aq) ¾Zymase
¾ ¾ ¾® 2 C2H5OH(aq) + 2 CO2(g)
Glucose Ethyl alcohol
(d) Conversion of starch into maltose : The diastase enzyme converts starch into maltose.
2(C6H10O5)n (aq) + n H2O(l) ¾Diastase

¾¾¾ ¾® n C12H22O11 (aq)
Starch Maltose
(e) Conversion of maltose into glucose : The maltase enzyme converts maltose into glucose.
C12H22O11 (aq) + H2O (l) ¾Maltose

¾¾¾ ¾® 2 C2H12O6(aq)
Maltose Glucose
(f) Decomposition of urea into ammonia and carbon dioxide : The enzyme urease catalyses
the decomposition of urea.
NH2CONH2 (aq) + H2O (l) ¾Urease
¾ ¾¾® 2NH3 (g) + CO2(g)
BIOMOLECULES 709
(g) In stomach the pepsin enzyme coverts proteins into peptides while in intenstine, pancreatic
trypsin converts proteins into amino acids by hydrolysis.
1. NATURE OF ENZYMES :
(i) Enzymes are globular proteins.
(ii) Like proteins enzymes are amphoteric by nature.
(iii) Enzymes also get denatured like proteins.
(iv) When purified enzymes are injected in the body, specific antibodies are produced.
(v) They are generally named after the compound or class of compounds on which
they are effective. For example, the enzyme is named maltase which catalyzes
hydrolysis of maltose.
Maltose ¾Maltase
¾¾¾ ¾® 2 Glucose.
(vi) Enzymes are also named after the reactions. For example the enzymes are named
as oxido reductase enzymes, when they catalyze the oxidation of one substrate
with simultaneous reduction of another substrate. The name of the enzyme always
ends with suffix-ase.
2. PROPERTIES OF ENZYMES :
(i) Catlytic efficiency : Enzymes are very efficient catalysts. A very small quantity of
any enzyme is needed to catalyse a reaction. For example, the enzyme rexin co-
agulate over a million times its weight of milk during cheese formation.
(ii) Specificity : Enzymes are highly specific in nature. An enzyme catalyses only a
particular reaction.
Invertase can break up sucrose into glucose and fractose, but fails to breake up a
similar disaccharide, maltose, which can only be broken by another enzyme maltase.
Similarly urease hydrolyses urea to ammonia and carbon dioxide but does not
hydrolyse N-methyl urea which has a similar structure.
NH2CONH2 + H2O ¾Urease
¾ ¾¾® 2NH3 + CO2
CH3NHCONH2 + H2O ¾Urease
¾ ¾¾® No action
(iii) Effect of temperature : Enzymes are most effective near body temperature i.e. the
rate of enzyme reaction becomes maximum at the optimum temperature with the
range 298 - 310K. In general all the chemical reactions proceed faster with increase
in temperature, bu the rate of enzyme catalyzed reaction first increases, become
maximum at about 35°C and then decreases at higher temperature.
(iv) Effect of pH : The rate of an enzyme-catalysed reaction is maximum at a particular

pH called optimum pH, which is between pH values 5-7.
(v) Effect of co-enzymes and activators : The enzymatic activity is increased in the
presence of small organic molecules called co-enzymes which are derived from
vitamins such as thiamine, riboflavin etc.
Metal ions like Na+, Mn2+, Co2+, Ca2+ etc when weekly bonded to enzyme molecules
increase their catalytic activity, for which there are called activators. For example
amylase in presence of sodium chloride are catalytically very active.
(vi) Influence of inhibitors : The enzyme activity can be reduced or inhibited by the
presence of certain compounds known as enzyme inhibitors.
22.6 HORMONES :
A hormone is a chemical released by one or more cells that affects cells in other part of the
organism. Only a small amount of hormone is required to alter cell metabolism. All multicellular
organisms produce hormones. Plant hormones are called Phytohormones. Hormones in animals
are often transported in the blood. Cells respond to a hormone when they express a specific
receptor for that hormone. The hormone binds to the receptor protein, resulting in the activation
of a signal transduction mechanism that ultimately leads to cell type - specific responses.
Endocrine hormone molecules are secreted by ductless glands directly into the blood
stream whereas exocrine hormone molecules are secreted directly into a duct and from the duct
they flow into the blood stream. Then they move to different parts of the body and exert strong
regulatory influence on the chemical processes taking place there.
Chemical classes of Hormones
Vertebrate hormones fall into three chemical classes.
(i) Amine derived hormones : Examples are catecholamines and thyroxine.
(ii) Peptide hormones : They are protein hormones and include insulin and growth hormone.
More complex protein hormones bear carbohydrate side chains and called glyocoprotein
hormones. Luteinizing hormone, follicle stimulating hormones and thyroid stimulating
hormones are glycoprotein hormones.
(iii) Lipid and phospholipid - derived hormones : They are the derivatives of linoleic acid
and arachidonic acid and phospholipids. The main classes are the steroid hormones that
derive from cholesterol and cortisol. Calcatriol is a sterol hormone. The adrenal cortex
and the gonads are the main sources of steroid hormones.
BIOMOLECULES 711
Some hormones in man are given in the following table.

Hormone Source Function
1. Adrenalin - Adrenal medulla - Increases pulse rate & blood pressure,
releases glucose from glycogen and fatty
acids from fats.
2. Testosterone - Testis - Normal functions of male sex organ.
3. Estrone or Estradiol - Ovary - Normal functioning of female sex organ.
4. Insulin - Pancreas - Metabolism of Glucose
5. Cortisone - Adrenal cortex - Metabolism of water, fats, proteins and
carbohydrates.
6. Pituitary hormone - Pituitary glands - Stimulation of thyroid gland, testis, ovary
and mammary glands.
Effects of Hormones : A few important effects of hormones are

1. Stimulation or inhibition of growth.
2. Mood swing
3. Induction or suppression of apoptosis (Programmed cell death)
4. Activation or inhibition of immune system.
5. Regulation of metabolism.
6. Preparation of the body for fighting sex, mating and other activity.
7. Preparation of the body for a new phase of life.
8. Control of reproductive cycle.
A hormone may also regulate the production and release of other hormones.
Plant Hormones : An example of plant hormone is a series of substances called auxins.
Auxins increase the length of most plant cells and thereby contribute to the growth and elongation
of the plant.
Another plant hormone is abscisic acid, which is produced in mature leaves and inhibits
growth in developing leaves and germinating seeds. Another hormone ethylene encourages
ripening and dropping of leaves and fruits from the trees.
Two important growth regulating hormones are the gibberellins and cytokinins.
Gibberellins affect plants by stimulating their growth via rapid stem elongation. Cytokinins induce
plant cells to undergo mitosis, therefore they encourage increased growth in the roots and stems
in plants. They also enhance flowering and stimulate some type of seeds to germinate.
22.7 VITAMINS :
Vitamins are defined as the naturally occurring organic compounds required in the diet in
very small quantities to maintain the normal health and development of the organism.
Vitamins, themselves do not supply much energy to the body, but in small quantities
perform specific and vital functions such as energy transformation reactions in the body. Dificiency
of a particular vitamin causes specific disease. Excess of vitamins is also harmful and hence
vitamin pills should not be taken without the advice of Doctor.
Classification of vitamins :
Vitamins can be categorized into two groups depending on their solubility in fat or water.
These are :
A. Fat soluble vitamins :
Vitamins like A, D, E and K are soluble in fat and oils, but isoluble in water. These are
found to be stored in liver and adipose tissues.
B. Water soluble vitamins :
Water soluble vitamins are vitamin C and vitamin B complex. These vitamins must be
supplied regularly in diet to our body as they are readily excreted in urine and can not be stored in
our body excepting B12.
The sources, properties and functions of some of the important vitamins are discussed
here.
1. Vitamin A (Retinol) : This belongs to a class of organic compounds called carotenoids
to which carotenes belong. Vitamin A is a carotene derivative, insoluble in water, but
soluble in fats and oils. It is not easily destroyed on heating. It is available in cod liver oil,
egg yolk, carrots, milk, butter and green vegetables.
Function : Deficiency of vitamin A results in the retarded growth and a change in epithelial
cells. Deficiency of this vitamin causes nightblindness, xerosis in which the skin becomes
dry and xerophthalmia in which the corneas of eyes become opaque.
2. Vitamin B Complex : This consists of a number of complex substances like vitamin B 1
or thiamine, vitamin B2 or riboflavin, vitamin B6 and vitamin B12 or cyanocobalamine.
(i) Vitamin B1 (Thiamine) : It is a water-soluble white crystalline compound and
stable up to 1000C in dry condition. Stability to heat decreases in moist condition.
Thiamine is available in milk, green vegetables, meat, egg, yeast, cereals, nuts and
rice polishings.
Function : Its deficiency in diet causes loss of appetite, and a severe disease called
beriberi.
BIOMOLECULES 713
(ii) Vitamin B2 (Riboflavin) : It is an orange yellow water-soluble crystalline compound

and quite stable to heat, but sensitive to light. Vitamine B 2 is available in milk,
green vegetables, egg, liver and rice polishings.
Function : Deficiency of vitamin B2 causes skin diseases, sore tongue and anaemia.
(iii) Vitamin B6 : It consists of three similar components pyridoxal, pyridoxine and
pyridoxamine and is water-soluble. It is easily destroyed by heat and ultraviolet
radiation. The chief source of vitamin B6 is cereal grain, egg yolk, meat, fish, milk
and cabbage.
Function : Deficiency of vitamin B6 causes nervous disturbances and convulsions.
(iv) Vitamin B12 (Cyanocobalamine) : It is a large complex molecule which has a
central cobalt atom coordinated to four nitrogen atoms. Vitamin B 12 is water-soluble
red crystalline solid. It is present in meat, fish, egg and curd.
Function : Lack of this vitamin causes a bad form of anaemia.
3. Vitamin C (Ascorbic acid) : It is insoluble in fats and oils, but soluble in water. Vitamin
C is destroyed in contact with oxygen of air even at room temperature since it undergoes
reversible equilibrium. It loses effectiveness upon open storing and therefore, vitamin C
tablets are kept in sealed strip foils. A major part of this vitamin is lost when vegetables
are cooked in open pans in contact with air. Therefore, cooking of vegetables in closed
pans or pressure cookers is considered desirable to avoid loss of vitamin C. It is present
in fresh vegetables, citrus fruits (lemon, orange), tomatoes, chillis, amla, papita etc.
Function : Absence of vitamin C is a diet causes scurvy and pain in joints.
4. Vitamin D (Calciferols) : It is a white crystalline solid soluble in fats and oils only and
present in milk, egg, liver, cod liver oil etc. Morning sun rays falling on the skin form
vitamin D from the sterols present under the skin.
Function : Vitamin D helps in the development of bones and teeth in growing children.
Its deficiency causes rickets in which the bones and legs get curved and the teeth get
deformed.
5. Vitamin E (a-Tocopherol) : This vitamin, also known as ‘‘antisterility’’ vitamin is a
light yellow oily substance soluble in fats and oils. It is present in animal and vegetable
oils, cotton seed oil, maize oil, pea-nut oil, wheat germ oil, sunflower oil etc.
Function : Deficiency of vitamin E causes damage to the reproductive system of both
males and females, and increased fragility of RBCs and muscular weakness.
6. Vitamin K : This vitamin is a mixture of vitamin K 1 and K2. It is fat soluble and stable to
heat. Vitamin K is present in leafy vegetables, fish, eggyolk and liver.
Function : It plays a vital role in coagulation properties of blood. Its deficiency leads to
profuse bleeding even from small wounds and causes disturbances in bleeding time and
clotting time of blood.
22.8 NUCLEIC ACIDS :

Nucleic acid was first isolated in 1871 by a Swiss physician and chemist Friedrich
Miescher. He isolated a substance from the nuclei of the pus cells and named it as nuclein. This
substance was quite different from the carbohydrates and proteins. Later, it was found that the
nuclein had acidic properties and it was renamed by Altman in 1889 as nucleic acid. Nucleic
acid is a substance, which is responsible for the transmission of hereditary characters.
Nucleic acids are long chain biopolymers present in most living cells either in the free
state or bound to proteins as nucleoproteins. The nucleic acids are biopolymers of high molecular
mass with nucleotide as their repeating units. As regards their elemental composition, the nucleic
acids contain carbon, hydrogen , oxygen , nitrogen and phosphorous.
(a) Composition of Nucleic acids :
We know, nucleotide is the monomeric unit of nucleic acid. A nucleotide is further made
up of a phosphoric acid unit and a nucleoside. A nucleoside is made up of two components,
that is a pentose sugar and a nitrogen containing heterocyclic base. Thus, in general, a nucleotide
and a nucleic acid can be represented as follows:
Base
O
||
Sugar — O — P — OH
|–
O
(A nucleotide)
Base Base
O O
|| ||
— Sugar — O — P — O — Sugar — O — P — O —
| |
–O –O
(A nucleic acid)
Two types of sugars are present in nucleic acids. They are b-D ribose and b-D-2-
deoxyribose. Both these pentose sugars are present in furanose form. The bases present in nucleic
acids are purine and pyrimidine.
5 5
HOH 2C O OH HOH 2C O OH
4 1 4 1
H H H H
H H H H
3 2 3 2
OH OH OH H
b-D ribose b-D-2- deoxyribose
BIOMOLECULES 715
The bases derived from purine are adenine (A) and guanine (G). Similarly, the bases
derived from pyrimidine are thymine (T), uracil (U) and cytosine (C).
The nucleic acid which contains only ribose is known as ribonucleic acid (RNA) and the
nucleic acid which contains deoxyribose is known as deoxyribonucleic acid (DNA). Nucleic
acids are long chain polymers of nucleotides and therefore they are known as polynucleotides.
DEOXYRIBONUCLEIC ACID (DNA) :

