Chemistry 1

UNIVERSITY OF KERALA POST GRADUATE PROGRAMMES IN CHEMISTRY (Under Semester System wit effect from 2001 admission) PREAMBLE There are three independent PG programmes in Chemistry, namely M.Sc. Programme in Branch III – Chemistry, M.Sc. Programme in Branch IV – Analytical Chemistry and M.Sc. Programme in Branch V – Applied Chemistry. All these three M.Sc. Programmes are equivalent in all respect for employment and higher studies. Each of these three PG programmes shall extend over a period of two academic years comprising of four Semesters, each of 450 hours in 18 weeks duration. The syllabi and schemes of examinations of these three programmes are detailed below. The theory courses of first three Semesters and the practical courses of the first two semesters of the three programmes are common, since all these three programmes are equated. Therefore, the Examinations of these three PG programmes are to be conducted by a common Board of Examiners, and questions for the first three Semesters will be common for all the these M.Sc. Programmes. These syllabi are effective from 2001 admission in affiliated colleges of the University. M.Sc. PROGRAMME IN BRANCH III – CHEMISTRY (Under Semester System with effect from 2001 admission) SYLLABUS AND SCHEME OF EXAMINATION Course No. & Title

Hours per week L

CH 211 Inorganic Chemistry-I CH 212 Organic Chemistry-I CH 213 Physical Chemistry-I CH 214 Inorganic Practical-I

5 5 5

CH 215 Organic Practical-I CH 216 Physical Practical-I

Duration of ESA in hours

Marks for CA

Marks for ESA

P SEMESTER I* 3 25 75 3 25 75 3 25 75 3 (To be continued in Semester II) 3 (To be continued in Semester II) 4 (To be continued in Semester II)

Total Marks for Semester I

Total Marks

100 100 100

300

*Distribution of teaching hours/week: - Theory – 15 hours, Practical – 10 hours (1 hour for Seminar) SEMESTER II* CH 221 Inorganic Chemistry-II CH 222 Organic Chemistry-II CH 223 Physical Chemistry-II CH 214 Inorganic Practical-I CH 215 Organic Practical-I CH 216 Physical Practical-I

5 5 5 3 3 4

3 3 3 6 6 6

35 25 25 25 25 25

75 75 75 75 75 75

Total Marks for Semester II *Distribution of teaching hours/week: - Theory – 15 hours, Practical – 10 hours (1 hour for Seminar)

100 100 100 100 100 100 600

CH 231 Inorganic Chemistry-III CH 232 Organic Chemistry-III CH 233 Physical Chemistry-III CH 234 Inorganic Practical-II

5 5 5

CH 235 Organic Practical-II CH 236 Physical Practical-II

SEMESTER III* 3 25 75 3 25 75 3 25 75 3 (To be continued in Semester IV) 3 (To be continued in Semester IV) 4 (To be continued in Semester IV) Total Marks for Semester III

100 100 100

300

*Distribution of teaching hours/week: - Theory – 15 hours, Practical –10 hours (1 hour for Seminar) SEMESTER IV* CH 241(a) Advanced Inorganic Chemistry CH 241(b) Advanced Organic Chemistry CH 241(c) Advanced Physical Chemistry CH 234 Inorganic Practical-II CH 235 Organic Practical-II CH 236 Physical Practical-II CH 242 Dissertation Comprehensive Viva Voce

** 15

3

25

75

100

3 3 4

6 6 6

25 25 ---

75 75 100 100

100 100 100 100

Total Marks for Semesters IV

600

Grand Total (for Semesters I – IV)

1800

*Distribution of teaching hours/week: - Theory – 15 hours ( 10 hours for Discussion on Project) Practical –20 hours (1 hour for Seminar) **Each student has to choose either (a),(b) or (c) as elective in accordance with the Dissertation chosen.

SYLLABUS FOR M.Sc. PROGRAMME IN BRANCH III – CHEMISTRY (Under Semester System w.e.f. 2001 Admission) SEMESTER I CH 211 INORGANIC CHEMISTRY – I Total 90 h Unit I Main Group and Transition Elements

18 h

Noble gas compounds: Preparation, properties, and structure and bonding. Halogens in positive oxidation states. Interhalogen compounds: Preparation, Properties, structure and bonding, and uses. Pseudohalogens: Preparation, properties, and structure and bonding. Polyhalide ions. Astatine: Synthesis, stability and properties. Survey of the transition elements. General characteristics of transition elements. Electronic configurations and oxidation states. Study of the following groups of elements and their compounds with peculiar structures, and their recent chemistry. Ti Zr Hf

V Nb Ta

Cr Mo W

Mn Tc Re

Unit II Isopoly and Heteropoly Acids

18 h

Isopoly and heteropoly acids of Mo and W: Preparation, properties and structure. Classification, preparation, properties and structures of borides, carbides, nitrides and silicides. Silicates: Classification and structure, Silicones: Preparation, properties and applications. Unit III Sulphur, Nitrogen, Phosphorus and Boron Compounds

18 h

Sulphur-Nitrogen compounds: Tetrasulphur tetranitride, disulphur dinitride and polythiazyl. SxNy compounds. S-N cations and an ions. Other S-N compounds. Sulphur-phosphorus compounds: Molecular sulphides such as P4S3, P4S7, P4S9 and P4S10. Phosphours-nitrogen compounds: Phosphazines. Cyclo and linear phosphaziens. Other P-N compounds. Boron-nitrogen compounds: Borzine, substituted borazines and boron nitride. Boron hydrides: Reactions of diborane. Structure and bonding. Polyhedral boranes: Preparation, properties, and structure and bonding. The topological approach to boron hydride structure. Styx numbers. Importance of icosahedral framework of boron atoms in boron chemistry. Closo, nido and arachno structures. Structural study by NMR. Wade’s rules. Carboranes. Metallocarboranes. Organoboron compounds and hydroboration. Unit IV Analytical Principles

18h

Evaluation of analytical data: Accuracy and precision. Standard deviaton, variance and coefficient of variation. Student ‘t’ test. Confidence limits. Estimation of detection limits. Errors: Classification, distribution, propagation, causes and minimization of errors. Significant figures and computation rules. Correlation analysis: Scatter diagram. Correlation coefficient 'r'. Calculation of 'r' by the method of least squares. Volumetric methods: Classification of reactions in volumetry. Theories of indicators: Acid-base, redox, adsorption, metallochromic, fluorescent and chemiluminescent indicators. Complexation titration: Titration using EDTA, NTA and Titriplex. Precipitation titrations. Redox titrations. Gravimetric methods: Mechanism of precipitate formation. Aging of precipitates. Precipitation from homogeneous solutions. Coprecipitation and postprecipitation. Contamination of precipitates. Washing, drying and ignition of precipitates. Orgnic reagents used in gravimetry: Oxine,dimethylglyoxime and cupferron. Thermal methods of analysis: Principles and instrumentation of TG and DTA. Complementary nature of TG and DTA. Differential scanning calorimeter (DSC). Applications of thermal methods in analytical chemistry and in the study of mineral and polymers. Unit V Nuclear Chemistry

18 h

Nuclear structure, mass and charge. Nuclear moments. Binding energy. Semiemperical mass equation. Stability ruels. Magic numbers. Nuclear models: Shell, Liquid drop, Fermi gas, Collective and Optical models. Equation of radioactive decay and growth. Half life and average life. Radioactive equilibrium. Transient and secular equilibria. Determination of half-lives. Nuclear reactions: Energetics of nuclear reactions. Types of nuclear reactions. Spontaneous and reduced fission. Neutron capture cross section and critical size. Principles of working of the reactors of nuclear power plants. Breeder reactor. Nuclear fusion reaction. Detection and measurement of radiation. Principles of working of different counters: GM, Proportional, Ionization and Scintillation counters. Applications of radioactivity. References 1. 2. 3.

M.C.Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press. F.A.Cotton and G.Wilkinson, “Advanced Inorganic Chemistry”, John Wiley & Sons J.E.Huheey, “Inorganic Chemistry-Principles of Structure and Reactivity”, Harper Collins College Publishers.

4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

C.J.Mooday and J.D.R.Tanas, “Noble Gases and Their Compounds”, Pergamon Press. J.H.Hollaway, “Noble Gas Chemistry”, Methuen, New York. H.R.Alcock, “Phosphorus-Nitrogen Compounds”, Academic Press K.F.Purcell and J.C.Kotz, “Inorganic Chemistry”, Saunders. A.I.Vogel,”A Text Book of Quantitative Inorganic Analysis”, Longman. D.A.Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College Publishing. W.W.Wendlandt, ‘Thermal Methods of Analysis”, John Wiley & Sons. G.Friedlander and J.W.Kennady, “Introduction to Radiochemistry”, John Wiley & Sons G.Fiedlander, J.W.Kennady and J.M.Mites, “Nuclear and Radiochemistry”, John Wiely & Sons. S.Glasston, “Source Book on Atomic Energy”, Associated East-West Press. H.J.Arnikar, “Essentials of Nuclear Chemistry” IV Edition, New Age International, New Delhi. CH 212 ORGANIC CHEMISTRY-I Total 90 h

