CHEMISTRY. FOR DEGREE STUDENTS B.Sc. Second Year. All Indian Universities As per UGC Model Curriculum

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2 CHEMISTRY FOR DEGREE STUDENTS B.Sc. Second Year All Indian Universities As per UGC Model Curriculum

3 CHEMISTRY FOR DEGREE STUDENTS B.Sc. Second Year All Indian Universities As per UGC Model Curriculum Part I : Inorganic Chemistry Part II : Organic Chemistry Part III : Physical Chemistry Dr. R.L. MADAN M.Sc., Ph.D. Former, Head of Chemistry Department Government Postgraduate College, Faridabad and Principal, Government College, Panchkula S. CHAND & COMPANY PVT. LTD. (AN ISO 9001: 2008 COMPANY) RAM NAGAR, NEW DELHI

4 S. CHAND & COMPANY PVT. LTD. (An ISO 9001 : 2008 Company) Head Office: 7361, RAM NAGAR, NEW DELHI Phone: , , Fax: Shop at: schandgroup.com; info@schandgroup.com Branches : AHMEDABAD : 1st Floor, Heritage, Near Gujarat Vidhyapeeth, Ashram Road, Ahmedabad , Ph: , , ahmedabad@schandgroup.com BENGALURU : No. 6, Ahuja Chambers, 1st Cross, Kumara Krupa Road, Bengaluru , Ph: , , bangalore@schandgroup.com BHOPAL : Bajaj Tower, Plot No. 2&3, Lala Lajpat Rai Colony, Raisen Road, Bhopal , Ph: , bhopal@schandgroup.com CHANDIGARH : S.C.O , First Floor, Sector - 22-C (Near Aroma Hotel), Chandigarh , Ph: , , chandigarh@schandgroup.com CHENNAI : No.1, Whites Road, Opposite Express Avenue, Royapettah, Chennai Ph , , chennai@schandgroup.com COIMBATORE : 1790, Trichy Road, LGB Colony, Ramanathapuram, Coimbatore , Ph: , coimbatore@schandgroup.com (Marketing Office) CUTTACK : 1st Floor, Bhartia Tower, Badambadi, Cuttack , Ph: ; , cuttack@schandgroup.com DEHRADUN : 1st Floor, 20, New Road, Near Dwarka Store, Dehradun , Ph: , , dehradun@schandgroup.com GUWAHATI : Dilip Commercial (Ist floor), M.N. Road, Pan Bazar, Guwahati , Ph: , guwahati@schandgroup.com HALDWANI : Bhatt Colony, Talli Bamori, Mukhani, Haldwani (Marketing Office) Mob HYDERABAD : Padma Plaza, H.No , Opp. Ratna College, Narayanaguda, Hyderabad , Ph: , , hyderabad@schandgroup.com JAIPUR : 1st Floor, Nand Plaza, Hawa Sadak, Ajmer Road, Jaipur , Ph: , , jaipur@schandgroup.com JALANDHAR : Mai Hiran Gate, Jalandhar , Ph: , , jalandhar@schandgroup.com KOCHI : Kachapilly Square, Mullassery Canal Road, Ernakulam, Kochi , Ph: , , cochin@schandgroup.com KOLKATA : 285/J, Bipin Bihari Ganguli Street, Kolkata , Ph: , , kolkata@schandgroup.com LUCKNOW : Mahabeer Market, 25 Gwynne Road, Aminabad, Lucknow , Ph: , , , , lucknow@schandgroup.com MUMBAI : Blackie House, IInd Floor, 103/5, Walchand Hirachand Marg, Opp. G.P.O., Mumbai , Ph: , , mumbai@schandgroup.com NAGPUR : Karnal Bagh, Near Model Mill Chowk, Nagpur , Ph: , nagpur@schandgroup.com PATNA : 104, Citicentre Ashok, Mahima Palace, Govind Mitra Road, Patna , Ph: , , patna@schandgroup.com PUNE : Sadguru Enclave, Ground floor, Survey No. 114/3, Plot no. 8 Alandi Road, Vishrantwadi Pune Ph: pune@schandgroup.com RAIPUR : Kailash Residency, Plot No. 4B, Bottle House Road, Shankar Nagar, Raipur , Ph: ,Mb. : , raipur@schandgroup.com (Marketing Office) RANCHI : Shanti Deep Tower, Opp.Hotel Maharaja, Radium Road, Ranchi Mob ranchi@schandgroup.com SILIGURI : 122, Raja Ram Mohan Roy Road, East Vivekanandapally, P.O., Siliguri, Siliguri , Dist., Jalpaiguri, (W.B.) Ph (Marketing Office) siliguri@schandgroup.com VISAKHAPATNAM : No /53/8, Plot No. 7, 1st Floor, Opp. Radhakrishna Towers, Seethammadhara North Extn., Visakhapatnam , Ph (M) , visakhapatnam@schandgroup.com (Marketing Office) 2011, Dr. R.L. Madan All rights reserved. No part of this publication may be reproduced or copied in any material form (including photocopying or storing it in any medium in form of graphics, electronic or mechanical means and whether or not transient or incidental to some other use of this publication) without written permission of the copyright owner. Any breach of this will entail legal action and prosecution without further notice. Jurisdiction : All disputes with respect to this publication shall be subject to the jurisdiction of the Courts, Tribunals and Forums of New Delhi, India only. First Edition 2011; Reprint with Corrections 2012 ; 2013 (Thrice) Reprint 2014 (Twice) ISBN : Code : 1004B 323 PRINTED IN INDIA By Rajendra Ravindra Printers Pvt. Ltd., 7361, Ram Nagar, New Delhi and published by S. Chand & Company Ltd., 7361, Ram Nagar, New Delhi