DNA is composed of two strands of polynucleotides coiled around each
other in the form of a double helix resembling a gently twisted ladder. This
information was given by James Dewey Watson who received Nobel prize along
with Francis Crick and Maurice Wilkins with the foundation of a new field of
Molecular Biology.
The bases (specific pyrimidine groups) on one strand of DNA are paired
with the bases (purine groups) on the other stand with the help of hydrogen
bonding, which is highly specific because the structures of bases allow only one
Double
mode of pairing. Adenine (A) pairs with only thiamine (T) via two hydrogen
strand helix
bonds while guanine (G) pairs with cytosine (C) through three hydrogen bonds. structure of
It is because the sequence of bases in one strand automatically determines that of DNA
other.
The complimentary pairing of nucleotides bases explains how indentical copies of parental
DNA pass on to two daughter cells thus transmitting inherent characters (heredity). Har Gobind
Khurana, an Indian Scientiest shared the Nobel prize for Medicine and Physiology for cracking
the genetic code while working at Cambridge, UK with Marshal Nirenberg and Robert Holley.
DNA FINGER - PRINTING :

Each person has unique finger prints which occur at the tips of the fingers being used for
indentification. But unfortunately now fingerprints can be easily altered by surgery.
A sequence of bases on DNA is also unique for a person and information regarding this is
called DNA finger printing. It is same for every cell and can not be altered by any treatment. For
this reason DNA fingerprinting is now used :
(i) to determine paternity of an individual
(ii) in forensic laboratories for identification of criminals.
(iii) to identify dead bodies in any accident by comparing the DNA’s of their parents or children.
(iv) to identify racial groups to rewrite biological evolution.
RIBONUCLEIC ACID (RNA) :

The process of translating coded message into action requires ribonucleic acid (RNA). The
chemical constitution of RNA is almost similar to that of DNA except that the sugar in RNA is
ribose and the base is uracil (U) in place of thymine (T) as in DNA. The structure of RNA in most
organisms is single stranded, but appears helical because at some places it is wound back upon
itself.
There are three kinds of RNA
(i) Messenger RNA (m-RNA) : This carries the genetic information from that template of
DNA chain to the site of protein.
(ii) Transfer RNA (t-RNA) : This is the smallest of all the RNAs, single stranded and occurs
free in the cytoplasm of the cell, one for each aminoacid found in protein.
(iii) Ribosomal RNA (r-RNA) : This is present in ribosome and constitutes about 80% of
total RNA. r-RNA helps in protein synthesis and carries no message of DNA.
BIOLOGICAL FUNCTIONS OF NUCLEIC ACIDS :

The two important biological functions of nucleic acids are replication and protein
synthesis.
(i) Replication is a process by which a single DNA molecule produces two identical
copies of itself. Replication is an enzyme catalysed process. The two identical copies of DNA
produced from the original DNA are then passed on to the two new cells resulting from cell
division. In this way hereditary characters are tranmitted from one cell to another. DNA is double
stranded.
(ii) Another important function of RNA is the synthesis of proteins. The RNA molecule
present in the cell nucleus is responsible for the synthesis of all the proteins present in a cell.
Protein synthesis is a very fast process.
1. Carbohydrates : Carbohydrates are polyhydroxy aldehydes or ketones and their derivatives

or substances that yield one of these compounds on hydrolysis.
2. Aminoacids : Aminoacids are regarded as building blocks of proteins.
3. Proteins : Proteins are linear or branched polymers of a-amino acids linked by peptide
bonds. Enzymes, many hormones and antibiotics are also proteins in nature.
4. Nucleic acids : Nucleic acids contain long chain of alternating sugar and phosphate units
with bases attached to the sugar residue. DNA contains deoxyribose sugar and bases are
adenine, guanine, cytosine and thiamine. RNA contains ribose suagr and bases like adenine,
guanine, cytosine and uracil. While DNA is present in the molecule of the cell, RNA is
BIOMOLECULES 717
present outside the nucleus in the surrounding fluid called cytoplasm. DNA is the chemical
bases of heredity and have the coded message for the proteins to be synthesised in the cell.
The three types of RNA i.e. m-RNA, t-RNA and r-RNA carry out the synthesis of proteins
in the cell. RNA is single stranded whereas DNA is double stranded.
5. Vitamins : Vitamins are specific organic compounds required by animals, bacteria and
micro-organisms in small amounts for the maintenance and normal growth of life. Vitamin
A, D, E and K are fat soluble while vitamin B and C are water soluble. Deficiency of these
vitamins causes diseases.
6. Enzymes : They are considered as conjugated proteins. They are globular proteins (soluble
in water, acid and alkali).
7. Hormones : Chemicals released by one or more cells that affect cells in other part of the
organism are called hormones. They may be amine-derived hormones (catecholamines,
thyroxine etc), peptide hormones or protein hormones, (insulin, TRH and growth hormones),
lipid and phospholipid derived hormones - steroid hormones (testoterone, cortisol, calcitriol
etc). Plant hormones are called auxins. Other plant hormones are gibberellins and cytokinins,
ethylene, abscisic acid etc.
QUESTIONS
A. VERY SHORT ANSWER QUESTIONS (1 MARK EACH)

1. Enzymes are type of proteins
2. The carbohydrate present in DNA molecule is
3. The general formula of a carbohydrate is
4. DNA stands for
5. RNA stands for
6. Name the nucleic acids which are used in protein synthesis
7. Name the bases present in both RNA and DNA.
8. Which vitamin is Ascorbic acid ?
9. Which vitamin is obtained from sunlight ?
10. Which elements are generally present in proteins ?
11. What are the hydrolysis products of sucrose ?
12. Name two carbohydrates which act as biofuels.
13. What causes the disease sickle cell anaemia ?
14. _________ is the chemical basis of heredity.
15. Name the building blocks of proteins.
16. Which polysaccharide is stored in the liver of animals.
[Answers. 1. Conjugated, 2. Deoxyribose, 3. Cx(H2O)y, 4. Deoxyribonucleic acid, 5.

Ribonucleic acid, 6. DNA & RNA, 7. Adenine, guanine and cytosine, 8. Vitamin C 9.
Vitamin D, 10. C, H, O, N, S & P., 11. Glucose & Fructose, 12. Starch and glycogen, 13.
Defective Haemoglobin, 14. DNA, 15. a - Amino acids, 16. Glycogen]
B. SHORT ANSWER QUESTIONS (2 MARKS EACH) :

1. What are oligosaccharides ? Give one example.
2. What are zwitter ions?
3. What is meant by inversion of sugar?
4. What are polysaccharides? Give one example.
5. What happens when protein is denatured?
6. What is a prosthetic group?
7. What are proteins?
8. What are monosaccharides ? Give one example.
9. Why can not vitamin C be stored in our body?
10. What are the different types of RNA found in the cell?
11. What is the difference between a nucleoside and a nucleotide?
12. What are enzymes?
13. What are anomers?
14. What are nucleic acids?
15. How does glucose differ from fructose?
C. SHORT ANSWER QUESTIONS (3 MARKS EACH) :

1. Classify Carbohydrates giving one example of each class.
2. What are the important units of protein ? What is the name of the bond between these
units ?
3. Give two biological functions of nucleic acids.
4. Differentiate between DNA and RNA.
5. Where does the water present in the egg go after boiling the egg?
6. How are the vitamins classified?
7. Explain mutarotation of D-glucose.
8. Name four important vitamins of vitamin B complex. Deficiency of which of these vitamins
causes beriberi ?
9. Name three hormones from three different classes of vertebrate hormones.
10. Name two plant hormones giving one function of each of them.
BIOMOLECULES 719
11. What are reducing and non-reducing sugars?

12. What is the basic differenc between starch and cellulose?
13. How can you explain the absence of aldehyde group in the pentaacetate of D-glucose.
14. Differentiate between globular and fibrous proteins.
15. Explain why glucose and fructose give the same osazone, on treatment with excess phenyl
hydrazine.
D. LONG QUESTIONS :
1. What are proteins ? How are they classfied ? Discuss their primary, secondary and tertiary
structures.
2. What are vitamins ? Classify the vitamins along with the roles of various vitamins in our
body.
3. How glucose is synthesized? Discuss the ring structure of D-Glucose.
4. What are monosaccharides? Elucidate the structure of D-Fructose.
5. What are hormones? How are they classified. Give one example of each along with its
functions.
6. What are plysaccharides? Discuss the structure of starch and cellulose.
E. MULTIPLE CHOICE QUESTIONS :

1. Which one of the following is a disaccharide ?
(a) glucose (b) starch (c) sucrose (d) cellulose
2. Ascorbic acid is the name of
(a) a vitamin (b) an enzyme (c) an aminoacid (d) a hormone
3. Which of the following is a monosaccharide ?
(a) maltose (b) fructose (c) sucrose (d) lactose
4. Ribose is an example of
(a) ketohexose (b) disaccharide (c) pentose (d) polysaccharide
5. Enzymes are
(a) proteins (b) minerals (c) oils (d) fatty acids
6. The main structural feature of protein is
(a) the ester linkage (b) the ether linkage (c) the peptide linkage (d) all of the above
7. In nucleic acids, the sequence is
(a) phosphate - base - sugar (b) sugar - base - phosphate
(c) base-sugar - phosphate (d) base- phosphate - sugar
8. a- and b- glucose differ in the orientation of –OH group around
(a) C1 (b) C2 (c) C3 (d) C4
9. Vitamin A deficiency leads to a disease known as

(a) Beriberi (b) Night blindness (c) Scurvy (d) All
10. Insulin is
(a) Antibiotic (b) Antiseptic (c) Hormone (d) Vitamin.
11. Which of the following is known as antiscurvy factor ?
(a) Vitamin A (b) Vitamin C (c) Vitamin D (d) Vitamin E
12. The fat -soluble vitamin is
(a) Retinol (b) Thiamine (c) Riboflavin (d) Pyridoxine
13. Vitamin B1 is called
(a) Riboflavin (b) Thiamine (c) Pyridoxine (d) Cyanocobalamine
14. Which of the following contains cobalt ?
(a) Chlorophyll (b) Haemoglobin (c) Vitamin C (d) Vitamin B 12
15. Hair, Finger nails, hoofs etc. are all made of
(a) Fat (b) Vitamins (c) Proteins (d) Iron
16. Proteins are polymers of amino acids. Which of the following is not a protein ?
(a) Wool (b) Nails (c) Hair (d) DNA
17. The chemical messengers produced in ductless glands are
(a) Vitamins (b) Hormones (c) Lipids (d) Antibiotics
18. The function of DNA is
(a) to synthesise RNA (b) to contain message to carry out specific protein synthesis (c) to
carry hereditary characteristics from generation to generation (d) all of the above.
19. Adenosine is an example of
(a) Nucleoside (b) Nucleotide (c) Purine base (d) Pyrimidine base
20. Two purine bases present in both DNA & RNA are
(a) Guanine & Adenine (b) Guanine and Uracil (c) Adenine & Thiamine (d) Cytosine and
Uracil
21. A mixture of amylose and amylopectin is called
(a) starch (b) cellulose (c) lactose (d) sucrose
22. Which vitamin is water soluble?
(a) Vitamin-K (b) Vitamin-B (c) Vitamin-E, (d) Vitamin-A
23. The number of chiral carbons in b- D(+) glucose are
(a) three (b) four (c) five (d) six
24. Which hormone contains iodine.
(a) Thyroxine (b) Insulin (c) Adrenaline (d) Testosterone
BIOMOLECULES 721
25. Sugars have the suffix

(a) –ol (b) –al (c) –ose (d) –one
26. The function of enzymes in the living system is to
(a) provide immunity (b) provide energy
(c) catalyse biochemical reaction (d) transport oxygen
27. The helical structure of protein is stabilised by
(a) Hydrogen bonds (b) Dipetide bonds
(c) Peptide bonds (d) van der Waals forces.
28. Vitamin A is called
(a) Ascorbic acid (b) Retinol
(c) Calciferol (d) Tocopherol
ANSWERS
1. (c) 2. (a) 3. (b) 4. (c)