Unit I Stereochemistry of Organic Compounds

18 h

Molecular chirality and stereochemical nomenclature. Molecules with chiral axes and planes. Molecular shape, topology and optical activity. Atropisomerism and its designation. Racemisation, resolution, prostereoisomerism, stereotopicity and enantiomeric excess. Non-carbon chiral centres. Introduction to chiroptical properties. ORD, CD and their application in assigning configuration and conformation. Octant and axial haloketone rules. Conformational analysis of cycloalkanes, decalins and their substituted derivatives. Unit II Structure, Reactivity and Intermediates 18 h Electronic and steric effects. Influence of structural features on acidity, basicty and reactivity of organic compounds. Structure, formation and properties of carbenes, nitrenes and arynes. Singlet and triplet carbenes, formation and reactions. Carbon free radicals: Structure, formation and stability. Radical reactions, autoxidation and radical chain reactions. Structure, stability and formation of carbocations and carbanious. Arynes: Formation and structure. Benzyne SNI and SNAr mechnaisms in aromatic nucleophilic substitution. Orientational effects of substituents in aromatic electrophilic substitutions. Unit III Substitution and Elimination Reactions

18 h

Nucleophilic substitution at sp3 carbon, its mechanisms and stereochemical aspects. Effect of solvent, leaving group and substrate structure. Neighboring group participation. Non-classical carbocations. Elimination reactions leading to C=C bond formation and their mechanisms. Stereospects of C=C bond formation. Effect of leaving group and substrate structure. Hoffman and Saytzeff elimination. Unit IV Reactivity of Unsaturated Systems

18 h

Stereoaspects of the addition of X2, HX, boranes and hydroxylation to C=C systems. Cis and trans Hydroxylation of cycloalkenes. Nucleophilic addition to activated C=C systems. Michael addition. Mechanism, with evidence, of Aldol (normal, crossed and directed), Perkin, Stobbe, Knovenagel, Darzen, Reformatsky and Benzoin condensations. Grignard, Cannizzaro Witting and Wittig-Horner reactions. Mechanism and stereochemistry pf addition to C=O systems. Cram’s rule. Mechanism of esterification and ester hydrolysis. Unit V Separation Techniques

18 h

Chromatographic methods: Classification of chromatographic separations. Theory of chromatography. Applications of chromatographic mehtods: Adsorption and partition chromatography. Paper, thinlayer and column chromatographic methods. LC, HPLC and GC. Column matrices. Detectors. Affinity and chiral columns. Solvent extraction. Liquid-liquid extraction. Distribution law. Successive extractions. Craig method. Uses of oxine, dithizone, high molecular weight amines, dithiocarbamates and crown ethers in extraction. Normal and ultracentrifugation.

Reference 1. 2. 3. 4. 5. 6. 7. 8.

D.Nasipuri, “Stereochemistry of Organic Compounds”, Wiley Eastern I.L.Finar, “Organic Chemistry” Vol 2, Longman P.Sykes, “A Guidebook to Mechnaisms in Organic Chemistry”, Longman S.N.Issacs, “Physical Organic Chemistry”, Longman J.March, “Advanced Organic Chemistry”, Wiley C.J.Moody and W.H.Whitham, “Reactive Intermediates”, Oxford University Press D.A. Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College Publishing. R.A.Day and A.L.Underwood, “Quantitative Analsis”, Prentice Hall. CH 213 PHYSICAL CHEMISTRY-I Total 90 h

Unit I Development of Quantum Mechanics

18 h

Introduction to Classical Mechanics: Newtonian Mechanics. Lagrange and Hamiltonian equation of motion. Conservation of angular momentum. Hamiltonian function and energy. Classical wave equation. Experimental foundation of quantum mechanics. The blackbody radiation, photoelectric effect, Compton effect and atomic spectra. Failure of classical mechanics to explain these phenomena. Quantum mechanical explanations. Formulation of quantum mechanics: The wave nature of sub-atomic particles – The de Broglie relation. Experimental proof for the de Broglie relation. Group velocity and phase velocity. The uncertainty principle and its consequences. The postulates of quantum mechanics. Setting up of the Schrodinger wave equation. Concept of operators. Laplacian, Hamiltonian, linear and Hermitian operators. Angular momentum operators and their properties. Commutator. Eigen function and eigen values. Physical interpretation of wave function. Orthogonality theorem. Orthonormality. Boundary conditions and well-behaved solutions. Solutions of Schrodinger wave equation for a free particle, particle on a ring, particle in one-dimensional box and particle in three-dimensional box. Unit II Application of Quantum Mechanics-I

18 h

Application of Quantum Mechanics to simple systems: Linear harmonic oscillator. Derivation of expression for frequency of oscillation. Classical treatment of simple linear harmonic oscillator and its limitation. Quantum mechanical treatment. Complete solution for linear harmonic oscillator in one dimension. Hermite polynomial, recurrence formula and orthogonality. Normalized solution and energy values. Hydrogen-like atom: Schrodinger wave equation in polar coordinates. Separation of Variables and complete solution of the Ø equation. Statement of the wave functions of the θ and radial parts (complete mathematical steps not required). Atomic orbitals. Total wave function of hydrogen atom. Space quantisation. Approximate methods: Perturbation theory. A set of successive corrections to an unperturbed problem. The variation principle. Secular equations. Many electron atoms: Slater’s treatment of complex atoms. Exchange of spectra. Degeneracies. Solutions of secular equations. Self-consistent field method. Electron correlation in the helium atom. Angular momenta. The spin of electrons. The exclusion principle. Vector atom model. Spin orbit coupling. Term symbols and explanation of atomic spectra. Slater’s approximation. Slater’s rules and their application in empirical calculation of ionization energy of multielectron atoms. Unit III Applications of Quantum Mechanics-II

18 h

MO theory of hydrogen molecule ion. Secular equation and its solution. Electron density distribution and stability of H2+ ion. MO and VB theories of H2. Resonance. MO theory of homonuclear diatomic molecules. Bond order and stability. MO theory of simple heterogeneous diatomic molecules like HF, LiH, CO and NO.

Directed Valences: The hybridization. Expressions for hybrid orbitals in terms of wave functions of s and p orbitals and explanation of directed valences of sp, sp2 and sp3 hybrid orbitals. The ‫ٱ‬-bonds and the treatment of delocalised electrons. Qualitative picture of butadiene and benzene. Bonding and hybridization involving dorbitals. Ionic Bonding: Ionic bonding and potential energy field. Lattice energy. Born theory and Born-Haber cycle. Elctronegativity: Pauling, Mullikan and Allred-Rochow scales. Electronegativity and percentage of ionic character. Secondary bond forces: The van der Waals' forces, ion-dipole, ion-induced dipole, dipole-dipole, dipoleinduced dipole and London dispersion forces. The hydrogen bond. Unit IV Chemical Kinetics

18 h

Complex reactions: Reversible, consecutive, concurrent and branching reactions. Free radical and chain reactions. Steady state treatment. Reactions like H2-Cl2, H2-Br2, and decompositions of ethane, acetaldehyde and N2O5. RiceHerzfeld mechanism. Unimolecular reaction. Lindemann treatment. Semenoff-Hinshelwood mechanism of chain reaction and explosion. Kinetics of fast reactions: Relaxation method, relaxation spectrometry, flow method, shock method, fast mixing method, field jump method and pulse method. Theories of reaction rate: Influence of temperature on reaction rate. Arrhenius equation and its limitations, activation energy. Collision theory and absolute reaction rate theory. Free energy of activation and volume of activation. Thermodynamic formulation of reaction rate. Effects of pressure and voulume on the velocity of gas reaction. Reactions in soulution: comparison between reactions in gas phase and in solution. Factors determining reaction rates in solution. Reaction between ions and influence of ionic strength. Primary and secondary kinetic salt effects. Influence of solvent on reaction rate. Significance of volume of activation. Hammet and Tafel equation. Photochemistry: Effect of radiation on the rate of reaction. Law of photochemistry. Quantum yield. Radiative and non-radiative transitions. Fluorescence and quenching of fluorescence. Photosensitization. Flash photolysis. Photochemical reactions of H2-Cl2 and H2-Br2. Photostationary state. Chemiluminescence. Unit V Surface Chemistry, Colloids and Catalysis

18 h

Different types of surfaces. Examination of surfaces using ESCA, Auger, SEM and STM. Properties of surface phase. Thermodynamics of surface. Surface tension of solutions. Gibbs’ adsorption equation and its verification. Surfactants and miscelles. Surface films: Different types. Surface pressure and surface potential, and their measurements and interpretation. The gas-solid inter phase: Types of adsorption. Hear of adosrption. The Langmuir theory-kinetic and statistical derivation. Multilayer adsorption- the BET theory and Harkins-Jura theory. Adsorption from solutions on solids. Langmuir and classical isotherms. Chemisorption-differences with physical adsorption. Adsorption isotherms. Adsorption with dissociation. Adsorption with interaction between adsorbate molecules. Measurement of surface area of solids: Harkins-Jura absolute method, entropy method, and the point B method. Use of Langmuir, BET and Harkins-Jura isotherms for surface area determination. The colloidal state: Multimolecular, macromolecular and associated colloids. Stability of collids. The zeta potential. Kinetic, optical and electrical properties of colloids. Electrokinetic phenomena: Electrophoresis, electroosmosis, sedimentation potential and streaming potential. Donnan membrane equilibrium. Catalysis: Mechanism and theories of homogeneous and heterogeneous catalysis. Acid-base and enzyme catalysis. Bimolecular surface reactions. Langmuir-Hinshelwood mechanism. At least 100 problems to be worked out from all units together. 30% of the questions for Examination shall contain problems.

References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.