5 PREFACE I feel pleasure in presenting this book to the teachers and students of B.Sc.-II year of all the Indian Universities. The book has been prepared keeping in view the syllabi prepared by different universities on the basis of Model UGC Curriculum. The present book has evolved out of my experience of more than three decades of classroom teaching at B.Sc. level. A long span of interaction with students has guided me to give special attention to dark areas which students find difficult to understand. Mathematics background required is simple and the necessary mathematical techniques have been developed within the text. Some salient features of the book are : The book has been written in a simple and comprehensible language. A large number of illustrations, pictures and interesting examples have been provided to make the reading interesting and understandable. The important laws, concepts and principles have been given either in italics or in bold type to help the students to focus on them. A large number of solved examples which have appeared in the examination papers of various universities have been given in each chapter, for the benefit of students. The questions that have been provided in the Exercise are in tune with the latest pattern of examination. I believe that the book contains all that is needed to understand the subject in a systematic manner. However, no work is perfect. I would welcome suggestions from the teaching fraternity and students for further improvement of the book. I express my gratitude to the staff of S.Chand & Company Pvt. Ltd., New Delhi for providing all assistance and bringing out the book in the present shape. Dr. R.L. Madan Mobile : Disclaimer : While the author of this book has made every effort to avoid any mistakes or omissions and has used his skill, expertise and knowledge to the best of his capacity to provide accurate and updated information, the author and S. Chand do not give any representation or warranty with respect to the accuracy or completeness of the contents of this publication and are selling this publication on the condition and understanding that they shall not be made liable in any manner whatsoever. S.Chand and the author expressly disclaim all and any liability/responsibility to any person, whether a purchaser or reader of this publication or not, in respect of anything and everything forming part of the contents of this publication. S. Chand shall not be responsible for any errors, omissions or damages arising out of the use of the information contained in this publication. Further, the appearance of the personal name, location, place and incidence, if any; in the illustrations used herein is purely coincidental and work of imagination. Thus the same should in no manner be termed as defamatory to any individual. (v)