5. (a) 6. (c) 7. (c) 8. (a)
9. (b) 10. (c) 11. (b) 12. (a)
13. (b) 14. (d) 15. (c) 16. (d)
17. (b) 18. (d) 19. (a) 20. (a)
21. (a) 22. (b) 23. (c) 24. (a)
25. (c) 26. (c) 27. (a) 28. (b)
qqq
UNIT - XV
CHAPTER - 23
POLYMERS
23.1 INTRODUCTION :
Polymers (Greek words, poly = many and meros = parts) are defined as the large molecules
having very high molecular mass consisting of a very large number of repeating structural units
joined together through covalent bonds in a regular fashion. The simple molecules from which
the repeating structural units are derived are called monomers and the process of formation of
polymers from their monmers is called polymerization.
For example,
(i) In case of polythene, polymer which is obtained by the polymerization of ethene
molecules the repeating structural unit CH2 – CH2 is derived from the
nonomers ethene.
Polymerization
n CH2 = CH2 ¾¾ ¾¾ ¾ ¾¾® ( CH – CH
2 2 n
Ethene Polythene
(Monomer) (Polymer)
(ii) In case of Nylon 6, 6, two different types of monomers used are hexamethylene
diamine and adipic acid interacting with each other with the repeating structural
unit
H H O O
N – CH2)6 – N – C – (CH2)4 – C
n NH2 (CH2)6 NH2 + n HOOC (CH2)4 COOH

Hexamethylene Adipic acid
diamine Polymerisation
H H O O
N – CH2)6 – N – C – (CH2)4 – C n + (2n–1) H2O

Nylon 6, 6
POLYMERS 723
Polymers because of their large size are also termed as macromolecules. But the reverse
is not true i.e. all polymers are macromolecules but all macromolecules are not polymers. For
example, proteins and nucleic acids are regarded as macromolecules but not polymers as these
molecules do not contain repeating structural units. Where as polythene can be regarded as both
a macromolecule and a polymer as it contains a number of repeating structural units.
23.2 CLASSIFICATION OF POYMERS :

Polymers can be classified into different categories basing upon different factors. These
are :
A. Classification based upon the sources :
Depending on the source from which they are derived, poymers can be categorized into
three classes, such as;
(a) Natural polymers : Polymers which are found in nature i.e. in animals and plants are
called natural polymers. Examples are :
(i) Proteins, silk, wool etc.
(ii) Polysacharides : Starch (potatoes, rice etc.), cellulose of cotton and wood.
(iii) Natural rubber
(b) Semi-synthetic polymers : These are chemically modified natural polymers. For example
cellulose on acetylation with acetic anhydride in presence of con. H 2SO4 gives cellulose
diacetate which is used for making threads of acetate rayon and other materials like
films, glasses etc. Other examples are gun cotton and vulcanized rubber.
(c) Synthetic polymers : Man made polymers like plastics (polyethylene, polypropylene),
fibres (nylon and terylene), rubbers (neoprene) adhesives, paints etc. are called synthetic
polymers.
B. Classification based on structure :
On the basis of structures, polymers can be classified into three types. These are:
(a) Linear polymers : In linear polymers the monomers are joined together to form long
straight chains of polymers molecules [Fig. 23.1(a)]. The various polymeric chains are
then stacked over one another to give a well packed structure resulting with high melting
point, high densities and high tensile strength. Examples of linear polymers are high
density polythene, nylon, polyester etc.
(b) Branched chain polymers : In these polymers the manomer units not only combine to
produce the linear chain called the main chain, but also form branches of different lengths
along the main chain [Fig. 23.1(b)]. Due to branching these polymers do not pack well
for which they have lower melting points, densities and tensile streangth than that of
linear polymers. Examples of this class are low density polythene, starch, glycogen,
amylopectin etc.
(c) Cross-linked or three demensional network polymers : In these type of polymers the
initially formed linear polymer chains are joined together to form a three-dimensional
network structure [Fig. 23.1(c)]. Only two cross-links per polymer chain are required to
join together all the long chain polymer molecules to form a giant molecule. Because of
the presence of cross-links, these polymers are called cross-linked polymers, which are
usually formed from bifunctional and trinfunctional monomers containing strong covalent
bonds between various linear polymer chains. Examples are bakelite, melamine etc.
(a) Linear structure
(b) Branched chain structure
(c) Three dimensional network or cross-linked structure

Fig. 23.1 : Different structures of polymers.
C. Classification based on the nature of repeating structural units :

Depending on the nature of repeating structural units, polymers are of two types:
(a) Homopolymers : Polymers containing only one type of monomers are called
homopolymers.
Polymerization
n CH2 = CH2 ¾¾ ¾¾ ¾ ¾¾® ( CH – CH
2 2 n
Ethene Polythene
(Monomer) (Polymer)
POLYMERS 725
Other examples are polyvinyl chloride (PVC), polyacrylonitrile (PAN), polypropylene

etc.
(b) Copolymers : Polymers whose repeating structural units are derived from two or more
types of monomers are called copolymers. Nylon-66 is a copolymers of hexamethylene
diamine and adipic acid.
n H2N – (CH2)6 – NH2 + n HOOC – (CH2)4 – COOH
Hexamethylene diamine Adipic acid (Monomer)
(Monomer) Polymerization
HN – (CH2)6 – NH – CO – (CH2)4 – CO n + (2n–1) H2O

Nylon 6, 6
(Copolymer)
Other examples are Buna–S–rubber, bakelite, polyethylene terephthalate (PET) etc.
D. Classification based on mode of polymerization :
Polymerization i.e. the process of synthesis of polymers can be carried out in two modes.
These are addition polymerization and condensation poymerization. Based on these two methods
of synthesis, the poymers can be classified into two categories.
(a) Addition polymers : Addition polymers are those polymers which are formed by the
repeated addition of monomers molecules possesing double or triple bonds without
elemination of simple molecules like water. These are also referred to as chain growth
polymers. For examples :
(i) ethene polymerises to from polyethylene.
Polymerization
n CH2 = CH2 ¾¾ ¾¾ ¾ ¾¾® ( CH – CH
2 2 n
Ethelene Polyethylene
(ii) Vinyl chloride polymerises to form polyvinylchloride (PVC).
Polymerization
n CH2 = CH ¾¾ ¾¾ ¾ ¾¾® ( CH – CH
2 2 n
½ ½
Cl Cl
Vinyl chloride PVC
(b) Condensation polymers : Polymers which are formed by the codensation reaction of
molecules having more than one functional group resulting with the removal of simple
molecules like H2O, NH3 or CH3OH. These are also termed as step growth polymers.
For examples :
(i) Dacron (polyester) is produced by successive condensation of ethylene glycol

molecules and terephthalic acid molecules.
n HO – CH2 – CH2 – OH + n HOOC –– –– COOH
Ethylene glycol Terephthalic acid
Polymerization
O O
O – CH2 – CH2 – O – C ––– –––– C n O –– + (2n – 1) H2O
Dacron (polyethylene terephthalate)
(ii) Similarly Nylon – 6, 6 is a condensation polymer.

O O
n HO – C – (CH2)4 – C – OH + n H2N – (CH2)6 – NH2

Adipic acid Hexamethylenediamine
Polymerization
O O
(2n – 1) H2O + C – (CH2)4 – C – NH – (CH2)6 – NH n
Nylon – 6, 6
E. Classification based on molecular forces :
Depending on the magnitude of intermolecular forces like hydrogen bond, van der Waals
forces and dipole–dipole interactions existing between the adjacent polymer chains, the polymers
can be classfied into four categories. These are :
(a) Elastomers : Polymers in which the intermolecular forces of attraction between the
polymer chains are the weakest resulting with high degree of elasticity are called
elastomers.
Elastomers are amorphous polymers consisting of randomely coiled molecular chains of
irregular shape having a few cross links. Under the application of an external force, these
randomly coiled chains straighten out and the polymer is stretched. But as soon as the
force is withdrawn, because of very weak van der Waal forces of attraction, the polymers
return to its original randomly coiled state. Thus, whereas weak van der Waals forces of
attraction permit the polymer chains to be stretched, the cross links help the polymer to
come back to the original position when the force is withdrawn. (Fig. 23.2)
POLYMERS 727
Cross lines
Cross links
Strech
Relax
Cross links
Unstretched Stretched
Fig. 23.2 : Unstretched and stretched forms of an elastomer
Most important examples of elastomers are buna-S, buna-N, neoprene etc.
(b) Fibres : Fibres are the thread forming polymers possessing very high tensile strength,
high modulus, but least elasticity which are attributed due to very strong inter molecular
forces of attractions like hydrogen bonding or dipole interactions (Fig. 23.3)
Most important examples are polyamides (nylons), polyesters (terylene, dacron) and
polyacrylonitrile (orlon, acrilan).
H O H
N C N
C N C
O H O
H O H
N C N
C N C
O H O
Fig. 23.3: Hydrogen bonding in Nylon-6,6

(c) Thermoplastic polymers : Thermoplastic polymers are the linear or slightly branched
long chain molecules which can be easily softened repeatedly on heating and hardened
on cooling with little change in their properties because of the inter molecular forces
being intermediate between elastomers and fibres.
When heated these polymers melt and form a fluid which can be moulded into any
desired shapes and then cooled to get the desired product.
Some common examples of thermoplastics are polythene, polypropylene, polystyrene,
polyvinyl chloride, teflon, polyacrylonitrile etc.
(d) Thermosetting polymers : Thermosetting polymers are semi-fluid substances with low
molecular masses which when heated in a mould undergo change in chemical composition
to give a hard, infusible and insoluble mass due to extensive cross-linking between
different polymer chains to give a three-dimensional network solid. (Fig. 23.4).
heat
Uncrosslinked polymer Highly cross-linked polymer
Fig. 23.4 : Conversion of uncrosslinked polymer into highly

cross-linked thermosetting polymer on heating.
In contrast to thermoplastic polymers thermosetting polymers can be heated only once
as these undergo prermanent change on melting and set into a new solid which can not
be remelted. Thus these can not be reused. Common examples are : phenol-formaldehyde
resins (bakelite), urea-formaldehyde resins etc.
F. Classification based on the basis of degradability of polymers by micro-organisms:
Polymers may be classified into biodegradable polymers and non-degradable polymers
on the basis of their degradability by micro-organisms.
(a) Biodegradable polymers : These are the polymers which are degraded by micro-
organisms during a certain period thus not posing any threat to our environment.
Some new biodegradable synthetic polymers have been designed and developed
containing functional groups similar to the functional groups present in biopolymers.
Biopolymers like starch, cellulose etc. disintegrate themselves in biological systems during
a certain period of time by enzymatic hydrolysis and to some extent by oxidation and
hence are biodegradable. Hence they do not cause any pollution. Examples of
biodegradable polymers are :
(i) Poly b-hydroxybutyrate-co-b-hydroxyvalerate (PHBV) : It is a copolymer of
3-hydroxybutanoic acid and 3-hydroxypentanoic acid in which two monomer units
are connected by ester linkages.
OH OH
n CH3 – CH – CH2 – COOH + n CH3 – CH2 – CH – CH2 – COOH

3-Hydroxy butanoic acid 3-Hydroxypentanoic acid
POLYMERS 729
O – CH – CH2 – C – O – CH – CH2 – C – O + (2n – 1) H2O

n
CH3 O CH2CH3 O
PHBV
PHBV is used in special packaging, orthopaedic devices and in controlled drug
release. When a drug is enclosed in a capsule of PHBV, it is released only when the
polymer is degraded in the body.
(ii) Poly-Glycollic acid - Poly Lactic acid : This is a copolymer of glycollic acid and
lactic acid, commercially called dextron. This was the first biodegradable polyester
used as sutures, that is for stitching of wounds after operation.
n HO – CH2 – COOH + n HO – CH – COOH
Glycollic acid
CH3
Lactic acid
Polymerization
O – CH2 – C – O – CH – C – O + (2n – 1) H2O

n
O CH3 O
(iii) Nylon 2 - Nylon 6 : It is an alternating copolymer of glycine and e-aminocaproic

acid and is biodegradable.
n H2N – CH2 – COOH + n H2N – (CH2)5 – COOH
Glycine e-amino caproic acid
HN – CH2 – C – NH – (CH2)5 – C + (2n – 1) H2O

n
O O
Nylon 2 - Nylon 6
All the above polymers are plyesters and are therefore, susceptible towards
hydrolysis of their ester links. Hence these are completely degraded and absorbed
by the body within 15 days to one month for which these are mainly used for
medical goods such as surgical sutures, tissue in growth materials or for controlled
drug release devices, plasma substitutes etc.
(b) Non-degradable polymers : The polymers which are not degraded by micro-organisms
within a suitable period and seriously affect the environment leading to environmental
pollution are called non-degradable polymers.
Most of the commercially synthesized polymers like polythene, PVC, teflon, nylons,
polyesters, bakelite etc are the examples of non-degradable polymers.
23.3 GENERAL METHODS OF POLYMERIZATION :