M.W.Hanna: “Quantum Mechanics in Chemistry”, Benjamin M.C.Day and J.Selbin: “Theoretical Inorganic Chemistry”, Affiliated East West Press I.N.Levine: “Quantum Chemistry”, Prentice Hall Manas Chanda: “Atomic Structure and Chemical Bond including Molecular Spectroscopy”, Tate McGrawHill Donald A McQuarrie: “Physical Chemistry-A Molecular Approach”, Viva Low Priced Edition C.A.Coulson: “Valence”, Oxford University Press G.W.Castellan: “Physical Chemistry”, Narosa Publishing House S.Glasstone and H.S.Taylor: “Treatise on Physical Chemistry”, D.Van Nostrand A.A.Frost and Pearson: “Kinetics and Mechanism”, John Wiley and sons K.J.Laidler: “Chemical Kinetics”, McGraw-Hill S.Glasstone, K.J.Laidler and H.Eyring: “ The theory of Rate Process”, McGraw Hill P.H.Emmet, “Catalysis – Vol I – Fundamental Principles”, John Wiley Sons A.E.Alexander and P.Johnson: “Colloid Science”, Oxford University Press J.N.Gurtu and H.Sneji: “Advanced Physical Chemsitry”, Pragati Prakash A.W.Adamson: “The Physics and Chemistry of Surfaces”, Interscience S.J.Gregg: “The Surface Chemistry of Solids”, Chapman and Hall N.K.Adam: “The Physics and Chemistry of Surfaces”, Oxford University Press F.Daniels and R.A.Alberty: “Physical Chemistry”, Wiley Eastern. CH 214 INORGANIC PRACTICLS-I Total 125 h

1. 2. 3. 4.

Sepration and identification of rare/less familiar metal ions such as Ti,W,Sc,Mo,Ce,Th,Zr,V,U,Li. Volumetric estimations using EDTA, ammonium vanadate, ceric sulphate, chloramine-T and potassium iodate. Colorimetric determinations of Cr,Fe,Mn,Ni,Ti,W and Cu. Preparations of atleast 8 metal complexes.

References 1. 2. 3. 4.

A.I.Vogel, “A Text Book of Quantitative Inorganic Analysis”, Longman. A.I.Vogel, “A Text Book of Qualitative Inorganic Analysis”, Longman. D.A.Skoog and D.M.West, “Analytical Chemistry: An Introduction”, Saunders College Publishing W.G.Palmer, “Experimental Inorganic Chemistry”, Cambridge University Press. CH 215 ORGANIC PRACTICAL-I Total 125 h

1.

General methods of separation and purification of organic compounds with special reference to: (a) Solvent extraction. (b) Fractional crystallization (c) Steam distillation and distillation under reduced pressure. (d) Column, paper and thin layer chromatography.

2.

Analysis of organic binary mixtures: Separation and identification of organic binary mixtures containing atleast one component with two substituents. (A student is expected to analyze atleast 10 different binary mixtures). Preparation of organic compounds: Single stage preparations by reactions involving nitration, halogenation, oxidation, reduction, alkylation, acylation, condensation and rearrangement. (A student is expected to prepare atleast 10 different organic compounds by making use of the reactions given above).

3.

References 1. 2. 3.

A.I.Vogel, “A Text Book of Practical Organic Chemistry”, Longman. A.I.Vogel, “Elementary Practical Organic Chemistry”, Longman. F.G.Manu and B.C.Saunders, “Practical Organic Chemistry” Longman. CH 216 PHYSICAL PRACTICAL-I Total 125 h

A student has to carry out atleast 35 experiments without omitting any of he topics given below: 1.

Phase rule

(a) Distribution Law: Partition of iodine between water and carbon tetrachloride. Equilibrium constant of I- + I2 □ I3-. Concentration of unknown potassium iodide. Partition of ammonia between water and chloroform. Equilibrium constant of Cu 2+ + 4NH3 □ Cu(NH3) 42+. Partition of aniline between benzene and water. Hydrolysis constant of aniline hydrochloride. Association of benzoic acid in benzene.

(b) Solid-Liquid Equlibria: Construction of phase diagrams of simple eutectics, systems with congruent melting points and solid solutions. Determination of composition of unknown mixtures. Analytical and synthetic methods for the determination of solubilities and heat of solution. (c) Partially Miscible Liquids: Critical solution temperature, influence of impurities on the miscibility temperature (KCl, NaCl and/or succinic acid). Determination of compositions of unknown mixtures. (d) Completely Miscible Liquid Systems: Construction of phase diagrams of two-component liquid system. Zeotropic and Azeotropic. (e) Three Component Systems: With one pair of partilally miscible liquids. Construction of phase diagrams and tie lines. Compositions of homogeneous mixtures. 2.

Dilute Solutions (a) Depression in Freezing Point: Determination of molar depression constant, molecular mass, mass of solvent and composition of solution using solid solvents. Study of dissociation and association of solutes. Atomicity of sulphur. Measurement of activity coefficient and partial molar properties. (b) Transition Temperature: Determination of molar transition point depression, molecular mass, mass of solvent and composition of solution.

3. Thermochemistry Determination of water equivalent, heat of neutralization, heat of ionization, integral heat of solution, heat of displacement and thermometric titrations. 4.Chemical Kinetics Acid hydrolysis and alkali hydrolysis of esters. Arrhenius parameters. Persulphate-iodide reaction. Effect of ionic strength and solvent on reaction rate.

5. Adsorption Verification of Langmuir and classical isotherms for adsorption of solutes on solids. Estimation of surface excess and molecular area. Preparation of simple colloids and determination flocculation value. References 1. 2. 3. 4. 5.

A.Finlay and J.Akitchener, “Practical Physical Chemistry”, Longman F.Daniels and J.H.Mathews, “Experimental Physical Chemistry”, Longman. A.M.James, “Practical Physical Chemistry”, J.A.Churchil. H.H.Willard, L.L.Merritt and J.A.Dean, “Instrumental Methods of Analysis”, Affiliated East-West Press. D.P.Shoemaker and C.W.Garland, “Experimental Physical Chemistry”, McGraw-Hill.

SEMESTER II CH 221 INORGANIC CHEMISTRY-II Total 90 h Unit I Theories of Metal Complexes

18 h

Valence bond theory and its limitations. Ligand field theory: Splitting of d orbitals in different ligand fields such as octahedral, tetragonal, square planar, tetrahedral trigonal bipyramidal and square pyramidal fields. Jahn-Teller effect. Ligand field stabilization energy (LFSE) and its calculations. Thermodynamic effect of LFSE. Factors affecting the splitting parameter Spectrochemical series. Molecular orbital theory based on group theoretical approach and bonding in metal complexes Σ and π bondings in complexes. MO diagrams of complexes with and without π bonds. Effect of π bond on the stability of Σ bond. Nephelauxetic series. Critical comparison of the three theories as applied to metal complexes. Unit II Spectral and Magnetic Properties of Metal Complexes

18 h

Spectral properties of complexes: Term symbols for d-ions. Characteristics of d-d transitions. Selection rules for d-d transitions. Orgel diagrams. Tanabe-Sugano diagrams. Effects of Jahn-Teller distortion and spin-orbit coupling on spectra. Charge transfer spectra. Magnetic properties of metal complexes: Types of magnetism shown by complexes. Magnetic susceptibility measurements. Gouy method. Spin-only value. Orbital contribution to magnetic moment. Ferromagnetism and antiferromagnetism in complexes. Application of magnetic measurements to structure determination of transition metal complexes. Unit III Reactions of Metal Complexes

18 h

Isomerism: Geometrical, optical and other types. Stepwise and overall formation (stability) constants. Chelate effect. Irwing-William order of stability. Factors affecting stability of complexes. Kinetics and mechanism of reactions involving complexes in solution. Inert and labile complexes. Ligand displacement (substitution) reactions in octahedral and square planar complexes. The trans effect. Ligand field effects on reaction rate. Influence of acid and base on reaction rate. Redox reactions in complexes: Electron transfer and electron exchange reactions. Outersphere and innersphere mechanisms of redox reactions. Unit IV Organometallic Compounds

18 h

Metal carbonyls, nitrosyls and cyanides. Synthesis, structure and bonding in polynuclear carbonyls with and without bridging. Complexes with liner π -donor ligands: Olefins, acetylenes, dienes and allyl complexes. Hapto nomenclature. Complexes with cyclic π -donors: Cyclopentadiene, benzene, cycloheptatriene and

cyclooctatetraene complexes, structure and bonding. Fluxional molecules. Catalysis by organometallic compounds: Hydrogenation, hydroformylation and polymerization reactions. Unit V Bioinorganic Chemistry

18 h

Metalloporphyrins: Porphyrin ring system. Chlorophyll – synthetic model for photosynthesis. Cytochromes: Biological importance of iron. Availability and transport of iron. Haemoglobin and myoglobin. Synthetic oxygen carrier. Iron in enzymes. Catalytic functions of metalloenzymes in biological processes. Cobaltamine in amin oacid catabolism. Synthetic model of enzyme action. Inhibition and poisoning by metal ions. Copper in cytochrome oxidase and in respiratory chain. Na and K in blood, in Urine, transport in kidney and in intracellular fluid. Zn in aldolase activity. Nitrogen fixation and nitrogenases. Dinitrogen complexes. References 1. 2. 3. 4. 5. 6. 7.

M.C.Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press. F.A.Cotton and G.Wilkinson, “Advanced Inorganic Chemistry”, John Wiley & Sons J.E.Huheey, “Inorganic Chemistry-Principles of Structure and Reactivity”, Harper & Collins College Publication. S.F.A.Kettle, “Coordination Chemistry”, Longman J.C.Bailar, “Chemistry of Coordination Compounds”, Reinhold F.Baselo and R.Johnson, “Coordination Chemistry”, Bejamin Inc. H.J.Emeleus and A.G.Sharp, “Modern Aspects of Inorganic Chemistry”, Van Nostrand.