6 I II III IV V VI UGC MODEL SYLLABUS CHEMISTRY B.Sc. SECOND YEAR CH-201 Inorganic Chemistry Chemistry of Elements of First Transition Series Characteristic properties of d-block elements. Properties of the elements of the first transition series, their binary compounds and complexes illustrating relative stability of their oxidation states, coordination number and geometry. Chemistry of Elements of Second and Third Transition Series General characteristics, comparative treatment with their 3d-analogues in respect of ionic radii, oxidation states, magnetic behaviour, spectral properties and stereochemistry. Oxidation and Reduction Use of redox potential data analysis of redox cycle, redox stability in water Frost, Latimer and Pourbaix diagrams. Principles involved in the extraction of the elements. Coordination Compounds Werner s coordination theory and its experimental verification, effective atomic number concept, chelates, nomenclature of coordination compounds, isomerism in coordination compounds, valence bond theory of transition metal complexes. Chemistry of Lanthanide Elements Electronic structure, oxidation states and ionic radii and lanthanide contraction, complex formation, occurrence and isolation, lanthanide compounds. Chemistry of Actinides General features and chemistry of actinides, chemistry of separation of Np, Pu and Am from U, similarities between the later actinides and the later lanthanides. VII Acids and Bases Arrhenius, Bronsted-Lowry, the Lux-Flood, solvent system and Lewis concepts of acids and bases. VIII Non-aqueous Solvents Physical properties of a solvent, types of solvents and their general characteristics, reactions in non-aqueous solvents with reference to liquid NH 3 and liquid SO 2. I CH-202 Organic Chemistry Electromagnetic Spectrum : Absorption Spectra Ultraviolet (UV) absorption spectroscopy absorption laws (Beer-Lambert Law), molar absorptivity, presentation and analysis of UV spectra, types of electronic transitions, effect of conjugation. Concept of chromophore and auxochrome. Bathochromic, hypsochromic, hyperchromic and hypochromic shifts. UV spectra of conjugated enes and enones. Infrared (IR) absorption spectroscopy molecular vibrations, Hooke s law, selection rules, intensity and position of IR bands, measurement of IR spectrum, fingerprint region, (vii)

7 II III IV V VI characteristic absorptions of various functional groups and interpretation of IR spectra of simple organic compounds. Alcohols Classification and nomenclature. Monohydric alcohols nomenclature, methods of formation by reduction of aldehydes, ketones, carboxylic acids and esters. Hydrogen bonding. Acidic nature. Reactions of alcohols. Dihydric alcohols nomenclature, methods of formation, chemical reactions of vicinal glycols, oxidative cleavage [Pb(OAc) 4 and HIO 4 ] and pinacol-pinacolone rearrangement. Trihydric alcohols nomenclature and methods of formation, chemical reactions of glycerol. Phenols Nomenclature, structure and bonding. Preparation of phenols, physical properties and acidic character. Comparative acidic strengths of alcohols and phenols, resonance stabilization of phenoxide ion. Reactions of phenols electrophilic aromatic substitution, acylation and carboxylation. Mechanisms of Fries rearrangement, Claisen rearrangement, Gatterman synthesis, Hauben-Hoesch reaction, Lederer-Manasse reaction and Reimer Tiemann reaction. Ethers and Epoxides Nomenclature of ethers and methods of their formation, physical properties. Chemical reactions cleavage and autoxidation, Ziesel s method. Synthesis of epoxides. Acid and base-catalyzed ring opening of epoxides, orientation of epoxide ring opening, reactions of Grignard and organolithium reagents with expoxides. Aldehydes and Ketones Nomenclature and structure of the carbonyl group. Synthesis of aldehydes and ketones with particular reference to the synthesis of aldehydes from acid chlorides, synthesis of aldehydes and ketones using 1, 3-dithianes, synthesis of ketones from nitriles and from carboxylic acids. Physical properties. Mechanism of nucleophilic additions to carbonyl group with particular emphasis on benzoin, aldol, Perkin and Knoevenagel condensations. Condensation with ammonia and its derivatives. Wittig reaction. Mannich reaction. Use of acetals as protecting group. Oxidation of aldehydes, Baeyer-Villiger oxidation of ketones, Cannizzaro reaction. MPV, Clemmensen, Wolff-Kishner, LiAlH 4 and NaBH 4 reductions. Halogenation of enolizable ketones. An introduction to unsaturated aldehydes and ketones. Carboxylic Acids Nomenclature, structure and bonding, physical properties, acidity of carboxylic acids, effects of substituents on acid strength. Preparation of carboxylic acids. Reactions of carboxylic acids. Hell-Volhard-Zelinsky reaction. Synthesis of acid chlorides, esters and amides. Reduction of carboxylic acids. Mechanism of decarboxylation. Methods of formation and chemical reactions of halo acids. Hydroxy acids : malic, tartaric and citric acids. Methods of formation and chemical reactions of unsaturated monocarboxylic acids. Dicarboxylic acids : methods of formaton and effect of heat and dehydrating agents. VII Carboxylic Acid Derivatives Structure and nomenclature of acid chlorides, esters, amides (urea) and acid anhydrides. Relative stability of acyl derivatives. Physical properties, interconversion of acid derivatives by nucleophilic acyl substitution. (viii)