The process of polymerization can be carried out by two methods.
A. ADDITION POLYMERIZATION :
The type of polymerization involving successive addition of monomer units to the growing
chain with a reactive intermediate such as a free radical, a carbocation or a carbanion is termed
as addition polymerization. This can also be termed as chain growth polymerization as after
each act of addition of monomer the reactive intermediate is regenerated leading to increase in
chain length.
The monomers used are unsaturated compounds like alkenes, alkadienes, and their
derivatives with free radical governed addition polymerization is the most common method.
(a) Free radical addition polymerization : Addition polymerization of alkenes or their
derivatives involves the chain reactions in which the chain carrier is a free radical formed
in the presence of a free radical generating initiator (catalyst) like benzoyl peroxide,
acetyl peroxide etc. This vinyl polymerization involves three steps.
(i) Initiation : The initiation of polymerization is a two step process. The first step is
the decomposition of the initiator to produce a free radical.
O O
D
C6H5 – C – O – O – C – C6H5 ¾¾®
Benzoyl peroxide
O
·
2 C6H5 – C – O · ® 2 C6H5 + 2 CO2
Bezoyloxy radical Phenyl radical
In the second step, the free radical interacts with the vinyl monomer to give rise the
initiated monomer radical.
· ·
C6H5 + CH2 = CH2 ® C6H5 – CH2 – CH2
Ethene
POLYMERS 731
(ii) Propagation : This step involves the addition of the new monomer radical to the
monomer molecules in rapid succession to form a growing polymer chain.
· ·
C6H5 – CH2 – C H2 + CH2 = CH2 ® C6H5 – CH2 – CH2 – CH2 – C H2
+ (n – 1) CH2 = CH2
·
C6H5 ( CH – CH
2 2 nCH2 – C H2
(iii) Termination : In the termination step, the growing chain radical deactivates either
by combination or by disproportionation to form a dead polymer.
Combination :
·
2 C6H5 ( CH – CH 2 2 n CH2 – C H2
C6H5 ( CH – CH
2 2 n CH2 – CH2 – CH2 – CH2 ( CH – CH
2 2 n C6H5
Polythene (Dead polymer)
Disproportionation :
·
2 C6H5 ( CH2 – CH2
n
CH2 – C H2
C6H5 ( CH – CH
2 2 n
CH = CH2 + C5H6 ( CH – CH
2 2 n CH2CH3
Dead polymers
(b) Cationic polymerization : Cationic polymerization takes place by the addition of a
positively charged ion to a vinyl monomer to form a carbocation as the reaction
intermedicate. The initiators used for the cationic polymerization include strong protic
acids like H2SO4 or Lewis acids like AlCl3, BF3 in the presence of water.
The reaction proceeds through three steps such as initiation, propagation and termination.
(i) Initiation : HB ® H+ + B–
Protic acid
+
H+ + CH2 = CH ® CH3 – CH
CH3 CH3
Propene
+ +
(ii) Propagation : CH3 – C H + CH2 = CH ® CH3 – CH – CH – C H
CH3 CH3 CH3 CH3

n CH2 = CH
CH3
+
CH3 – CH ( CH2 – CH
n
CH2 – C H
CH3 CH3 CH3

(iii) Termination : Transfer to counter ion
+
CH3 – CH ( CH – CH
2 n CH2 – C H + B
–
CH3 CH3 CH3
2 n
CH = CH + HB
CH3 CH3 CH3
Polypropene
Transfer to monomer :
+
2 n CH2 = C H + CH2 = CH
CH3 CH3 CH3 CH3
+
2 n CH = CH + CH3 – C H
CH3 CH3 CH3 CH3

(c) Anionic polymerization : Anionic polymerization involves the successive addition of
vinyl monomers to a negatively charged species known as carbanion as reaction
intermediate formed by the reaction of a negative ion or group to the monomer molecule.
The initiators used for the anionic polymerization are strong bases like potassium amide
or lithium amide. The steps involved are :
POLYMERS 733
(i) Initiation :
+– - - +
K NH2 + C H2 = CH ® H2N – CH2 – C H K
Cl Cl
(ii) Propagation :
- + - +
H2N – CH2 – C H K + CH2 = CH ® H2N – CH2 – CH – CH2 – C H K
Cl Cl Cl Cl
+ n CH2 = CH
Cl
- +
H2N – CH2 – CH ( CH – CH
2 n CH2 C H K
Cl Cl Cl
The most important aspect of the anionic plymerization is that the termination is
absent in this case. If inert solvents and pure reactants are used, the system will
result in the formation of carbanion end-group. Hence the anionic polymers are
also termed as living polymers.
B. CONDENSATION POLYMERIZATION :
Condensation polymerizaton is the type of polymerization involving the condensation
between two bifunctional monomers with the loss of simple molecules like H 2O, NH3, HCl etc.
leading to the formation of high molecular mass polymers.
The reaction regenerates a bifunctional species for which the sequence of condensation
goes on till any one of the reactants is totally consumed. This type of polymerization is therefore
termed as step growth polymerization.
The simplest example of the condensation polymer is the polyethylene terephthalate
(PET) formed by the condensation of ethylene glycol and terephthalic acid with the elimination
of water molecules.
n HOH2C – CH2OH + n HOOC–– –– COOH

– (2n –1) H2O
O O
O – CH2 – CH2 – O – C–– –– C
n
Polyethylene terephthalate (Terylene or Dacron)
23.4 COPOLYMERIZATION :
A polymer consisting of two or more chemically different types of monomer units in the
chain is called a copolymer and the process of synthesis of copolymer is called copolymerization
which may be a chain growth polymerization or a step growth polymerization.
For example, a mixture of 1, 3 – butadiene and styrene can form a copolymer.
CH = CH2
n CH2 = CH – CH = CH2 + n
1, 3 – Butadiene Styrene
CH2 – CH = CH – CH2 – CH – CH2

n
Butadiene-styrene copolymer
The properties of copolymers are quite different from that of homopolymers. For example,
butadiene-styrene copolymer is quite tough and is a good substitute for natural rubber and is
used for the manufacture of floor tiles, cable insulation, autotyres etc.
Copolymers can be classified into four types basing on the distribution of different
monomers in the chain. Suppose A and B are two monomers.
(i) Random copolymers : These are the copolymers in which the monomers are randomly
arranged.
–A–B–A–A–A–B–B–A–
(ii) Alternating copolymers : In case of alternating copolymers the monomers are arranged
alternately in the chain.
–A–B–A–B–A–B–
(iii) Block copolymers : Block copolymers contain long sequence of monomers in a linear
chain.
–A–A–A–A–B–B–B–B–A–A–A–A–
(iv) Graft copolymers : Graft copolymers consist of main homopolymer chain with branches
of another type of homopolymer.
POLYMERS 735
–A–A–A–A–A–A–A
| |
B B
| |
B B
| |
B B
| |
B B
| |
23.5 SOME IMPORTANT POLYMERS :

A. POLYTHENE :
It is a polymer of ethylene. Two types of polythenes can be synthesized depending on the
conditions of synthesis with different types of intiators having widely different properties. These
are :
(a) Low density polythene : The low density polythene is manufactured by heating pure
ethylene to 350 - 570 K under pressure of 1000 - 2000 atmospheres and in presence of a
trace of oxygen or peroxide following free radical mechanism.
It consists of highly branched chain molecules, for which these molecules do not pack
well resulting with low density and low melting point. Low density polythene is a
transparent polymer of moderate tensile strength and high toughness. It is mainly used
(i) as a packing material in the form of thin plastic film bags (ii) for insulating wires and
cables, and (iii) in manufacturing toys, squeeze bottles and flexible pipes.
350 - 570 K
n CH2 = CH2 ~~~ CH2 – CH – CH2 – CH2 ~~~
1000 - 2000 atm
|
Ethene CH2
|
CH2
Low density polythene

(b) High density polythene : High density polythene is prepared by co-ordination
polymerization where ethene is heated to 330 – 350 K under a presure of 6–7 atmospheres
in the presence of a catalyst consisting of triethyl aluminium and titanium tetrachloride
(Ziegler-Natta catalyst).
330 – 350 K, 6 – 7 atm.

n CH2 = CH2
(Et)3 Al + TiCl4
( CH – CH
2 2 n
High density polythene

This polymer consists of linear chains, for which the molecules can be closely packed in
space resulting in very high density and high melting point. It is quite harder, tougher
and has greater tensile strength than low density polythene.
It is used for (i) manufacturing containers like buckets, dustbins, bottles etc and (ii)
manufacturing different housewares, pipes etc.
B. POLYACRYLONITRILE (PAN) OR ORLON :
Vinyl cyanide (acrylonitrile) on polymerization in the presence of a peroxide catalyst
results in the formation of polyacrylonitrile.
CN
Polymerization
n CH2 = CHCN
Peroxide catalyst
(CH2 – CH n
Acrylonitrile Polyacrylonitrile
PAN also known as acrilon or orlon is used for (i) making blankets, sweaters, bathing
suits etc. (ii) for making synthetic carpets.
C. POLYTETRAFLUOROETHYLENE (PTFE) OR TEFLON :
Telfon is an addition polymer of tetrafluoroethylene formed on heating in the presence
of a free radical initiator at high pressure.
Catalyst
n CF2 = CF2
Heat, High pressure
( CF – CF
2 2 n
Tetrafluoroethene Teflon
Teflon is a very tough meterial and is resistant towards heat, action of chemicals such as
acids and bases. it is used:
(i) as material resistant to heat and chemical attack
(ii) for coating articles and cookware to make them non-sticky as non-sticky utensils.
(iii) for making gaskets, pump packings, valves, seals etc.
D. POLYAMIDES OR NYLONS
Polyamides with amide linkages (– CO – NH –) in the chain are formed by the
condensation polymerization of diamines with dibasic acids and also of amino acids and their
lactams. Polyamides popularly known as nylons are of different types as follows :
(a) Nylon - 6, 6 : Nylon - 6, 6 can be prepared by heating equimolar mixture of hexamethylene
diamine and adipic acid under high pressure. It is given the name nylon - 6, 6 since both
hexamethylene diamine and adipic acid contain six carbon atoms each.
POLYMERS 737
n H2N – (CH2)6 – NH2 + n HOOC – (CH2)4 – COOH

Hexamethylene diamine Polymerization Adipic acid
553K
High pressure
O O
( NH – (CH ) – NH – C – (CH ) – C
2 6 2 4 n + (2n – 1) H2O
Nylon – 6, 6
Nylon - 6, 6 is used for making tyre cord, fishing nets, climbing ropes, strings for sports
rackets and bristles for brushes.
(b) Nylon - 6 : Nylon -6 can be synthesized by heating caprolactam with water at a high
temperature.
N
|
H
H2C C=O O H
H2O
533 – 543K
( C – (CH ) – N
2 5 O–
H2C CH2
Nylon - 6
H2C CH2
Caprolactam
Nylon - 6 is used for the manufacture of ropes, tyre cords and fabrics.
E. POLYESTERS : O
Polyesters are the polymers with ester linkages (– C – O –) which can be formed by the
condensation of dicarboxylic acids with diols.
Dacron or terylene is the best example of polyester, being prepared by the condensation
of ethylene glycol and terephthalic acid with elimination of water at 420 – 460 K in the presence
of a catalyst consisting of a mixture of zinc acetate and antimony trioxide.
O O
n HO – CH2 – CH2 – OH + n HO – C –– –– C – OH
Polymerization 420 – 460 K

O O
( O – CH – CH – O – C ––
2 2 –– C n + (2n – 1) H2O
Terylene or Dacron
It is used for (i) making textile, sarees, dress materials and curtains.
(ii) making sails of sail-boats.
(iii) making water houses for fire-fighting operations.
(iv) making conveyor belts.
F. PHENOL-FORMALDEHYDE RESIN (BAKELITE) :
When phenol reacts with formaldehyde in the presence of either an acid or a base catalyst,
polymer of high molecular mass is obtained. The process starts with the initial formation of
ortho and para hydroxymethyl phenol derivatives which further react with phenol to form
compounds having rings joined to each other through methylene bridges resulting initially with
a linear polymer called Novolac.
OH OH OH
CH2OH
H+
+ HCHO +
or OH–
o-Hydroxybenzyl CH2OH
alcohol p-Hydroxybenzyl
alcohol
OH OH OH
CH2OH CH2 CH2
Polymerization
Novolac
Novolac an heating with formaldehyde undergoes cross linking to form an infusible

solid mass called Bakelite.
D
Novolac + n HCHO
– n H2O
OH OH OH
H2C CH2 CH2 CH2
CH2 CH2 CH2
H2C CH2 CH2 CH2
OH OH OH
Bakelite
POLYMERS 739
Bakelite is used for