CH 222 ORGANIC CHEMISTRY-II Total 90 h Unit I Molecular Rearrangements

18 h

Mechanism, with evidence, of Wagner – Meerwein, Pinacol, Demjanov, Hafmann, Curtius, Schmidt, Lossen, Beckmann, Wolff, Fries, Arylazo, Fischer – Hepp, Hofmann-Martius, von Richter, Orton, Bamberger, Smiles, Dienone-Phenol, Benzilic acid, Benzidine, Favorskii, Stevens, Witting, Sommelet-Hauser, Baeyer-Villiger, Hydroperoxide and borane rearrangements. Dakin reaction. Unit II Aromaticity and Symmetry Controlled Reactions

18 h

Symmetry properties of Mos. LCAO-MO theory of simple conjugated polyenes and cyclic polyenes. Aromaticity and antiaromaticity. Homo, hetero and nonbenzenoid aromatic systems. Aromaticity of annulenes. mesoionic compounds, metallocenes, cyclic carbocations and carbanions. Classification of pericyclic reactions. Mechanism and stereo course of electrocyclic, cycloaddition and sigmatropic reactions. Woodward-Hoffmann rules. FO, CD and Huckel-Mobius analysis of electrocyclic and cycloaddition reactions. FO analysis of [l,j] and [3,3] migration. Claisen rearrangement. Steroaspects of Diels-Alder reaction and Cope rearrangement. Fluxional molecules. Retro Diels-Alder, Ene, cheletropic and cis elimination reactions. Synthetic applications. Unit III Organic Photochemistry

18 h

Photochemical processes. Energy transfer, sensitization and quenching. Singlet and triplet states and their reactivity. Photoreactions of carbonyl compounds, enes, dienes, and arenes. Norrish reactions of acyclic ketones. Patterno-Buchi, Barton, photo-Fries and Di-π methane rearrangement reactions. Photoreactions of Vitamin D. Photochemistry of vision and photosynthesis. Singlet oxygen generation and reactions. Applications of photoreactions in laboratory and industrial synthesis. Unit IV Chemistry of natural products

18 h

Structure and synthesis of alpha-Pinene, Camphor, Cadenine and Caryophyllene. Hofmann, Emde and von Braun degradations in alkaloid chemisty. Structure elucidation of Papaverine, Quinine and Morphine. Synthesis of Quinine and Papaverine. Structure and synthesis of beta-Carotene, Flavone, Isoflavone, Cyanin and Quercetin.

Biosynthesis of terpenes and alkoloids. Classification and structure of lipids and their biofunctions. Nomenclature, structure (not elucidation) and biosynthesis of Prostaglandins PGE 2 and PGF 1V Unit V Chemistry of Biomolecules

18 h

Nomenclature, reactivity and stereochemistry of steroidal system. Stereochemistry and structure elucidation of cholesterol (no synthesis). Synthesis of Testosterone, Andestrone, Estrone and Progesterone. Steroid biosynthesis. Structure and synthesis of Vitamins A, C, B1 and Biotin. Structure of penicillins. Synthesis of paracetamol, phenobarbital, diazepam, sulfamethoxazole, benzyl penicillin and chloramphenicol. Reference 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

L.M.Harwood, “Polar Rearrangements”, Oxford University J.March, “Advanced Organic Chemistry”, Wiley S.N.Issacs, “Physical Organic Chemistry”, Longman P.Y.Bruice, “Organic Chemistry”, Prentice Hall H.Arora, “Organic Photochemistry and Pericyclic reactions” C.H.Dupuoy, and O.L.Chapman, “Molecular Reactions and Photochemistry”, Prentice Hall J.M.Coxon and B.Holton, “Organic Photochemistry”, Cambridge University Press S.H.Pine, “Organic chemistry”, McGraw-Hill I.L.Finar, “Organic Chemistry”,Vol2, Longman ersity Press. J.Kagan, “Organic Photochemistry”, Academic Press. R.J.Simmonds, “Chemistry of Biomolecules”, Royal Society of Chemistry. J.Mann and others, “Natural Products – Their Chemistry and biological significance”, Longman I.L.Finar, “ Orgnic Chemistry” Vol 2, Longman W.Kar, “Medicinal Chemistry”, Wiley Eastern

CH 223 PHYSICAL CHEMISTRY-II Total 90 h Unit I Molecular Symmetry and Basics of Spectroscopy

18 h

Symmetry and Character Tables: Symmetry elements and symmetry operations. Point groups. Multiplication of operations. Conditions for a set of elements to form a group. Group multiplication table. Similarity transformation and classification of symmetry operations. Matrix representation of point group. Reducible and irreducible representations. Character of a matrix. Orthogonality theorem. Rules derived from orthogonality theorem (proof not required). Setting up of the character tables of simple groups such as C 2v and C 3v on the basis of the rules. The four areas of the character table. Basics of molecular spectroscopy: origin of spectra. Energy levels in molecules. Origin of rotational, vibrational, electronic and Raman spectra and the regions of electromagnetic spectrum where they appear. Intensity of absorption: Beer-Lambert’s law, selection rule of rotational, vibrational, electronic and Raman spectra. Basic elements of practical spectroscopy-signal to noise ratio, width and intensity of spectral transitions. BornOppenheimer approximation. Unit II Spectroscopy-I

18 h

Microwave spectroscopy: Rotation of diatomic molecules. Rotational spectrum: Intensity of spectral lines. Calculation of internuclear distance. Non-rigid rotors and centrifugal distortion. Rotational spectra of polyatomic molecules- linear and symmetric top molecules. Introduction to instrumentation. Infrared spectroscopy: Vibrational spectra of harmonic and anharmonic diatomic molecules. Morse function. Fundamentals and overtones. Determination of force constants. Interaction of rotation and vibration. Different branches of spectrum. Asymmetry of vibrational-rotational spectrum. Vibrational spectra of polyatomic molecules. Vibrations of polyatomic molecules, normal modes, classifications of vibrations: Stretching, bending, symmetric, asymmetric, parallel and perpendicular vibrations. Overtones, combinations and Fermi resonance. Finger print and group frequencies. Introduction to instrumentation and FT-IR.

Raman spectra: Scattering of light. Raman scattering. Polarisability and classical theory of Raman spectrum. Rotational and vibrational Raman spectrum. Raman spectra of polyatomic molecules. Complimentarity of Raman and IR spectra. Mutual exclusion principle. Introduction to instrumentation. Laser Raman spectrum. Electronic spectra: Term symbols of molecules. Electronic spectra of diatomic molecules. Vibrational coarse structure and rotational fine structure of electronic spectrum. Franck-Condon principle. Types of electronic transitions. Fortrat diagram. Predissociation. Calculation of heat of dissociation. Electronic spectra of polyatomic molecules: Electronic transitions among molecular orbitals and absorption frequencies. Effect of conjugation on absorption frequencies. Introduction to instrumentation Unit III Spectroscopy-II

18 h

Resonance spectroscopy: NMR spectrum. Nuclear spin. Interaction between nuclear spin and applied magnetic field. Proton nmr spectrum. Population of energy levels. Nuclear resonance Chemical shift. Relaxation methods. Spin-spin coupling. Fine structure. Elementary idea of 2D and 3D nmr. Mention of nmr spectra of other nuclei. Introduction to instrumentation. ESR spectrum: Electron spin of molecules. Interaction with magnetic field. The g factor. Determination of g values. Fine structure and hyperfine structure. Elementary idea of ENDOR and ELDOR. Mossbauer spectroscopy: principle, Doppler effect, recording of the spectrum, chemical shift, and quadrupole effect. Photoelectron spectroscopy: Introduction to UV photoelectron and X-ray photoelectron spectroscopy. Electron diffraction of gases. Incoherent scattering, Vierl’s equation, correlation and radial distribution. Polarisation and dipole moment: Debye and Calusius- Mossotti equation. Determination of dipole moments. Structural information from dipole moments. Spectral methods: UV-Visible spectrophotometry: fundamental laws of photometry. Basic instrumentation. Simultaneous determination of two components. Flame emission and atomic absorption spectroscopy. Instrumentation for AAS. The flame spectra and flame characteristics. Atomiser used in spectroscopy. Hollow cathode lamp. Interference in AAS. Application of AAS. Mossbauer spectroscopy: principle and application. Unit IV Basics of Chemical Thermodynamics

18 h

Thermodynamic properties: State and path properties. Intensive and extensive properties. Exact differentials. Intrinsic energy, enthalpy, entropy, free energy and their relations and significances. Eulers relation. Jacobians. Maxwll relations. Thermodynamic equations of state. Joule-Thomson effect. Joule-Thomson coefficient for van der Waals’ gas. The third law of thermodynamics. Need for the third law. Nernst heat theorem. Apparent exceptions to third law. Application of third law. Properties of solutions: Thermodynamics of ideal solutions. Partial molar quantities. Chemical potentials. Duhem-Margules equation. Nonideal solutions. Excess thermodynamic functions. Determination of partial molar properties. Fugacity and activity: Fugacity of gases. Determination. Variation of fugacity with temperature and pressure. Fugacity of liquids and solids. Fugacity of mixtures of gases. Lewis-Randall rule. Fugacity in liquid mixtures. Activity and activity coefficients. Standard states. Determination of activity and activity coefficients of electrolytes and nonelectrolytes. Unit V Application of Thermodynamics