8 Preparation of carboxylic acid derivatives, chemical reactions. Mechanisms of esterification and hydrolysis (acidic and basic). VIII Organic Compounds of Nitrogen Preparation of nitroalkanes and nitroarenes. Chemical reactions of nitroalkanes. Mechanisms of nucleophilic substitution in nitroarenes and their reductions in acidic, neutral and alkaline media. Picric acid. Halonitroarenes : reactivity. Structure and nomenclature of amines, physical properties. Stereochemistry of amines. Separation of a mixture of primary, secondary and tertiary amines. Structural features effecting basicity of amines. Amine salts as phase-transfer catalysts. Preparation of alkyl and aryl amines (reduction of nitro compounds nitriles), reductive amination of aldehydic and ketonic compounds. Gabriel-phthalimide reaction, Hofmann bromamide reaction. Reactions of amines, electrophilic aromatic substitution in aryl amines, reactions of amines with nitrous acid. Synthetic transformations of aryl diazonium salts, azo coupling. I II Thermodynamics I CH-203 Physical Chemistry Definition of thermodynamic terms : system, surroundings etc. Types of systems, intensive and extensive properties. State and path functions and their differentials. Thermodynamic process. Concept of heat and work. First Law of Thermodynamics : statement, definition of internal energy and enthalpy. Heat capacity, heat capacities at constant volume and pressure and their relationship. Joule s law-joule-thomson coefficient and inversion temperature. Calculation of w,q, du & dh for the expansion of ideal gases under isothermal and adiabatic conditions for reversible process. Thermochemistry : standard state, standard enthalpy of formation. Hess s Law of heat summation and its applications. Heat of reaction at constant pressure and at constant volume. Enthalpy of neutralization. Bond dissociation energy and its calculation from thermo-chemical data, temperature dependence of enthalpy. Kirchhoff s equation. Thermodynamics II Second law of thermodynamics : need for the law, different statements of the law. Carnot cycle and its efficiency, Carnot theorem. Thermodynamic scale of temperature. Concept of entropy : entropy as a state function, entropy as a function of V & T, entropy as a function of P & T, entropy change in physical change, Clausius inequality, entropy as a criteria of spontaneity and equilibrium. Entropy change in ideal gases and mixing of gases. Third law of thermodynamics : Nernst heat theorem, statement and concept of residual entropy, evaluation of absolute entropy from heat capacity data, Gibbs and Helmholtz functions; Gibbs function (G) and Helmholtz function (A) as thermodynamic quantities, A & G as criteria for thermodynamic equilibrium and spontaneity, their advantage over entropy change. Variation of G and A with P, V and T. III Chemical Equilibrium Equilibrium constant and free energy. Thermodynamic derivation of law of mass action. Le Chatelier s principle. Reaction isotherm and reaction isochore Clapeyron equation and Clausius-Clapeyron equation, applications. (ix)