(i) making combs, fountain pen barrels, gramophone records etc.
(ii) making electrical goods like switches, plugs etc.
G. RUBBER
(a) Natural Rubber : Rubber is a natural linear polymer of isoprene (2-methy - 1, 3 -
butadiene)
CH3 CH3
Polymerization
n CH2 = C – CH = CH2 ¾¾ ¾ ¾ ¾ ¾¾® ( CH – C = CH – CH
2 2 n
Isoprene Poly isoprene
In polyisoprene each repeating unit contains a double bond, it exhibits cis-trans isomerism.
Natural rubber has all cis-configuration having weak van der Waals interactions between
various chains thus resulting with a coiled structure. Hence natural rubber can be stretched
like a spring and exhibits elastic properties.
CH3 H
CH2 CH2 C=C CH2 CH2
C=C CH2 CH2 C=C
CH3 H CH3 H
Cis-polyisoprene
(Natural rubber)
In contrast synthetic rubber (gutta percha) obtained by free radical plymerization isoprene
has all trans-configurations.
CH2 H
C=C CH2 H
CH3 CH2 C=C CH2 H
CH3 CH2 C=C
CH3 CH2
Trans-isoprene
(Gutta-percha)
Vulcanization of rubber :
The process of heating natural rubber with sulphur and an appropriate additive like zinc
oxide at temperature 373K to 415K to improve its properties is called vulcanization.
The vulcanized rubber has excllent elasticity, low water absorption tendency and resistant
to the action of organic solvents and oxidising agents in contrast to the natural rubber
which is soft and sticky, having high water absorption capactiy, low tensile strength and
resistance to abrasion.
During vulcanization linear chains of isoprene units present in natural rubber get cross-
linked through sulphur bridges at the allylic positions, which make rubber hard and
stronger removing sticky quality of the natural rubber since the individual chains can no
longer slip over the other because of locking together in a giant size molecule.
The structures of vulvanized rubber can be represented as :
CH3 CH3
CH2 C CH CH2 CH C = CH CH2
S S S
CH2 C CH CH2 CH C = CH CH2
CH3 CH3
The extent of hardness or toughness depends on the amount of sulphur added. For making
tyre rubber 5% sulphur is used, whereas for ebonite 20 – 25% sulphur and for making
battery case rubber 30% sulphur is used.
(B) Synthetic Rubber :
(i) Cis-polybutadiene : Polymerization of 1, 3-butadiene in the presence of Zeigler - Natta
catalyst results with cis-polybutadiene having properties similar to that of natural rubber.
It is used for making footwear, tyres and toys etc.
n CH2 = CH – CH = CH2 ¾Zeigler - Natta catalyst

¾ ¾¾ ¾ ¾¾ ¾ ¾¾® CH2 CH2
1, 3 - Butadiene (C2H5)3 Al + TiCl3
C=C
H H n
Cis - 1, 4 - Polybutadiene
POLYMERS 741
(ii) Neoprene : Neoprene is prepared by the free radical polymerization of chloroprene (2-
chloro -1, 3- butadiene).
Cl Cl
Polymerization
n CH2 = C – CH = CH2 ¾¾ ¾ ¾ ¾ ¾¾® (
CH2 – C = CH – CH2 n
Chloroprene Neoprene
Neoprene is used
(i) for manufacturing hoses, shoes heel, stoppers etc as it is resistant to oils, gasoline
and other solvents and stable towards aerial oxidation.
(ii) as an insulator.
(iii) for making conveyer belts and printing rollers.
(iii) Buna-N : Buna-N is a copolymer of 1, 3-butadiene and acrylonitrile prepared by free
radical polymerization.
n CH2 = CH – CH = CH2 + n CH2 = CH
1, 3- Buadiene Acrylonitrile
CN
Polymerization
( CH – CH = CH – CH – CH – CH
2 2 2 n
CN
Buna - N is used for making oil seals, manufacture of hoses and tank linings.
(iii) Buna-S : It is a copolymer of 1, 3 butadiene and styrene.
n CH2 = CH – CH = CH2 + n CH2 = CH
1, 3 - Butadiene Styrene
Polymerization
( CH – CH = CH – CH – CH – CH
2 2 2 n
Buna - S
It is used for the manufacture of automobile tyres, rubber soles, water proof shoes, belts
etc.
1. Polymers are macromolecules built up by repeating structural units joined by the

covalent bonds, whereas all macromolecules are not polymers.
2. Monomers are the simple raw materials (molecules) from which polymers are
synthesized.
3. Polymers can be classfied on different basis i.e. natural or synthetic, homopolymer
or copolymer, linear or branched chain polymer etc.
4. The process of polymerization may be addition polymerization or chain growth
polymerization and condensation polymerization or step growth polymerization.
5. Polythene, polystyrene, teflon, orlon etc are examples of addition polymers where
as Nylon, Bakelite and Dacron are the examples of condensation polymers.
6. Bifunctionality is the minimum criterion for a molecule to act as monomer.
7. Natural rubber is a cis-1,4-polyisoprene the properties of which can be modified by
vulvanization process on heating with sulphur. Neoprene, Buna-S & Buna-N are the
examples of synthetic rubbers.
8. In order to avoid the hazardous effect of polymeric wastes, biodegradable polymers
like PHBV, Nylon-2, Nylon-6 have been synthesized successfully.
QUESTIONS
A. VERY SHORT QUESTIONS (1 mark each) :
(a) Bakelite is formed by the chemical combination of phenol and ––––.
(b) Name the linkage (bond) prevailing in the proteins.
(c) Write any two uses of Neoprene.
(d) Mention two uses of Buna-S.
(e) What is Buna-N?
(f) What is neoprene?
(g) Name the monomer used for the preparation of Teflon.
(h) What is PHBV?
(i) What is a copolymer?
(j) Name the monomer of Nylon-6
(k) What are thermosetting polymers?
(l) Name the monomers used for Novolac.
(m) What are the monomers required for terylene?
(n) Define the term polymerization.
POLYMERS 743
B. SHORT ANSWER QUESTIONS (2 marks each) :

(a) What are polymers ? Give two examples.
(b) What is Tefflon ? Give one of its uses.
(c) What is natural rubber? Why it can not be used for making foot-ball bladders?
(d) What is terylene? How is it prepared?
(e) What are biodegradable polymers? Give two examples.
(f) What is Nylon-6, 6? How is it prepared?
(g) What are natural and synthetic polymers? Give one example of each.
(h) What do you mean by vulvanization of rubber?
(i) Define copolymerization and give one example.
(j) What do you mean by free radical polymerization ? Name one initiator used for it.
C. SHORT ANSWER QUESTIONS (3 marks each) :

Distinguish between
(a) Thermoplastic and thermosetting polymers.
(b) Homopolymers and copolymers.
(c) Natural rubber and synthetic rubber.
(d) Addition polymerization and condensation polymerization.
(e) Nylon-6 and Nylon-6, 6
(f) Buna-N and Buna-S
(g) Novolac and Bakelite
D. LONG QUESTIONS (7 marks each) :

(a) What are polymers ? What are the different methods of their preparation? Name
an important polymer and describe a method of its preparation with chemical
equation.
(b) What are polymers? How are they classified on the basis of
(i) structure (ii) synthesis and (iii) molecular forces involved. Give one example of
each kind.
(c) What are natural rubbers and what are synthetic rubbers? What is vulcanisation?
How does it improve the characteristics of rubbers?
(d) What is free radical addition polymerization? What are the intiators used for it?
Discuss the mechanism of free radical polymerization taking one example.

1. Chloroprene is the repeating unit in
(a) PVC (b) Polythene
(c) Neoprene (d) Polystyrene
2. Orlon is a polymer of
(a) Vinyl chloride (b) Styrene
(c) Butadiene and adipic acid (d) Acrylonitrile
3. Which of the following is a condensation polymer?
(a) Teflon (b) Bakelite
(c) Buna-S (d) Neoprene
4. Natural rubber is a polymer of
(a) Acrylonitrile (b) Isoprene
(c) Vinyl chloride (d) Tetrafluoroethylene
5. Which of the following is not a condensation polymer?
(a) Bakelite (b) Nylon
(c) Dacron (d) Teflon
6. Teflon is a type of
(a) Condensation polymer (b) Synthetic rubber
(c) Addition polymer (d) None of these
7. Which of the following is synthetic rubber?
(a) Buna-S (b) Polyisoprene
(c) Dacron (d) None of these
8. Which is naturally occurring polymer?
(a) Rayon (b) Nylon
(c) Protein (d) PVC
9. Which of the followings is called a polyamide?
(a) Rayon (b) Terylene
(c) Nylon (d) Teflon
10. A raw material used in making nylon is
(a) Adipic acid (b) Butadiene
(c) Ethylene (d) Methyl methacrylate
11. Teflon is a polymer of
(a) Monofuoroethene (b) Difluoroethene
(c) Trifluoroethene (d) Tetrafluorethene
12. Which of the following is used to make non-stick cookware?
(a) PVC (b) PET
(c) Teflon (d) Nylon
POLYMERS 745
13. Nylon-6,6 is obtained from

(a) Propene and adipic acid (b) Phenol and formalehyde
(c) Hexmethylene diamine and (d) Adipic acid and phthalic acid
adipic acid
14. Nylon-6 is made from
(a) 1, 3 - Butadiene (b) Chloroprene
(c) Adipic acid (d) Caprolactam
15. Baby feeding bottles are generally made up
(a) Polystyrene (b) Polyurethane
(c) Polyamide (d) Polyester
16. Teflon, styrene and neoprene are all
(a) Monomers (b) Homopolymers
(c) Copolymers (d) Condesation polymers
ANSWER FOR MULTICPLE CHOICE QUESTIONS
1. (c) 2. (d) 3. (b) 4. (b) 5. (d) 6. (c) 7. (a) 8. (c) 9. (c) 10. (a)
11. (d) 12. (c) 13. (c) 14. (d) 15. (a) 16. (b)
qqq
UNIT - XVI
CHAPTER - 24
CHEMISTRY IN EVERYDAY LIFE
24.1 INTRODUCTION :
Life without Chemistry is totally impossible, because the basic needs of human being
i.e. food, cloth and shelter involve the basic principle of Chemistry. Thus Chemistry has played
a vital role in everyday life. For example, clothes like wool, silk, cotton, nylon etc. we wear,
soaps and detergents used to wash them are all organic compounds. The food (carbohydrates,
proteins, oils and fats etc.) we eat to nourish and build up our body are organic in nature. The
house where we live uses cement, paints, adhesives, marbles etc., all involving the chemical
processes. The medicines protecting us from diseases like antibiotics, sulphadrugs etc. are also
boon of Chemistry. So the basic principles of Chemistry have influenced every sphere of human
life.
24.2 CHEMICALS IN MEDICINE :
Chemical substances of natural or synthetic origin used for curing diseases and reducing
suffering from pain are called medicines or drugs. The branch of science which deals with the
treatment of diseases using suitable chemicals is known as chemotherapy.
Though all drugs are medicines and all medicines are drugs, medicine is safer to use
having negiligible toxicity without causing addiction, whereas drug causes addiction with serious
side effects.
Medicines are generally classified basing on the purpose for which they are used. Different
classes of medicines are :
A. ANALGESICS
An analgesic may be defined as a drug that selectively relieves pain by acting on the
central nervous system and on peripheral (external) pain mechanisms without significantly altering
consciousness. Simply analgesics may be referred to the medicines used for getting relief form
pain.
Analgesics are categorized into two classes :
CHEMISTRY IN EVERYDAY LIFE 747
(a) Narcotics : Drugs which produce sleep and unconsciousness are called narcotics,
and are mainly used for the relief of post-operative pain, cardiac pain, pains of terminal cancer
and in child birth.
Narcotic analgesics are mostly opium products which contains morphine and codeine.
These are very effictive analgesics, but regular doses cause addiction. Other examples are heroin
and marijuana.
HO H3CO
NCH3 NCH3
H
HO HO
MORPHINE CODEIN
(b) Non-narcotics : Regular doses of this type of analgesics do not cause addiction.
They give temporary relief from pain and possess anti-inflammatory property. Examples of non-
narctoic analgesies are aspirin, analgin and paracetamol.
H3C C N CH3
OCO CH3 HN C N C6H5
COOH + C
CH2SO3Na HO NHCOCH3
O
ASPIRIN ANALGIN PARACETAMOL
There have antipyretic properties also. Aspirin is the commonly used analgesic which
gives relief from headache, muscular pain and toothache. The toxic side effect of using aspirin is
gastric irritation leading to ulceration. Thus it should not be administered in empty stomach. But
its calcium salt i.e. DISPRIN which is water soluble, is better than Aspirin having few side
effects. Because of the side effects other analgesics like ibuprofen, naproxen are now being
used. However because of anti blood clotting action af aspirin, it is still the drug of choice for
prevention of heart attacks and reliever of angina pains.
B. TRANQUILIZERS
Tranquilizers may be defined as the neurologically active drugs which help in reducing
stress and fatigue by inducing a sense of well being.
These affect the message transfer mechanisms from nerve to receptor for which they are
used for the treatment of mild or even severe mental diseases. They form an essential component
of sleeping pills.
Tranquilizers are of different types. Such as :
(a) Sedatives : These drugs are suitable for violent patients who are mentally upset.
Examples are calmpose and equanil.
CH3 O
N C O CH3 O
H2N –– C –– O –– CH2 –– C –– CH2 –– O –– C –– NH2

N
Cl
C3H7
EQUANIL
CALMPOSE
(b) Antidepressants : These drugs are also called mood elevators, which are given to
those patients who lose self-confidence and are much depressed, thus improving their efficiency.
Examples are amphetamine and methamphetamine.
CH2 –– CH –– NH2 CH2 –– CH –– NHCH3

CH3 CH3
AMPHETAMINE METHAMPHETAMINE
(Benzedrine) (Methedrine)
(c) Hypnotics : Luminal and Seconal are some important hypnotics producing sleep
which are the derivative of barbituric acid called barbiturates. These are habit forming drugs.
O H O H
C2H5 C N H2C = HC – CH2 C N

C C=O C C=O
C2H5 C N H3C – CH2 – CH2 – CH C N
O H CH3 O H
LUMINAL SECONAL
C. ANTISEPTICS AND DISINFECTANTS :