18 h

Chemical equilibrium: Equilibrium constant in real systems. Equilibrium in homogeneous and heterogeneous system. Reaction quotient. Reaction isotherm and spontaneity of reaction. Variation of eqilibrium constant with temperature and pressure. Variation of standard free energy with temperature. Simultaneous equilibria and addition of free energies. Standard free energy of formation and its determination. Free energy functions. Phase equilibria: Criteria of eqilibrium. Derivation of phase rule. Discussion of two component systems forming solid solutions with and without maximum or minimum in freezing point curve. Systems with partially miscible solid phases. Three component systems: Graphical representation. Three component liquid systems with

one pair of partially miscible liquids. Influence of temperature. Systems with two pairs and three pairs of partially miscible liquids. Two salts and water systems. Isothermal evaporation. Transition point and double salt formation. Thermodynamics of irreversible processes: Simple examples of irreversible processes. General theory of near equilibrium processes. Entropy production from heat flow. Matter flow and current flow. Generalized equation for entropy production. The phenomenological relations. Onsager reciprocal relation. Application of irreversible thermodynamics to diffusion. Thermal diffusion. Thermoosmosis and thermomolecular pressure difference. The Glansdorf-Prigogine theorem. Quantitative introduction to treatment of far from equlibrium states. At least 100 problems to be worked out from all the units put together 30% of the questions for examination shall contain numerical problems. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.

F.A.Cotton, “Chemical Applications of Group Theory”, John Wiley & Sons. V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry” Vishal Publications. H.H.Jaffe and M.Orchin, “Symmetry in Chemistry” John Wiley and Sons P.J.Wheately, “The Determination of Molecular Structure”, Oxford University Press R.L.Carter, “Molecular Symmetry and Group theory”, John Wiley & Sons C.N.Banwell, “Fundamentals of Molecular Spectroscopy”, McGraw Hill Manas Chanda, “Atomic Structure and Chemicl Bonding including Molecular Spectroscopy”, Tate McGraw Hill G.Herzherg, “Molecular Spectra and Molecular Structure”, D.van Nostrand. S.Glasston, “Theoretical Chemistry”, D van Nostrand. D.C.Gilbert: “Investigation of Molecular Structure”, ELBS R.A.Roberty and R.J.Silbey, “Physical Chemisty”, John Wiley & Sons P.W.Atkins, “Physical Chemistry”, Oxford University Press. D.A.Skoog,D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College Publishing. R.A.day and A.L.Underwood, “Quantitative Analysis”, Prentice Hall A.I.Vogel, “Textbook of Quantitative Inorganic Analysis”, Longman. S.Glasstone: “Thermodynamics for Chemists”, Affiliated East West Publishers. S.Flasstone and H.S.Taylor, “Ttreatise of Physical Chemistry”, D van Nostrand I.Pregogine, “Introduction to Thermodynamics of Irreversible Processes”, Inter science. SEMESTER III CH 231 INORGANIC CHEMISTRY –III Total 90 h

Unit I Crystalline State

18 h

Crystal systems and lattice types. Bravais lattices. Crystal symmetry. Point groups and space groups (No detailed study). Miller indices. Reciprocal lattice concept. Close packed structures: BCC, FCC and HCP. Voids. Coordination number. Crystal binding: Molecular, covalent, metallic and hydrogen-bonded crystals. X-Ray diffraction by crystals: Functions of crystals. Transmission grating and reflection grating. Braggs equation. Diffraction methods. Powder, rotating crystal, oscillation and Weisenbeerg methods. Indexing and determination of lattice type and unit cell dimensions of cubic crystals. Structure factor. Fourier synthesis. Unit II Solid State Chemistry

18 h

S Electronic structure of solids. Band theory. Refinements to simple band theory; k space and Brillouin zones. Conductors, insulators and semiconductors. Band structure and applications. Colour in inorganic solids.

Crystal defect: Perfect and imperfect crystals. Point, line and plane defects. Thermodynamics of Schottkyand Frenkel defects. Colour centers in alkali halide crystals. Defect clusters. Extended defects: Crystallographic shear structure and stacking faults. Dislocations and crystal structure. Unit III Electrical and Magnetic Properties of Solids Electrical properties of solids: Conductivity of pure metals. Photovoltaic effect. Dielectric properties. Dielectric materials.

18 h Superconductivity.

Photoconductivity.

Ferroelectricity, pyroelectricity and piezoelectricity. Applications of ferro, piezo and pyroelectrics. Magnetic properties of solids: Behaviour of substances in a magnetic field. Diamagnetism, paramagnetism, ferromagnetism, antiferromagnetism and ferrimagnetism. Effect of temperature. Curie and CurieWeiss laws. Calculation of magnetic moments. Magnetism of ferro and antiferromagnetic ordering. Super exchange. Lasers and their applications. Unit IV Lanthanides and Actinides

18 h

Lanthanides: Characteristic properties. Electronic configurations and tern symbols Occurrence and extraction. Separation techniques. Oxidation states. Spectral and magnetic properties. Shapes of f orbitals and their splitting in cubic ligand field. Actinides: Occurrence and general properties. Electronic configuration and tern symbol. Oxidation states. Spectral and magnetic properties. Comparative properties of lanthanides and actinides. Trans-uranium elements and their stabilities. Applications of lanthanide and actinide compounds. Comprehensive study of the chemistry of beach sands of Kerala and their important components such as monazite, illmenite zircon and siliminite. Unit V Nonaqueous Solvents

18 h

Nonaqueous solvents: General properties and classification of solvents. Self-ionization and leveling effect. Reactions in nonaqueous solvents: Solute-solvent interaction. Reactions in liquid NH3. Solutions of metals in liquid ammonia. Reactions in anhydrous sulphuric acid, liquid SO2, liquid HF, liquid halogens and interhalogens, and liquid dinitrogen tetroxide. Titrations in nonaqueous solvents: Acid-base and redox titrations. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

L.V.Azaroff, “Introduction to Solids”, McGraw-Hill. N.B.Hannay, “Solid State Chemistry”, Prentice Hall. F.C.Phillips, “An Introduction to Crystallography” Longman. C.Kittel, “Introduction to Solid State Physics”, John Wiley & Sons. T.Moeller, “The Chemistry of the Lanthanides”, Reinhold. G.T.Seaborg, J.J.Katz and W.M.Manning, “The Transuranium Elements”, McGraw-Hill G.T.Seaborg, “Manmade Transruanium Elements”, Prentice Hall F.A.Cotton (Ed.), “Progress in Inorganic Chemistry”, Interscience. Simon Cotton, “Lanthanides and Actinides”, Macmillan H.Sisler, “Chemistry of Nonaqueous Solvent. Day and J.Selbin, Theoretical Inorganic Chemistry”, East-West Press J.Kucharsky and L.Safarik, Titrations in Nonaqueous Solvents”, Elsevier.

CH 232 ORGANIC CHEMISTRY –III Total 90 h Unit I UV-VIS, IR and Mass Spectroscopy

18 h

Electronic transitions in enes, enones and arenes. Woodward-Fieser rules. Effect of solvent polarity on UV absorption. Principle of characteristic group frequency in IR. Identification of functional groups and other structural features by IR. Hydrogen bonding and IR bands. Sampling techniques. FTIR and its instrumentation.

Organic mass spectroscopy. Ion production methods: EI, CI,FAB, Electrospray and MALDI, Magnetic, TOF, Quadrupole and Ion cyclotron mass analyzers. MS n technique. Characteristic EIMS fragmentation modes and MS rearrangements. Unit II NMR Spectroscopy and Structure Elucidation

18 h

Chemical shifts, anisotropic effects and coupling constants in organic compounds. Spin-spin interactions in typical systems. Analysis of 1st order spectra. Simplification methods ofr complex spectra: use of high field NMR, shift reagents, chemical exchange and double resonance. Introduction to FT (pulse) NMR; NOE; DEPT and 2DNMR. 13C NMR and 13C chemical shifts. Spectral interpretation and structure identification. Spectral interpretation using actural spectra taken from standard texts. Solving of structural problems on the basis of numerical and spectrum-based data. Unit III Organic Synthesis

18 h

C-C and C=C bond forming reactions – Mannich, Reimer-Tiemann, Simon-Smith, Vilsmeier-Haack, reformatsky and Ullmann reations. Stork enamine reaction. Shapiro, Witting – Horner, Peterson, Heck, Stille and McMurray reactions. Ring formation by Dieckmann, Thorope and Acyloin condensations. Robinson ring annulation. Synthesis of small rings. Simon-Smith reaction. Reduction and oxidation in synthesis. Catalytic hydrogenation. Alkali metal reduction. Birch eduction. Wolff-Kishner reduction. Huang-Milon modification. Clemmenson reduction. Boranes. LAH, Sodium borohydride as reductants. Dehydrogenations. Oppenauer oxidation. HIO4, OsO4 and m-ClC6H4COOOH and their applications. Unit IV Chemistry of Biopolymers

18 h

Peptides and their synthesis. Protecting groups and peptide bond formation in SPPS. Helical and sheet conformations of polypeptides. Structure organization of proteins. Chemistry of nucleic acid bases A.G.C.T and U and their synthesis. Synthesis of adenosine and ATP. Structure of DNA. Automated oligonucleotide synthesis by Phosphoramidite method – Reagents and protecting groups. Sequencing of polynucleotided and polypetides. Structure of Starch, Cellulose, Glycogen and Chitin. Unit V Chemistry of Polymers