9 IV V VI Phase Equilibrium Statement and meaning of the terms-phase, component and degree of freedom, derivation of Gibbs phase rule, phase equilibria of one component system-water, CO 2 and S systems. Phase equilibria of two component system-solid-liquid equilibria, simple eutectic-bi-cd, Pb-Ag systems, desilverisation of lead. Solid solutions-compound formation with congruent melting point (Mg-Zn) and incongruent melting point, (NaCl-H 2 O), (FeCl 3 -H 2 O) and CuSO 4 -H 2 O) system. Freezing mixtures, acetone -dry ice. Liquid-liquid mixtures-ideal liquid mixtures, Raoult s and Henry s law, Non-ideal systemazeotropes-hcl-h 2 O and ethanol-water systems. Partially miscible liquids-phenol-water, trimethylamine-water, nicotine-water systems. Lower and upper consolute temperature. Effect of impurity on consolute temperature. Immiscible liquids, steam distillation. Nernst distribution law-thermodynamic derivation, applications. Electrochemistry-I Electrical transport-conduction in metals and in electrolyte solutions, specific conductance and equivalent conductance, measurement of equivalent conductance, variation of equivalent and specific conductance with dilution. Migration of ions and Kohlrausch law, Arrhenius theory of electrolyte dissociation and its limitations, weak and strong electrolytes, Ostwald s dilution law its uses and limitations. Debye-Huckel-Onsager s equation for strong electrolytes (elementary treatment only). Transport number, definition and determination by Hittorf method and moving boundary method. Applications of conductivity measurements : determination of degree of dissociation, determination of K a of acids, determination of solubility product of a sparingly soluble salt, conductometric titrations. Electrochemistry-II Types of reversible electrodes-gas-metal ion, metal-metal ion, metal-insoluble salt-anion and redox electrodes. Electrode reactions, Nernst equation, derivation of cell E.M.F. and single electrode potential, standard hydrogen electrode-reference electrodes-standard electrode potential, sign conventions, electrochemical series and its significance. Electrolytic and Galvanic cells-reversible and irreversible cells, conventional representation of electrochemical cells. EMF of a cell and its measurements. Computation of cell EMF. Calculation of thermodynamic quantities of cell reactions ( G, H and K), polarization, over potential and hydrogen overvoltage. Concentration cell with and without transport, liquid junction potential, application of concentration cells, valency of ions, solubility product and activity conefficient, potentiometric titrations. Definition of ph and pk a determination of ph using hydrogen, quinhydrone and glass electrodes, by potentiometric methods. Buffers-mechanism of buffer action, Henderson-Hazel equation. Hydrolysis of salts. Corrosion-types, theories and methods of combating it. (x)

10 CONTENTS OF B.Sc. I AND B.Sc. III BOOKS B.Sc. I PART I: INORGANIC CHEMISTRY 1. Atomic Structure 2. Periodic Properties 3. Covalent Bond 4. Ionic Bond 5. s-block Elements 6. p-block Elements 7. Chemistry of Noble Gases PART II: ORGANIC CHEMISTRY 1. Structure and Bonding 2. Mechanism of Organic Reactions 3. Stereochemistry of Organic Compounds 4. Alkanes and Cycloalkanes 5. Alkenes, Cycloalkenes, Dienes and Alkynes 6. Arenes and Aromaticity 7. Alkyl and Aryl Halides PART III: PHYSICAL CHEMISTRY 1. Mathematical Concepts and Computers 2. Gaseous States 3. Liquid State 4. Solid State 5. Colloidal State 6. Chemical Kinetics 7. Catalysis 8. Thermodynamics I (Thermochemistry and First Law) (xi) B.Sc. III PART I: INORGANIC CHEMISTRY 1. Hard and Soft Acids and Bases 2. Metal Ligand Bonding in Transition Metal Complexes 3. Magnetic Properties of Transition Metal Complexes 4. Electronic Spectra of Transition Metal Complexes 5. Thermodynamic and Kinetic Aspects of Metal Complexes 6. Organometallic Chemistry 7. Bioinorganic Chemistry 8. Silicones and Phosphazenes PART II: ORGANIC CHEMISTRY 1. Spectroscopy 2. Organometallic Compounds 3. Organosulphur Compounds 4. Heterocyclic Compounds 5. Organic Synthesis via Enolates (Acetoacetic Ester, Malonic Ester, 1,3-Dithianes, Enamines) 6. Carbohydrates 7. Amino Acids, Peptides, Proteins and Nucleic Acids 8. Fats, Oils, Soaps and Detergents 9. Synthetic Polymers 10. Synthetic Dyes PART III: PHYSICAL CHEMISTRY 1. Elementary Quantum Mechanics 2. Spectroscopy 3. Photochemistry 4. Physical Properties and Molecular Structure 5. Solutions, Dilute Solutions and Colligative Properties 6. Statistical Mechanics

11 Chemistry for Degree Students (B.Sc. 2nd Year) 10% OFF Publisher : SChand Publications ISBN : Author : R L Madan Type the URL : Get this ebook

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