Antiseptics and disinfectants are the chemicals which either kill or prevent the growth of
micro-organisms.
(a) Antiseptics : Antiseptics are applied to the living tissues such as wounds, cuts, ulcers
and diseased skin surface in order to kill or prevent the growth of micro-organisms in the form of
antiseptic creams like furacin, soframycin etc.
Antiseptics has the ability to reduce the odour produced as a result of bacterial
decomposition of organic matter on the body or in the mouth for which they are added to face
powders and breath purifiers.
More examples of antiseptics are :
(i) Dettol, most commonly used antiseptic, is a mixture of chloroxylenol and terpineol.
CH3
CH3
Cl
H3C OH H3C OH
CH3
CHLOROXYLENOL
TERPINEOL
(ii) Bithional is added to soaps to impart antiseptic properties to reduce the odour
produced by bacterial decomposition of organic matter on the skin.
(iii) Iodine is a very powerful antiseptic used as tincture of iodine which is 2–3%
solution of iodine in alcohol and water.
(iv) Very dilute aqueous solution of boric acid is used as a mild antiseptic for eye
wash.
(v) Iodoform is used as antiseptic powder for wounds.
(vi) 2–5% mercurochrome solution is a very good antiseptic for skin, mucous surfaces
and wounds.
(vii) Salol is used as an intenstial antiseptic for throat ailments.
(b) Disinfectants : Disinfectants are the chemical substances which kill micro-organisms
but are not safe to be applied to the living tissues, but can be applied to abiotic objects such as
floors, drains, toilets, instruments etc. Examples are :
(i) Solution of cresols : (i.e. o–, m– and p– methyl phenols) in soapy water is called
lysol which is used as a disinfectant.
(ii) Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution is a disinfectant.
(iii) SO2 in very low concentration acts an disinfectant.
(iv) One percent solution of phenol is disinfectant whereas 0.2 percent solution acts as
an antiseptic.
D. ANTIMICROBIALS
Antimicrobials are defined as the drugs used to destroy or prevent development or inhibit
the pathogenic action of micro-organisms such as bacteria, viruses, fungi or other parasites.
Microbial diseases can be controlled by the following ways :
(i) By using a bactericidal drug which kills the organisms in our body.
(ii) By checking the growth of organisms using a bacteriostatic drug.
(iii) By improving the resistance power of the body towards infection i.e. increasing
the immunity power.
Examples of antimicrobial drugs are
(i) antibiotics- Penicillin, Tetracycline, Ofloxacin
(ii) Sulpha drugs - Sulphanilamide, Sulphapyridine.
O H H S
|| CH3
C6H5 – CH2 – C – NH
CH3 H2N SO2NH2
N COOH
O Sulphanilamide
H
Pencillin - G
E. ANTIBIOTICS
The term antibiotic has been derived from the word "antibiosis" which means survival of
fittest i.e. a process in which one organism may destroy another to preserve itself. That means
antibiotics are chemical substances produced by or derived from living cells which is capable in
small concentration of inhibiting the life proceses or even destroying the micro-organisms.
But with development of synthetic methods producing compounds which are same as
derived from micro-oganisms, the definition of antibiotics needs modification.
An antibiotic is now defined as the chemical substance produced wholly or partially by
chemical synthesis, which in low concentration either kills or inhibits the growth of
micro-ogranisms by intervening in their metabolic processes.
I. Conditions for a chemical substance to be an antibiotic :

All chemical substances produced by or derived from living cells can not be antibiotics.
These have to satisfy the following conditions.
(i) Antibiotics must be a product of metabolism although it might have been
synthesized.
(ii) If the antibiotic is a synthetic product, it should be a structural analogue of naturally
occurring antibiotic.
(iii) It must be effective at low concentrations.
(iv) In order to act as therapeutic agent, it must have the following characteristics.
(a) It must be effective against a pathogen.
(b) It should not have any toxic side effects.
(c) It should be stable and can be stored for a longer time.
II. Classification of anibiotics :
(a) Basing on their action on micro-organism antibiotics are of two types:
(i) Bactericidals which kill the organisms in the body. Examples : Penicillin,
Ofloxacin.
(ii) Bacteriostatic which checks the growth of micro-organisms. Examples :
Erythromycin and Tetracycline.
(b) The broad based classification of antibiotics classifies them into two types :
(i) Broad spectrum antibiotics : These include the antibiotics which are
effective for a number of microbial diseases.
Examples are penicillin, chloramphenicol etc.
(ii) Narrow spectrum antibiotics : These are the antibiotics which are highly
specific in their action. Examples are bacitracin and nystatin.
(c) On the basis of the type of bacteria the antibiotic can destroy, the antibiotics are of
two types. These are :
(i) Gram positive bacteria and
(ii) Gram negative bacteria.
III. Examples of antibiotics :
(i) Penicillin : The first antibiotic penicillin was discovered by Alexander Fleming in
1929, who along with H.W. Florey received Nobel Prize for medicine in 1945 for
their contribution to the development of penicillin.
Penicillin can not be taken orally. To persons who are allergic, it can cause fatal
coma. The general structure of pencillins can be represented as :
O
|| H H S CH3
R – C – NH
CH3
N COOH
O
For Penicillin - G R = – CH2 – C6H5

and Penicillin - V R = – CH2 – O – C6H5
Penicillin is very much effective for pneumonia, bronchitis, sore throat, and other
infectious diseases caused by various cocci and some gram positive bacteria.
(ii) Streptomycin : Streptomycin is a very effective drug for the treatment of
tuberculosis, meningitis, pneumonia and also for common infections like throat,
lungs etc.
(iii) Tetracyclines : Terramycin and Auromycin are the best examples of tetracyclines,
which are highly effective against a number of bacteria, viruses, protozoa, parasites
etc. Unlike penicillin and streptomycin tetracyclines can be taken orally as these
are absorbed from the gastrointestinal tract. Due to this advantage streptomycin is
largely replaced by tetracyclines.
(iv) Chloramphenicol (Chloromycetin) : As an antibiotic chloramphenicol is having
certain advantages over others. These are :
(a) Chemically it is the first antibiotic to be synthesized on a commercial scale.
(b) It can be taken orally and very effective in the treatment of typhoid, dysentry,
acute fever, urinary infections, meningitis and pneumonia.
(c) It is the first natural compound found to contain a nitro group and the presence
of –CHCl2 group is most unusual.
NHCOCHCl2
O2N CH –– CH –– CH2OH
OH
CHLORAMPHENICOL
F. ANTIFERTILITY DRUGS
Antifertility drugs may be defined as the chemical substances which are used to check
pregnancy in women having control over the female menstrual cycle and ovulation.
Rising social problems like environmental pollution, insufficient food resources,
unemployment etc. due to high population growth have become serious global problems which
gave birth to the idea of family planning which is possible by birth control pills or oral
contraceptives.
These antifertility drugs contain a mixture of synthetic estrogen and a progesterone
derivative which are more potent than the natural hormones. For example, a common brand
name Enovid E contains norethindrone (a progesterone derivative) and mestranol (an estrogen).
However all these drugs have side effects and should be used only under doctor's advice.
OH OH
CH3 CH3
C º CH C º CH
H H H
H H
O H3CO
Norethindrone Mestranol
Mifepristone the synthetic steroid is now widely used as "morning after pill" that blocks
the effects of progesterone.
CH3
N
H3C OH
CH3 C º C – CH3
Mifepristone
G. ANTACIDS
Antacids are defined as the chemical substances which neutralize the acid secreted in the
stomach and raise the pH to an appropriate level.
The most common disease now the people are suffering is gastritis, which is due to the
presence of excess hydrochloric acid in the gastric juice. Over productions of acid in the stomach
causes irritation and pain with the development of ulcers. The various antacids used to check the
gastritis are :
(i) Sodium hydrogen carbonate. But excessive use of it may make the stomach
alkaline and accelerates the production of more acid.
(ii) Metal hydroxides:- a mixture of aluminium and magnesium hydroxide.
(iii) The drug cimetidine (Tegamet) was a better invention in the field of antacids as it
prevents the interaction of histamine which actually stimulates the secretion of
pepsin and hydrochloric acid in the stomach, with the receptors present in the
stomach wall resulting in the production of low amount of acid.
(iv) Now another drug ranitidine (Zantac) has now prevailed in the medicinal field as
a very effective antacid.
(v) Recently omeprazole and lansoprazole have been used as antacids preventing the
formation of acid in the stomach.
CH3
HN HN N – CN
S C
N
N NH2 N NH CH3
Histamine Cimetidine H
H3C CHNO2
N S C
H3C N
O NH CH3
Ranitidine H
H
N O N
S CH3
N
CH3 OCH3
Omeprazole
H
N O N
S
N
CH3 OCH2CF3
Lansoprazole
H. ANTIHISTAMINES
Antihistamines are defined as the antiallergy drugs used to treat allergy such as skin
rashes, inflammation of tissues, asthma and itching of hives due to the release of histamine is the
body.
Histamine is a potent vasodilator with various functions. These are :
(i) It contracts the smooth muscles in the bronchi and gut and relaxes other muscles,
such as those in the walls of fine blood vessels.
(ii) It is also responsible for the nasal congestion associated with common cold.
Antihistamines work on different receptors for which these are completely different from
antacids. They interfere with the natural action of histamine by competing with histamine for
binding sites of receptor where histamine has its impact. These are mainly used for treatment of
(i) hay fever
(ii) conjuctivitis
(iii) seasonal rhinitis (inflammation of nasal mucosa) i.e. sneezing, nasal discharge
(iv) itching of eyes, nose and throat
(v) nausea in pregnancy
(vi) post operative vomiting.
Commonly used antihistmine drugs are : diphenylhydramine, cetrizine, promethazine,
brompheniramine (Dimetapp) and terfenadine (Seldane).
CH3
CH3
CH2 – CH – N
C6H5 CH3
CH3
CH – O – CH2 – CH2 – N N
C6H5 CH3
Diphenylhydramine
S
Promethazine
N
N
N
Br Ph OH
Brompheniramine HO
(Dimetapp) Ph Terfenadine (Seldane)
24.3 CHEMICALS IN FOOD :

All those chemicals which are added to food to improve its shelf life, taste, appearance,
odour and nutritive (food) value are termed as food additives. Main types of food additives are:
(i) preservatives
(ii) food colours
(iii) flavouring agents
(iv) artificial sweetners
(v) antioxidants
(vi) fortifiers
(vii) emulsifiers
(viii) antifoaming agents
(ix) nutritional supplements such as minerals, vitamins and amino acids.
I. PRESERVATIVES
Preservatives may be defined as the chemicals which are capable of inhibiting or arresting
the process of fermentation, acidification or other decomposition of food caused by bacteria,
yeasts and moulds.
(a) Preservatives used in a common man's house are salt, sugar, spices and oil to check
the growth of micro-organisms in food.
(i) The preservation of food like raw mango, amla, fish, meat etc by adding excess
salt is called salting which prevents the availability of water for bacterial growth.
(ii) Sugar syrup is used for the preservation of fruits like mango, apples, carrot etc,
which checks the growth of micro-organisms by dehydrating them.
(iii) Oil and spices are commonly used as preservaties for pickles, jams, squashes etc.
(b) Sodium benzoate : Sodium benzoate is used as preservative in soft drinks and acidic
foods. It is metabolized by conversion into hippuric acid, C 6H5CONHCH2COOH which is
ultimately excreted in urine.
(c) Sodium metabisulphite (Na2S2O5) : Sodium or potassium metabisulphite is used as
a preservative for pickles, jams and squashes. Its preservative action is due to SO 2 which dissolves
in water to give sulphurous acid.
Na2S2O5 ® Na2SO3 + SO2
SO2 + H2O ® H2SO3
Sulphurous acid inhibits the growth of yeasts, moulds and bacteria.
(d) Epoxides : Epoxides such as ethylene oxide and propylene oxide are used to preserve
low moisture foods such as spices, dried fruits and nuts. These foods are expossed to these
gaseous chemicals in closed chamber for sufficient time when all types of micro-organisms
including spores and viruses get killed.
(e) Sodium and Calcium propionate : These are used in bread and cakes to inhibit the
growth of moulds.
(f) Sorbic acid and its salts : Sodium and potassium sorbates are now used for controlling
the growth of yeasts and moulds in processed cheese, pickles, baked food items, certain meat
and fish products.
(g) p-Hydroxy benzoate esters : The methyl, ethyl, propyl and heptyl esters of p-hydroxy
benzoic acid are used to preserve baked food, beer, soft drinks and syrups. They are highly
effective in inhibiting the growth of moulds and yeasts but less effective on bacteria.
II. ARTIFICIAL SWEETENING AGENTS :
Most commonly used natural sweetners are sucrose and fructose which not only add to
our calorie intake, but also causes tooth decay. Particularly for diabetic patients who want to
control their sugar intake, calorie free artificial sweetners have been synthesised. Some commonly
used artificial sweetners are :
(a) Saccharin : Ortho-sulphobenzoimide also called saccharin is the first most popular
sweetening agent which is about 550 times as sweet as cane sugar.
It is insoluble in water but its soidum salt is soluble in water. Chemically it is 1, 2 -
benzisothiazolin - 3 - one - 1, 1 - dioxide (o-sulphobenzoimide) and accurs as white crystals.
O O
+
NH N Na
SO2 SO2
Saccharin Sodium salt of Saccharin