18 h

Types and mechanism of polymerization reactions. Step-growth, free radical, addition, ionic, ring opening and gorup transfer polymerizations. Copolymers. Characterization of polymers. Methods of mesurement of molecular mass and size. Sterochemistry of polymers. Steroregularity and its control. Ziegler-Natta catalysts. Gelation and network formation. Polymer architecture, configuration and conformation. Frictional properties and mechanical properties. Glassy and rubbery states, visco-elasticity, crystallization and melting of polymers. Relation between structure, property and performance. Manufacture and applications of polyolefins, thermoplastics, polyamides, polyesters, polyurethanes, epoxies and industrial polymers. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

D.H.Williams and I.Fleming, “Spectroscopic Methods in Organic Chemistry”, Wiley. W.Kemp, “Organic Spectroscopy”, Longman J.March, “Advanced Organic Chemistry”, Wiley R.O.C.Norman and A.Coxon, “Modern Synthetic Reactions”, Chapman and Hall M.B.Smith, “Organic Systhesis”, McGraw-Hill R.K.Bansal, “Synthetic Applications in Organic Chemistry”, Narosa R.J.Simmonds, “Chemistry of Biomelecules”, Royal Society of Chemistry I.L.Finar, “Organic Chemistry” Vol 2, Longman R.J.Young, “Introduction to Polymer Science”, John Wiley & Sons F.wW.Billmayer, Text Book of Polymer Science”, John Wiley & Sons G.Odian, “Principles of Polymerization”, John Wiley & Sons J.M.G.Cowie, “Polymers: Chemistry and Physics of Modern Material”, Blackie K.J.Saunders, “Organic Polymer Chemistry”, Chapman and Hall

CH 233 PHYSICAL CHEMISTRY –III Total 90 h Unit I Gases Liquids and Liquid Crystals

18 h

Random movement of molecules. Brownian movement and determination of Avogadro number. The distribution of molecular velocities. Deviation and discussion of Maxwells equation Gamma function. Deviation of average and most probable velocities from Maxwells equation. Influence of temperature on molecular velocities. Molecular collisions and mean free path. Homogeneous and heterogeneous collisions. Collision of molecules with a surface and effusion. Effect of molecular interaction on collision. Transport properties: Viscosity, thermal conductivity and diffusion. Determination of viscosity of gases. Influence of temperature and pressure on transport properties. Liquid state: X-ray diffraction study of simple liquids and their structure. Theories of liquid state. Oscillator, free space and van der Waals therories. Lennard-Jones theory of melting. Specific heat of liquids. Liquid crystals: Mesomorphic state, types, examples and application of liquid crystals. Theories of liquid crystals. Chiral thermotropic liquid crystal polymers. Nematic liquid crystals formed from flexible molecules. Molecular field theory. Order and odd-even effects in thermotropic nematic polyesters. Photoconducting liquid crystals. Electro-optic effects in smectogenic polysiloxane side chain liquid crystal polymer. Unit II Statistical Thermodynamics

18 h

Statistical thermodynamics: Mechanical description of molecular systems. Thermodynamic property and entropy. Microstates. Canonical and grand canonical ensembles. Equation of state for ideal quantum gases. Maxwell-Boltzman distribution. The partition functions. Partition function for free linear motion, for free motion in a shared space, for linear harmonic vibration. Complex partition functions and partition functions for particles in different force fields. Langevins partition function and its use for the determination of dipole moments. Electrostatic energies. Molecular partition functions. Trnslational, rotational, vibrational and electronic partition functions. Total partition functions. Partition functions ant thermodynamic properties. Unit III-Quantum Statistics and Heat Capacity

18 h

Quantum Statistics-Bose-Einsein statistics. Bose-Einstein distribution, Thermodynamic probability, Bose Einstein Distribution Function, Example of particles. Theory of paramagnetism. Bose-Einstein condensation. Kiquid helium. Supercooled liquid. Fermi-Dirac statistics. Fermi-Dirac Distribution, Examples of particles. Fermi-Dirac Distribution Function, Thermionic emission. Relations between Maxwell-Boltzman, Bose-Einstein and Fermi-Dirac statistics. Heat capacity of gases. Equipartition principle and quantum theory of heat capacity. Calculation of Heat Capacity of gases-Limitation of the Method. Heat capacity of solids. Dulong and Petit’s Law, Kopp’s Law, Classical theory and its limitation, The vibrational properties of solids. Einstein theory of heat capacity. The spectrum of normal modes. Limitation of Einstein theory, The Debye theory. The electronic specific heat. Unit IV Electrochemistry

18 h

Ionics: Ions in solution. Deviation from ideal behaviour. Ionic activity. Ion-solvent interaction. Born equation. Ion-ion interaction. Activity coefficient and its determination. Debye-Huckel limiting law. Equation for appreciable concentration. Osmotic coefficient. Activities in concentrated solutions. Robinson-Stoke theory. Ion association. Strong electrolytes. Ion transport. Debye-Huckel treatment. Onsager equation. Limitation of the model. Conductance of high frequencies and high potentials.

Electrodics: Different types of electrodes. Electrochemical cells. Concentration cell and activty coefficient determination. Origin of electrode potential. Liquid junction potential. Evaluation of thermodynamic properties. The electrode double layer: Electrode-electrolyte interface. Theory of multiple layer capacity. Electrocapillary. Loppmann potential. Membrane potential. Elecrokinetic phenomena. Mechanism of charge transfer at electrode-electrolyte interface. Electrolysis. Current-potential curves. Dissolution, deposition and decomposition potentials. Energy barriers at metal-electrolyte interface. Different types of over potentials. ButterVolmer equation. Tafel and Nemst equations. Rate determining step in electrode kinetics. The hydrogen over voltage. The oxygen over voltage. Theories of over voltage. Unit V Electroanalytical Methods

18 h

Potentiometric methods: Reference electrodes and indicator electrodes. The hydrogen calomel, Ag-AgCl electrodes. The glass electrode – its structure, perofrmance and limitations. Measurement of pH. Petentiometric titrations. Redox and precipitation titrations. Electrogravimetry: Principle and method. Determination of Cu. Separation of metals. Conductometry: Principle and method. Conductance measurements. Conductometric titrations. Coulometry: Principle and method. Coulometric titrations. At least 150 problems to be worked out from all the units put together. 30% of the questions for Examination shall contain numerical problems. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.

G.W.Castellan, “Physical Chemistry”, Addison-Lesley Publishing Co. E.A.Moelwyn Hughes, “Physical Chemistry”, Pergamon Press L.C.Chapoy, “Recent Advances in Liquid Crystalline Polymers”, Elsevier. Denbigh, “Chemical equilibria”, D Van Nostrand. F.W.Sears and Salinger, “An introduction to Thermodynamics, Kinetic Theory of Gases and Statistical Mechanics”, Addison Wesely. M.C.Gupta, “Elements of Statistical Thermodynamics”, New Age International (P) Ltd. L.K.Nash, “Elements of Statistical Thermodynamics”, Addison Wesley Publishing Co. Kestin and Dofman, “Statistical thermodynamics”, J.Rose, “Dynamic Physical Chemistry”, Sir Issac Pitman & Sons A.W.Adamson, “The Physics and Chemistry of Surfaces”, Interscience D.R.Crow, “The Principles of Electrochemistry”, Chapman and Hall J.O.M.Bokris and A.K.N.Reddy, “Modern Electrochemistry”, Plenum Rosatta. D.A.MacInnes, “ The Principles of Electrochemistry”, Dover Publishers D.A.Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College Publishing C.L.Wilson and D.W.Wilson, “Comprehensive Analytical Chemistry”, D van Nostrand. J.G.Dick, “Analytical chemistry”, McGraw Hill

CH 234 INORGANIC PRACTICAL-II Total 125 h 1.

Estimation of simple mixture of metal ions in solution (involving quantitative separation) by volumetric and Gravimetric and methods.

2.

Analysis of some typical ores and alloys: Carbonate ore, sulphide ore, ilmemte, monazite, brass bronze and type metal.

3.

Ion-exchange separation of binary mixtures such as those of zinc and magnesium and cobalt and nickel.

References 1. 2. 3.

A.I.Vogel, “A Textbook of Quantitative Inorganic Analysis”, Longman. A.I.Weining and W.P.Schoder, “Technical Methods of Ore Analysis”. W.R.Schoder and A.R.Powell, “Analysis of Minerals and Ores of Rare Elements”.

CH 235 ORGANIC PRACTICAL-II 125 Hrs (1) Quantitative analysis: Determination of (a) carboxylic acid ester in a mixture, (b) equivalent weight of a carboxylic acid, (c) reducing sugars using Fehling’s solution, (d) phenol, salicylic acid aspirin and aniline using bromate-bromidemixture, (e) ketomethyl group in water soluble ketone such as MEK and Acetone, (f) iodine and saponification values of vegetable oils, and (g) nitrogen by semimicro Kjeldahl method and sulphur gravimetrically. (2) Preparation of the following organic compounds by the indicated routes: (a) p-Nitroaniline: Acetanilide --> p-nitroacetanilide --> p-nitroaniline. (b) 1,3,5-Tribromobenzene: Aniline --> 2,4,6-tribromoaniline --> 1,3,5-tribromobenzene (c) Methyl organe: Aniline --> sulphanilic acid --> methyl orange. (d) p-Aminoazobenzene: Aniline --> diazoaminobenzene --> P-aminoazobenzene (e) N-Acetyl anthranilic acid: o-Toluidine --> o-methylacetanilide --> N-acetyl anthranilic acid (f) P-Chlorobenzoic acid: p-Toluidine --> p-chlorotoluens --> P-chlorobenzoic acid (g) m-Nitroaniline: Nitrobenzene --> m-dinitrobenzene --> m-nitroaniline (h) Benzilic acid: Benzoin --> benzil --> benzilic acid (i) m-Nitrobenzoic acid: Methyl benzoate --> m-nitromethyl benzoate --> mnitrobenzoic acid (j) Benzanilide: Benzophenone --> oxime --> benzanilide References 1. 2. 3.

A.I.Vogel, “A Textbook of Practical Organic Chemistry”, Longman A.I.Vogel, “Elementary Practical Organic Chemistry – Part 3: Quantitative Organic Analysis”, Longman F.G.Mann and B.C.Saunders, “Practical Organic Chemistry”, Longman CH 236 PHYSICAL PRACTICAL-II Total 125 h

A student has to carry out at least 35 experiments without omitting any of the topics given below: 1. Physical properties of liquids (a) Viscosity: Viscosity of liquids and mixtures of liquids. Verification of Kendall’s equation. Composition of unknown mixtures. Determination of molecular masses polymers by viscosity measurements. (b) Surface tension: Surface tension and parachor of liquids by stalagmomenter and differential capillary methods. Calculation of atomic parachor. Variation of surface tension with concentration. Unknown concentration of a mixture. Interfacial tension. Determination of surface excess and area per molecule.

2.Beckmann method Determination of molar depession constants of benzene and water using Beckmann thermomenter. Determination of molecular mass. Study of he complex, K2HgI4. 3.Optical methods (a) Polarimetry: Measurement of specific rotation. Concentrations of glucose and sucrose in a mixture. Tate of inversion of sucrose.

(b) Spectrophotometry:

Absorption spectra of coloured compounds. Verification of Beer’s law. Determination of equlibrium constants of acid-base indicators. Determination of rate constant. Simultaneous determination of Mn and Cr in a solution of KmnO 4 and K 2Cr2O7.

4.Refractometry Refractive index and molar refraction of liquids. Atomic refractions. Composition of mixtures. Molar refraction of solid solutes. Study of the complex, K2HgI4. Molecular and ionic radii from molar refractions. 5.Electrochemistry (a) Conductance: Equivalence conductance of solutions of strong electrolytes and ewak electrolytes. Application of Kohlrausch’s law. Onsager constant. Solubility of sparingly soluble substances. Ostwald’s dilution law. Hydrolysis of salts. Ionic products of solvents. Basicity of acids. Dissociation constants of acids and bases. Conductometric titrations involving acid-base and precipitation. Solubility of calcium sulphate in water-alcohol mixture. (b) Electromotive force: Cell potentials. Electrode potentials. Concentration cells. Redox potentials. Determination of activity coefficeint. Degree of hydrolysis. Determination of pH using quinhydrone, antimony and glass electrodes. Potentiometric titrations involving acid-base, redox and precipitation. Application of Henderson’s equation. (c) Polarography: Determination of half-wave potentials of single ions and mixture of ions. Determination of formulae and stability constants of complexes. Polarographic titrations. References 1. 2. 3. 4. 5.

A.Finlay and J.A.Kitchener, “Practical Physical Chemistry”, Longman F.Daniels and J.H.Mathews, “Experimental Physcial Chemistry”, Longman A.M.James, “Practical Physical Chemistry”, J.A.Churchil H.H.Willard, L.L.Merritt and J.A.Dean, “Instrumental Methods of Analysis”, Affiliated East-West Press D.P.Shoemaker and C.W.Garland, “Experimental Physical Chemistry”, McGraw-Hill SEMESTER IV CH 241(a) – ADVANCED INORGANIC CHEMISTRY Total 90 h

Unit I Group Theory

18 h

Properties of a group. Point groups. Abelian groups. Cyclic group. Subgroup. Similarity transformation. Classes of symmetry operation. Matrix representation of symmetry operation. Representation of groups. Trace of a matrix. Reducible and irreducible representations of groups. Orthogonality theorem. Rules of irreducible representation and their properties. Construction of character tables for C2v and C3v systems.

Unit II Applications of Group Theory

18 h

Hybrid orbitals and molecular orbitals for simple molecules. Transformation properties of atomic orbitals. Hybridization schemes for σ and π bonding with examples. MO theory for ABn type molecules. Molecular orbitals for regular octabedral, tetrahedral and metal sandwich compounds. Ligand field theory: Splitting of d orbitals in different environments using gorup theoritical considerations. Construction of energy level diagrams. Correlation diagram. Method of descending symmetry. Tanabe-Sugano diagrams. Molecular orbitals in octahedral complexes. Formation of symmetry adapted group orbitals of ligands. MO diagram. Symmetry and selection rules: Symmetry properties of common orbitals. Application of character tables to infrared and Raman spectroscopes. Unit III Bonding, Symmetry and Structure of Solids

18 h

Types of solids: Ionic, covalent, molecular, metallic and hydrogen bonded solids. Cohesive forces in crystals. Lattice energy. Madelung constant. Determination of lattice energy. Zone theory. Superconductivity. High temperature superconductivity Packing of atoms and ions in solids. Voids. Coordination of voids. Crystal systems. Bravais lattices. Crystal symmetry. Point groups. Representation as stereogarms. Examples from orthorhombic, cubic and hexagonal systems. Space groups. Representation as parallelograms. Some important structural types: Rutile, pervoskits, rock salt, zinc blende, antifluorite, wurtzite and nickel, arsenide. Spinels and inverse spinels. Unit IV Properties of Solids

18 h

Diffusion in solids: Types of diffusion. Mechanisms of diffusion. Theories of diffusion. Diffusion and defects. Diffusion controlled reactions. Order-disorder transformations. Super strictires. Crystal growth. Electrical properties: Electrical conductors. Dielectric properties. Piezoelectricity, ferroelectricity and ionic conductivity. Optical properties: Photoconductivity, luminescence, colour centers, lasers, refractions and bifringence. Magnetic properties: Diamagnetism, paramagnetism,ferromagnetism, antiferromagnetism and ferrimagnetism. Thermal properties: Thermal conductivity. Specific heat. Thermal decomposition of solids. Photographic process. Self-heating and explosion. Unit V Solid State Reaction Kinetics

18 h

Isothermal and nonisothermal decompositions. Types of solid-state reactions. Analysis of decomposition data using different methods: Approximation, differential and integral methods Choosing Horrowitx-Metzger, Coasts-Redfern and Freeman-Carroll methods as examples. Evaluation of kinetic parameters such as order parameter, pre-exponential factor, energy of activation and entropy of activation from these methods. Critical comparison between the three different methods. Factors influencing the rate of solid-state reactions. Elucidation of mechanisms of decomposition reactions of solids. References 1. 2. 3. 4. 5. 6. 7. 8.

F.A.Cotton, “Chemical Applications of Group Theory”, Interscience. M.C. Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press. P.K.Bhattacharya, “Group Theory and its Chemical Application”, Himalayan Publishing House V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry”, Vishal Publications L.V.Azaroff, “Introduction to Solids”, McGraw-Hill Antony R.West, “Solid State Chemistry and its Applications”, Wiley Eastern N.B.Hannay, “ Solid State Chemistry”, Prentice Hall D.A.Young, “Decomposition of Solids”, Pergammon Press

9. 10. 11. 12.

R.M.Rose and J.Wulf, “The Structure and Properties of Materials” ,Vol I & II, Wiley Eastern William W.Portfield, “Inorganic Chemistry – A Unified Approach”, II Edition, Academic Press W.W.Wendlandt, “Termal Methods of Analysis”, John Wiley & Sons T.Hatakeyama and F.X.Quinn, “Thermal Analysis”, John Wiley & Sons

CH 241 (b) – ADVANCED ORGANIC CHEMISTRY Total 90 h Unit I Physical Organic Chemistry

18 h

Reactivity in relation to molecular structure and conformation. Steric effect. F strain. Ortho effect. Bond angle strain. Conformational effects on the reactivity of substituted cyclohexanes. The Hammett equation and its applications. Taft equation. Linear free energy relationships. Solvent polarity and parameters. Y,Z and E parameters and their applications. Primary and secondary kinetic isotope effects. Salt effects and special salt effects in SN reactions. Kinetic and thermodynamic control of reactions. The Hammond postulate. Principle of microscopic reversibility. Marcus theory. Methods of determining reaction mechanisms. Phase transfer catalysis and its applications. Unit II Methods in Organic Synthesis

18 h

Retrosynthetic analysis and disconnection approach. Synthetic strategy and synthons. Regioselectivity in enol and enamine alkylations Steroselective and stereospecific synthesis. Mitsonobu reaction. 1,3-dipolar cycloaddition in the construction of rings. Story synthesis. Olefin synthesis by extrusion reactions. Olefin metathesis. FMOC, BOC, Z, trityl, phthalimide, benzyl, tetrahydropyranyl, silyl, t-butyl, trichloroethyl, acetal and thioacetal as amino, hydroxy, thiol, caroxyl and carbonyl protecting groups in synthesis. Umpolung. Electrochemical reduction and oxidation reactions. Cathodic reduction of organic halogen, nitro and carbonyl compounds. Reductive coupling reactions. Conversions of C=O to C=CH2; epoxide to alkene and alkene to cis and trans diols. Prevost and woodward procedures. Unit III Reagents in Organic Synthesis