(Insoluble in water) (Soluble in water)
It is not biodegradable and is excreted as such in urine. So it does not possess any calorific
value and is used as sweetening agent by diabetic patients.
(b) Cyclamate : Cyclamate is seven times sweeter than sucrose. However a mixture of
cyclamate and saccharin in the ratio 10:1 is found to be sweeter than either of the two individual
compounds. Its structure is: H
N
SO3H
Cyclamate or N - cyclohexylsulphamate
Its use has been banned because of its suspected link with cancer.
(c) Aspartame : Aspartame is the most efficient and widely used artificial sweetner
which is the methyl ester of the dipeptide derived from phenylalanine and aspartic acid.
Å
COOCH3 O NH3
C6H5 – CH2 – CH – NH – C – CH – CH2 – COO

Aspartame
It is approximately 100 times as sweet as cane sugar, but it has short shelf life. It
decomposes at baking or cooking temperature and its use is limited to cold foods and soft drinks.
Again people suffering from the disease phenylketone urea are advised not to use aspartame
since their metabolism converts it to phenylpyruvic acid, accumulation of which is harmful
especially to infants due to mental retardation and brain damage.
(d) Sucralose : Sucralose is a trichloro derivative of sucrose which is roughly 600 times
as sweet as sucrose. It tastes and looks like sucrose and is quite stable at baking and cooking
temperature. It neither provides calories nor causes tooth decay.
Cl CH2OH
H O
H H
HO H OH H
H OH CH2Cl
O
H OH
O H
ClH2C
Sucralose
(e) Alitame : Alitame is 2000 times as sweet as sucrose. It is a high potency sweetner,
but it is very difficult to control the sweetness of the food to which it is added.
H3C CH3
O NH2 O CH3 O
HO – C – CH2 – CH – C – NH – CH – C – NH –– S
Alitame
CH3 CH3
III. ANTIOXIDANTS
Antioxidants are defined as the chemicals which are added to processed foods like potato
chips, biscuits, breakfast cereals etc. to prevent the oxidation of fats and subsequent spoilage of
the food.
(i) The most common antioxidants are butylated hydroxytoluene (BHT), butylated
hydroxyanisole (BHA) and several esters of gallic acid such as propyl gallate.
OH OH
(CH3)3C C(CH3)3 C(CH3)3
CH3 OCH3
Butylated hydroxytoluene Butylated hydroxyanisole
(BHT) (BHA)
COOH COO CH2 CH2CH3
HO OH HO OH
OH OH
Gallic acid Propyl gallate
(ii) Antioxidants are also termed as sacrificial materials as they are more reactive
towards oxygen than the materials they are protecting. They also reduce the rate of
involvement of free radicals in the ageing process.
(iii) The addition of BHA to butter increases its shelf-life from months to years.
(iv) Sulphur dioxide and sodium metabisulphite which are used as preservatives, are
also used an antioxidants for wine, beer, sugar syrups, dried fruits and vegetables.
(v) Ascorbic acid prevents browning caused by enzymatic oxidation of phenolic
compounds.
24.4 CLEANSING AGENTS :

I. (a) Soaps : Soaps are the sodium or the potassium salts of higher fatty acids like
stearic acid, palmitic acid, oleic acid etc. They are prepared by the alkaline hydrolysis i.e.
saponification of oils and fats. Soaps may also be obtained by the direct neutralisation of higher
fatty acids, like stearic acid, palmitic acid and oleic acids with alkali, such as NaOH or KOH.
O
(i) CH2 – O – C – C17 H35
O
CH – O – C – C17 H35 + 3 NaOH ® 3C17H35COONa
O Sodium stearate (Soap)
CH2 – O – C – C17 H35
Glyceryl ester of stearic acid CH2 – OH
+ CH – OH
CH2 – OH
Glycerol
(ii) C17H35 – COOH + NaOH ¾Direct neutralization

¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® C17H35 COONa + H2O
Stearic acid Soap (Sodium stearate)
The saturated fats and oils give hard soaps than the unsaturated one. Also sodium salts of
a given fat or oil is harder and less soluble than the potassium salts. Hence, soft soaps are
particularly of potassium salts of higher unsaturated fatty acids and hard soaps are sodium salts
of higher saturated falty acids.
(b) Types of soaps : Saponification of oils or fats produces soap. However, different
soaps are prepard by varying diffeent raw materials.
(i) Washing soaps : These are made from cheaper fats like mohwa oil, rosin etc using
caustic soda for their saponification. Sodium silicate is added to these soaps as a
filler. Some cheap starch or white clay is added to increase the weight and reduce
the cost.
(ii) Toilet soaps : Toilet soaps are made from best animal or vegetable fats or mixture
of both with removal of excess alkali. Then colour, perfume and germicide etc. are
added to the soap during crutching or shredding.
(iii) Transparent soaps : These are made by dissolving the soap in ethanol followed
by evaporation of the excess solvent.
(iv) Shaving soaps : During preparation of shaving soaps glycerol is added to prevent
rapid drying. Rosin, a gum is added while making them which forms sodium rosinate
responsible for lather.
(v) Laundry soaps : These soaps contain fillers like sodium silicate, sodium rosinate,
borax and sodium carbonate.
(c) Advantages and disadvantages of soaps : Soap is an effective cleaning agent and is
completely biodegradable. Micro-organisms present in sewage water can oxidise soap completely
to carbon dioxdes and hence does not create any pollution.
However soaps are having the following limitations.
(i) Ordinary soaps are unsuitable for washing of silk, wool etc. as the alkali present
causes harm to the fibre.
(ii) Soaps can not be used in acidic medium because they change the soaps into free
carboxylic acids which strick to the fabrics being incapable of removing oil and
grease from fabrics.
(iii) Soaps can not be used in hard water because hard water contains calcium and
magnesium ions which form insoluble calcium and magnesium soaps when sodium
or potassium soaps are dissolved in hard water.
2 C17H35 COONa + CaCl2 ® 2NaCl + (C17H35 COO)2Ca
Sodium stearate Calcium stearate
(Soap) (Soluble) (Insoluble)
Insoluble soaps separate as scum in water and are hindrance to good washing. This
causes wastage of soap and also discolours and hardens the fabric being washed.
II. SYNTHETIC DETERGENTS :
Synthetic detergents are generally sodium salts of long-chain alkyl hyrogen sulphate or
sodium salts of long chain alkyl benzene sulphonic acids which act as cleansing agents having
all the properties of soaps, but do not contain any soap. These are also referred to as syndets or
soapless soaps.
In contrast to soaps, synthetic detergents can be efficiently used even with hard water,
because calcium and magnesium salts of synthetic detergents like their sodium and potassium
salts are also soluble in water. Hence they do not form curdy white precipitates with hard water.
Again they can also be used for acidic solutions. However, unlike soaps they are not completely
biodegradable and hence result in water pollution.
Synthetic detergents are of three types. These are :
(a) Anionic detergents : These are so called because a large part of their molecules are
anions. These are of two types:
(i) Sodium alkyl suphates : These are the sodium salts of sulphonated long chain
alcohols formed by the treatment of long chain alcohol with concentrated sulphuric
acid followed by neutralisation with sodium hydroxide. Examples are sodium lauryl
sulphate and sodium stearyl sulphate.
H SO 4
CH3(CH2)10CH2OH ¾¾2¾¾ ® CH3(CH2)10CH2OSO3H
Lauryl alcohol –H2O Lauryl hydrogen sulphate
–H2O ¯ NaOH(aq)
CH3(CH2)10 CH2O SO–3Na+
Sodium lauryl sulphate
These sodium alkyl sulphates are 100% biodegradable.
(ii) Sodium alkyl benzene sulphonates : These are obtained by Friedel-Craft's
alkylation of benzene with a long chain alkyl halide or an alkene or an alcohol
followed by sulphonation and neutralization with NaOH. Most widely used
detergent is sodium n–dodecylbenzenesulphonate (SDS), which is also referred to
as LAS detergents (linear alkyl sulphonates) where as an example of ABS detergents
(alkyl benzene sulphonates) with a branched chain alkyl groups is
CH3 CH3
CH3 ––– CH – CH2––– CH ––– ––– SO–3Na+

3
Hard or non-biodegradable ABS detergent
CH3 – (CH2)11 ––– ––– SO–3Na+
Soft or biodegradable LAS detergent.

(Sodium n-dodecylbenzene sulphonate)
Sodium n-dodecylbenzene sulphonate can be prepared as follows:
CO(CH2)10CH3
Anhydrous AlCl3
+ CH3 (CH2)10COCl
– HCl
Zn/Hg–HCl
(CH2)11CH3 (CH2)11CH3 (CH2)11CH3
NaOH (aq) ConcH2SO4

– H2O – H2O
Dodecylbenzene
SO–3 Na+ SO3H
Sodium dodecyl- Dodecylbenzene

-benzenesulphonate sulphonic acid
(b) Cationic detergents : Cationic detergents are quarternary ammonium salts of amines
with chlorides, bromides or acetates as anions containing one or more long chain alkyl groups
and a positive charge on nitrogen atom, for which these are called cationic detergents.
Being more expensive than the anionic detergents, they find limited use. However they
are extensively used as germicides.
Cetyltrimethylammonium bromide is a popular cationic detergent and is used in hair
conditioners.
CH3
+
CH3(CH2)15 ––––– N ––––– CH3 Br–
CH3
Cetyltrimethyl ammonium bromide (germicide)

Other examples of cationic detergents are:
CH3
+
––– CH2 ––––– N ––––– C12H25 Cl– (CH3)3 N+ (C18H37) Br–
Trimethyl stearyl
CH3 ammonium bromide
Benzalkonium chloride
(an antibacterial)
(c) Neutral or non-ionic detergents : Non-ionic detergents do not contain any ion in
their structure. One most widely used neutral detergent is formed when stearic acid reacts with
polyethylene glycol.
n HO – CH2 – CH2OH + CH2 – CH2 ® HO (CH2CH2O)n CH2CH2OH
Ethylene glycol Polyethylene glycol
O
Ethylene oxide
CH3 (CH2)16 COOH + HO (CH2CH2O)n CH2CH2OH

Stearic acid Polyethylene glycol
¯ – H2O
CH3 (CH2)16 COO (CH2CH2O)n CH2CH2OH
Non-ionic detergent
Another example of non-ionic detergent is lauryl alcohol ethoxylate which is 100%

biodegradable. This can be synthesized as follows :
CH3 (CH2)10 CH2OH + 8 CH2 – CH2
n – Lauryl alcohol Ethylene oxide
¯ Base
CH3 (CH2)10 CH2 (OCH2CH2)8OH
Lauryl alcohol ethoxylate
Non-ionic detergents are liquid dish washing detergents.
Advantages and disadvantages of synthetic detergents over soaps :
(a) Advantages : Synthetic detergents find wide application these days as cleasing agents
having the following advantages over soaps.
(i) Synthetic detergents can be used even in hard water.
(ii) Synthetic detergents can be used even in acidic medium because these are the salts
of strong acids and are not decomposed in the acidic medium.
(iii) These are more soluble in water than soaps.
(iv) They have stronger cleansing power than soaps.
(v) Synthetic detergents are prepared from the hydrocarbons obtained from petroleum.
This saves vegetable oils used as food.
(b) Disadvantages of synthetic detergents over soaps :
Synthetic detergents having branched chain hydrocarbon chains are not biodegradable
and cause water pollution making it unfit for use by the aquatic life. However, this difficulty has
been overcome now by using a straight chain hydrocarbon in the detergent instead of branched
chain hydrocarbon making it biodegradable. But all soaps are biodegradable.
Difference between Soaps and Detergents :

Main points of difference between soaps and synthetic detergents are given in Table
24.1.
Table 24.1
Difference between soaps and synthetic detergents.
Soaps Synthetic detergents
1 These are alkali metal salts of long chain 1. There are sodium salts of long chain alkyl
fatty acids sulphates or long chain alkylbenzene
sulphonates.
2. These can not be used in hard water. 2. These can be used even in hard water
3. These can not be used in acidic solutions. 3. These can be used even in acidic
solutions.
4. These are obtained from vegetable oils. 4. These are prepared from hydrocarbons
obtained from petroleum.
5. These are biodegradable. 5. Some of the synthetic detergents are not
biodegradable.
III. CLEANSING ACTION OF SOAPS AND DETERGENTS :

The cleaning action of a soap or a detergent is called its detergent action or detergency.
All the soaps and detergents contains two characteristics groups i.e.
(i) Non-polar hydrocarbon chain which is oil soluble (lyophilic or lipophilic) and is called
hydrocarbon tail or oil-soluble non-polar part of the soap or detergent molecule.
(ii) Polar end which is water soluble (hydrophilic) and is called negative end or water soluble
polar part of the soap or detergent molecule.
O
Å
CH3 – CH2 – (CH2)15 C – O Na (Soap)
Non polar hydrocarbon chain Polar part
(Oil soluble) (Water soluble)
Å
CH3 – (CH2)10 – CH2 O SO2 O Na (Detergent)
Oil soluble non-polar part Water soluble polar part
Cleansing action of soaps and detergents takes place in two steps :
(i) Wetting : This results from lowering of surface tesnsion of water by mixing soap with it.
As a result the oil droplets of the dirt are wetted on the surface and form a colloidal
suspension in the medium of water. The soap forms a protective film on their surface to
prevent coagulation. Such colloidal particles are then washed away with water.
(ii) Emulsification : When dirty cloth is immersed into the mixture of soap and water, the
non-polar part of the soap or detergent dissolves in oil or grease and the polar part of the
soap or detergent is held by the surrounding water as shown in Fig. 24.1. The grease
layer is then dislodged from skin by rubbing or from garment by tumbling and strirring.
Na+
Oil or grease droplet

(Dirt particle)
Polar end
Non-polar end
Fig. 24.1 : Cleansing action of soap and detergents
Each oil droplet is surrounded by an ionic atmosphere with negative heads outwards in
water. Due to repulsion between similar charges, oil or grease particles change into very
small drops and a stable emulsion of oil in water is obtained. The emulsified grease
particles bearing dirt can be easily washed with water. Thus soap and detergent clean by
emulsifying the fat and grease containing the dirt.
1. Chemicals in medicine : Chemical substances used for curing diseases and reducing
suffering from pain are called medicines or drugs. The branch of science which deals
with the treatment of diseases using suitable chemicals is known as chemotheraphy.
(a) Analgesics : Analgesics decrease pain. These are of two types. (i) Narcotics :
Examples are morphine and heroin. (ii) Non-narcotics : Examples are aspirin and
phenacetin.
(b) Tranquilizers : These are medicines used to treat mental diseases. Examples are
equanil, seconal and luminal.
(c) Antiseptics : These are applied to skin, on wounds and cuts to kill or prevent the
growth of micro-organisms. Examples are dettol, savlon and acriflavin.
(d) Disinfectants : These are the chemicals which kill micro-organisms, but not safe
for human beings.
(e) Antimicrobials : Drugs used to cure diseases caused by fungi, bacteria and viruses
are called antimicrobials. Examples are penicillin, streptomycin and AZT widely
used against AIDS.
(f) Antifertility drugs : These are used to check pregnancy in women. Example is
Enovid E.
(g) Antibiotics : These are chemical substances produced by some micro-organisms
and can be used to kill other micro-organisms which cause infections. Examples
are tetracyclin, chloramphenicol, penicillin.
(h) Antacids : These are the chemicals used to remove the excess acid and raise the
pH to on appropriate level in stomach. Examples are omeprazole and lansoprazole.
(i) Antihistamines : Allergy is caused by liberation of histamines. The drugs used to
treat allergy are called antihistamines. Examples are diphenylhydramine and
promethazine.
2. Chemicals in food : Food additives are those chemicals which are added to food to
improve its keeping qualities, appearance, taste, colour, odour and food value. These
are :
(a) Preservatives : These are used to protect food against bacteria, yeasts and moulds.
Examples are: Sodium metabisulphite, Sorbic acid and Sodium benzoate.
(b) Artificial sweetening agents : Aspartame, Alitame and Saccharin are the artificial
sweetners having no calorie intake for which used by the diabetic patients.
(c) Antioxidants : These are used to prevent oxidation of fats in processed foods such
as potato chips, biscuits etc. Examples are BHT and BHA.
3. Cleansing Agents (Soaps and Detergents)
(a) Soaps are sodium and potassium salts of higher fatty acids like stearic acid, palmitic
acid, oleic acid etc. Washing soaps contain sodium salts of fatty acids while soft
soaps contain potassium salts.
(b) Synthetic detergents are generally sodium salts of long chain alkyl hydrogen
sulphates or sodium salts of long chain alkyl benzene sulphonic acids.
QUESTIONS
A. VERY SHORT QUESTIONS (One mark each) :
(a) Give the name of the first antibiotic.
(b) Name a substance which can be used as an antiseptic as well as disinfectant.
(c) What are tranquilizers?
(d) What type of medicine chloramphenicol is?
(e) Name two antipyretic drugs.
(f) Name two analgesic drugs.
(g) Aspirin is an –––––– .
(h) Streptomycin is a –––––– spectrum antibiotic.
(i) What is the name given to medicines used for getting relief from pain?
(j) Name the antibiotic used specifically for treatment of typhoid fever.
(k) Name one broad spectrum antibiotic.
(l) What is the difference between a preservative and an antioxidant?
(m) Name an antacid which prevents the formation of acid in the stomach.
(n) What structural unit makes detergents non-biodegradable?
(o) What type of detergents are used for dish washing?
(p) Give an example of a bactericidal antibiotic.
(g) In transparent soaps –––––– is used.
(h) Name two artificial sweetening agents.
(i) –––––– is the sweetening agent used in the preparation of sweets for a diabetic
patient.
B. SHORT QUESTIONS (Two marks each) :
(a) What are detergents? Name one from each type of detergent.
(b) Write down the difference between soap and detergent.
(c) What are broad spectrum antibiotics? Give two examples.
(d) What are antipyretics? give two examples.
(e) Whay soap is not used for hard water?
(f) What are antifertility drugs? Give one example.
(g) What are the main constituents of Dettol?
(h) What are food preservatives? Give two examples.
(i) Why are Cimetidine and Ranitidine better antiacids than sodium hydrogen carbonate
or magnesium hydroxide?
(j) Why is the use of aspartame limited to cold foods and drinks?
(k) What problem arises in using alitame as artificial sweetener?
C. SHORT QUESTIONS (Three marks each) :
(a) How are antiseptics different from disinfectants ? Give one example of each of
them.
(b) What are soaps and detergents?
(c) Discuss the cleansing action of soaps?
(d) Why does a detergent act even with hard water? Is it always biodegradable?
(e) Give the composition of one oral contraceptine.
(f) What are detergents? Give their scheme of classification.
(g) What are antioxidants? How do they differ from preservatives.
(h) What is tincture of iodine? What is its use?
(i) What are biodegradale and non-biodegradable detergents? Give one example of
each.
(j) Low level of noradrenaline is the cause of depression. What type of drugs are
needed to cure this problem? Name two drugs.
D. LONG QUESTIONS (7 marks each) :
(a) What are food additives? Discuss briefly the various types of food additives.
(b) What are soaps and synthetic detergents? In what respects detergents preferred
over soaps? Discuss the cleansing action of soaps and detergents.
(c) Write notes on :
(i) Antibiotics
(ii) Antacids
(iii) Analgesics
1. The oils from which soaps are prepared belong to a class of compounds known as
(a) Amine (b) Acid
(c) Hydrocarbon (d) Ester
2. Novalgin is a common
(a) Analgesic (b) Antibiotic
(c) Antipyretic (d) Antimalarial
3. Equanil is a drug to control
(a) Pneumonia (b) Malaria
(c) Ordinary fever (d) Mental disease
4. Medicine which is an antibiotic is

(a) Ampicilin (b) Aspirin
(c) Calmpose (d) Chloroquine
5. A detergent is a
(a) Drug (b) Catalyst
(c) Surface active agent (d) Soap
6. Which of the following is used as a preservative to protect processed food?
(a) Saccharin (b) BHT
(c) Sodium sulphate (d) Sodium metabisulphite
7. The drugs used to get relief from pain are called.
(a) Antibiotics (b) Antipyretics
(c) Analgeics (d) Antiseptics
8. Which of the following is an antihistamine drug?
(a) Ciprofloxacin (b) Chloroquine
(c) Chloramphenicol (d) Chlorpheniramine maleate
9. Which of the following is a tranquilizer?
(a) Morphine (b) Seconal
(c) Phenacetin (d) Streptomycin
10. 2-Acetoxy benzoic acid is called
(a) Mordant dye (b) Aspirin
(c) Antiseptic (d) Antibiotic
11. Morphine is
(a) Antiseptic (b) Antibiotics
(c) Analgesics (d) Antimalarial
12. Heroin is a derivative of
(a) Nicotine (b) Morphine
(c) Caffeine (d) Cocains
13. Which of the followings is used as germicide?
(a) Sodium lauryl sulphate (b) Cetyltrimethylammonium chloride
(c) Lauryl alcohol ethoxylate (d) Sodium-2-dodecylbenzene sulphonate
14. Which of the followings is an anionic detergent?
(a) C6H5 – SO3Na (b) CH3 (CH2)16 N+ (CH3)3 Cl–
(b) CH3 (CH2)16 CH2OSO3Na (d) CH3 (CH2)16 COO (CH2CH2O)n –
– CH2CH2–OH
15. The oxidant which is used as an antiseptic is

(a) KMnO4 (b) KBrO3
(c) CrO3 (d) KNO3
16. Which of the followings is used as a "morning after pill"?
(a) Norethindrone (b) Mifepristone
(c) Promethazine (d) Bithional
17. Tincture of iodine is
(a) aqueous solution of I2 (b) alcoholic solution of I2
(c) aqueous solution of KI (d) solution I2 in aqueous KI
18. Pick out the wrong statement.
(a) BHT is an antioxidant (b) Alitame is an artificial sweetener
(c) Sodium alkyl sulphate is a (d) Tetrazine is a harmful edible colour.
cationic detergent
19. Pick out the wrong statement for a detergent molecule.
(a) It is not easily biodegraded. (b) It is sodium salt of fatty acid.
(c) It is a source of active agent. (d) It has both non-polar organic part
and a polar group.
20. Detergents can be made biodegradable by taking
(a) Cyclic hydrocarbon chain (b) Unbranched hydrocarbon chain
(c) Benzenoid with hydrocarbons (d) Hydrocarbon with more branching
ANSWERS FOR MULTIPLE CHOICE QUESTIONS
1. (d) 2. (a) 3. (d) 4. (a) 5. (c) 6. (d) 7. (c) 8. (d) 9. (b) 10. (b)
11. (c) 12. (b) 13. (b) 14. (c) 15. (a) 16. (b) 17. (b) 18. (c) 19. (b) 20 (b)
qqq
I. LOGARITHMS
LOGARITHMS 773
II. LOGARITHMS
III. ANTILOGARITHMS
ANTILOGARITHMS 775
IV. ANTILOGARITHMS

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What are the intended users/audience of the textbook?

BUREAU’S

HIGHER SECONDARY (+2)

Dr. Sakuntala Jena

First Edition : 2000 / 7000

© Reserved by the Odisha State Bureau of Textbook Preparation and Production,

Typesetting and Diagram by :

Sri Umakanta Tripathy

Bhubaneswar Board of Writers

Unit IV : Chemical Kinetics

Unit V : Surface Chemistry

Unit VI : General Principles and Processes of Isolation of Elements

Unit VII : p - Block Elements

Unit VIII : d and f Block Elements

Unit IX : Coordination Compounds

Unit X : Haloalkanes and Haloarenes

Unit XI : Alcohols, Phenols and Ethers

calcination and roasting, smelting, reduction of metal oxide to

CHAPTER - 8 : GROUP 16 ELEMENTS : OXYGEN FAMILY 260 - 294

CHAPTER - 9 : EQUILIBRIA 295 - 324

CHAPTER - 10 : GROUP 18 ELEMENTS : NOBLE GASES 325 - 341

CHAPTER - 12 : THE f-BLOCK ELEMENTS 361 - 371

compounds, 13.8. Bonding in co-ordination compounds: The

HALOARENES (ARYL HALIDES) 422 - 446

tertiary alcohols, 15.9. Tests for alcoholic –OH group,

CHAPTER - 16 : PHENOLS 487 - 500

CHAPTER - 17 : ETHERS 501 - 521

CHAPTER - 20 : AMINES 643 - 673

CHAPTER - 21 : ARYL DIAZONIUM SALTS 674 - 684

THE SOLID STATE

1.1 CHARACTERISTIC PROPERTIES OF SOLIDS :

1. Shape : A solid has a definite shape.

4. Compressibility : Solids are mainly incompressible. This is because the particles

7. Crystalline state : Solids possess a crystalline structure. This is due to orderly

1.2 CLASSIFICATION OF SOLIDS :

Classification of Crystalline solids :

Fig. 1.1 Sodium chloride crystal

1.3 CRYSTAL LATTICES AND UNIT CELLS :

Fig. 1.2 Space lattice and a unit cell

Close packing in Crystalline solids :

(i) Close packing in two dimensions :

Fig. 1.5 Packing of second layer (B) on first layer (A)

1.4 TYPES OF CUBIC CRYSTALS :

Fig. 1.9 Body centred cubic arrangement.

Fig. 1.10 Cubic close packed or face centred cubic

1.5 CALCULATION OF DENSITY OF UNIT CELLS :

Mass of unit cell

No. of atoms in the unit cell× Mass of each atom

where n = No. of atoms in the unit cell

1.6 INTERSTICES OR INTERSTITIAL VOIDS :

Tetrahedral hole Tetrahedral hole

Fig. 1.11 Tetrahedral void.

Fig. 1.12 Octahedral site

1.7 CO-ORDINATION NUMBER :

(a) O Anion (b)

C.N. increases from 6 to 8