18 h

Applications of hydrogenation catalysts, hindered boranes, bulky metal hydrides, NaCNBH3. DIBAL, Li trialkyl borohydrides, tri-n-butyl tin hydride, diimide, Kindlar catalysts and Rosenmund reduction. McFadeyanStevens reactions. Oxidation using SeO2, lead tetraacetate, ozone, peracids, DDQ and Cr(VI) reagents. Swern oxidation, Moffatt oxidation, allylic and benzylic oxidation Sommelet reaction. Elbs reactions. Oxidative coupling of phenols. Sharpless assymetric epoxidation Chemo and regioselectivity in reductions and oxidation. Use of XeF2, SbF5,VF5,MoF6,CF3OF,SF4, HF and F2 as fluorinating agents Unit IV Organometallic Chemistry

18 h

Preparation of organo Mg, Li, Cu, Zn and Re compounds. Reactions of Grignard reagents in organic synthesis – Alkylation, oxirane addition, carbon dioxide addition, carbonly addition enone addition (1,2- and 1,4additions), reduction and enolisation reaction. Reactions of organolithium reagents – Li exchange reaction and its use in the preparation of Rli compounds, addition to C=O COOH and CONR2, Li dialkylcuprates (Gilman reagent) – preparation reaction with alkyl halides with acyl halides and with enones. Alkynyl Cu(I) reagents. Glaser coupling. Dialkyl Cd compounds preparation and reaction with acyl halides. Benzenetricarbonyl Chromium – preparation and reaction with carbanions. Tebbe reagent Unit V Molecular Tecognition and Supramolecular Chemistry

18 h

The concepts of molecular recognition, host, guest and receptor systems. Forces involved in molecular recognition. Hydrogen bonding, ionic bonding, π – stacking, van der Walls and hydrophobio interactions. Introduction to molecular receptors: Tweezers, Cryptands and Carcerands, Cyclophanes Cyclodextrins and

Calixarenes-Typical examples. Non-covalent interactions in biopolymer strructure organization. Importance of molecular recognition in DNA and protein structure, their function and Protein biosynthesis. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

N.S.Issacs, “Physical Organic Chemistry”, Longman R.A.Y.Jpmes, “Physical and Mechnaistic Organic chemistry”, Cambridge Univ. Press J.Hine “Physical Organic Chemistry”, Academic M.B.Smith, “Organic Synthesis”, McGraw Hill H.O.House, “Modern Synthetic Reactions” Benjamin Cummins R.K.Mackie, D.M.Smith, and R.A.Aitken, “Guide Book to Organic Synthesis Longman, 2Edn W.Carruthers, “Some Modern Methods of Organic Synthesis”, Cambridge Univ. Press M.Bochmann, “Organomettalics Vols. I and II” Oxford Chem. Primer No. 12 ann 13, OUP R.M.Merhora and Singh, “Organometallic Chemistry” H.Vogtle, Supramolecular Chemistry”, Wiley J.M.Lehn, “Supramolecular Chemistry”, VCH D.Nasipuri, “Stereochemistry of Organic Compounds”, Wiley. J.Mann and others, “Natural Products – Their Chemistry and Biological Significance Longman D.Voet and J.G.Voet, “Biochemistry”, Wiley H.Dugas, “Bioorganic Chemistry” 3Edn, Springer CH 241(C) – ADVANCED PHYSICAL CHEMISTRY Total 90 h

Unit I Molecular Symmetry and Character Table

18 h

Molecular symmetry: Symmetry elements and symmetry operations. Point groups Properties of a group. Abelian, cyclic and subgroups. Classification of elements. Groups representation and character table. Derivation of character tables of point groups such as C2h C 4v and D3h. Mullikans symbols. Transformation properties of dipole moment components. Rotational motion of molecules. Polarisability tensors. Construction of representation using different base vectors such as Cartesian coordinates, mathematical functions and atomic orbitals. Reduction formula: Reduction of reducible representations to irreducible representations. Transformation properties of atomic orbitals in various point groups. Construction of hybrid orbitals. Identification of atomic orbitals participating in the hybridization of triangular planar-AB3, tetrahedral-AB4, square planar-AB4, square pyramidal-AB4, triangular bipyrmaidal-AB5, square pyramidal-AB5 and octahedral-AB6 molecules. Unit II Application of Character Table

18 h

Spectroscopic Applications: Transition moment integral and transition moment operator. Vasishing matrix element- symmetry and selection rules for IR, Raman and electronic spectra. Dipole and polarisability transition moment operators. Identification of IR and Raman active normal modes in molecules coming under different point groups such as C2v, C3v, C4v, D3h, Td and Oh. Verification of mutual exclusion and complimentarity principles of IR and Raman spectra and their use in identification of molecular structure. Probability of overtones and combination bands. Identification of allowed and forbidden electronic transitions in carbonly group. Vibronic transitions. Application to MO theory: Symmetry adapted LCAO-MO theory of π -bonded bydrocarbons. Projection operator and its use in the construction of wave functions of π molecular orbitals, secular equations and use of symmetry for simplifying the calculations of energy and wave function. HMO calculation of energy and wave functions of ethylene, butadiene and carbocyclic systems such as benzene and naphthalene. Unit III Exactly Solvable systems

18 h

Recapitulation of simple harmonic oscillator: Wave equation, soulution and Hermite polynomial. The three dimensional harmonic oscillator. Potential energy in three dimension and Schrodinger wave equation in

Cartesian coordinate. Degeneracy.

Separation of variables and solution of he equations for energy and wave function.

Rigid Rotor: Schrodinger in polar coordinates. Angular momentum operator for rigid ortor, separation of variables and complete solution of the Ø and θ equations. Legendre polynomials and associated Legendre funcions. Normalisation of associated Legendre fuction and evolution of the values of orbital angular momentum quantum number. Recurrence relation. Rigid rotor wave function and energy. The spherical harmonics. The Hidrogen atom: Schrodinger wave equation in polar coordinates. Separation of variables and complete solution of the radial part. The associated Laguarre polynomial. Normalisation. The evolution of the values of the principal quantum number. The spherical harmonic and radial part of the wave functions. The total wave function of H-atom. The wave functions of H-atomic orbitals and explanation of the shapes of various orbitals. Unit IV Approximate Systems I

18 h

Schrodinger wave equations for belium atom and anharmonic oscillator and difficulty to get the exact solution of these equations. The variation method: Variation theorem and its proof. The variation integral and its properties. Variational parameters. Trial wave functions. Illustration of use of trial wave function for calculation of energy taking H atom as example. Setting up of secular determinants. Trial functions as linear combination of orthonormal functions. Linear combination of functions containing variational parameters as trial function. Variation methods of normal state of helium atom- use of atomic units, the more generalized variation method. The self-consistent field method, SCF and variation method. Strength and limitations of the method. The WKG approximation: Schrodinger wave equation in powers of h/2... and solution to obtain the general form of the wave function. Validity of the approximation. Unit V Approximate Systems II

18 h

The perturbation theory: The generalized perturbation theory and the idea of successive correction to uperturbed problem. First order perturbation. Correction of wave function and energy. Theory of non-degenerate level perturbation. The mormal helium atom. The first order perturbation of the degenerate level. The hydrogen atom. Second order perturbation theory. Correction for wave function and energy, Stark effect. Time dependent perturbation theory: Variation in the state of a system with time. Emission and absorption of radiation. The Eistein transition probabilities and their calculations. Selection rule and intensity of spectrum for harmonic oscillator, rigid rotor and hydrogen atom. Slater’s treatment of complex molecules: Wave function for the system of three hydrogen atoms. Generalized valence bond method. The generalized Hellmann-Feynmann theorem and its significance. At least 100 problems to be worked out from all the units together 20% of the questions for examination shall contain problems. References 1. 2. 3. 4. 5. 6. 7. 8.

F.A.Cotton, “Chemical Applications of Group Theory”, John Wiley & son V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry”, Vishal Publications J.D.Donaldson and F.D.Ross, “Symmetry and Stereochemistry”, Inter text R.L.Cater,” Molecular Symmetry and Group Theory”, John Wiley & Son J.M.Anderson, “Mathematics for Quantum Chemistry”, W.A.Benjamin D.A.McQuarrie, “Physical Chemistry- A Molecular approach”, Viva Low-priced Student Edition S.Glasstone, “Theoretical Chemistry”, D van Nostrand L.Pauling and E.B.Wilson, “Introduction to Quantum Mechanics”, McGraw Hill

9.

G.W.Castellan, “Physical Chemistry”, Narosa Publishing House. CH 242 DISSERTATION Total 180 h

Each of the students has to carry out original research in a topic in accordance with the Elective paper chosen for Semester IV under the guidance and supervision of a teacher in the concerned Department of the College. Instructions to Question Paper Setters The syllabus of each theory paper has five Units. While setting the question papers, equal weight is to be given to each of the Units for choosing questions. Each question paper is of 3 hours duration and has three Sections, namely Section A, Section B and Section C constituting a total of 75 marks as detailed: Section A – Five questions, one from each Units containing three short answer questions marked (a), (b), and (c), each of which has 2 arks. One has to answer any two of (a), (b), or (c) from each of the five questions. (2 x 10 = 20 marks) Section B – Five questions, one from each Unit containing two short essay questions marked (a) and (b), each of which has 5 marks. One has to answer either (a) or (b) from each of the five questions. (5 x 5 = 25 marks) Section C – Five essay questions, one from each Unit having 10 marks. One has to answer any three questions from the five questions asked. (10 x 3 = 30 marks)