SFS, GURUKUL MARG, MANSAROVAR, JAIPUR SCHEME OF EXAMINATION AND COURSES OF STUDY MASTER OF SCIENCE (M.SC.) CHEMISTRY First Semester – Fourth Semester I Semester Examination November 2008 II Semester Examination April 2009 III Semester Examination November 2009 IV Semester Examination April 2010 Syllabus applicable for the students seeking admission to the M.Sc.Chemistry in the academic year 2008-09 Semester I Paper I CHY- 121 Bonding and Reaction Mechanism of Co-ordination Compounds 60 hrs (4 hrs/week) Objectives: To learn about kinetics and reaction mechanism of transition metal complexes and acquaint them with the nature of metal-ligand bonding in coordination compounds. I Stability of Complex ions in Solutions 10 hrs Stepwise and overall formation constants, effect of ligands and metals on stability constants of complexes, chelate effect; determination of the composition and formation constants of complexes – mole ratio method, solubility method, spectral methods (slope-ratio and Job’s method) and Bjerrum’s method (pH-metry). Self Study: Kinetic and thermodynamic stability of complex ions. II Reaction Mechanism of Transition Metal Complexes-I 14 hrs Ligand Substitution Reactions : patterns of reactivity, classification of mechanisms, energy profile of reaction transition states; inert and labile complexes; kinetics of substitution reactions in octahedral complexes, factors affecting SN 1 and SN 2 mechanism acid hydrolysis and factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidence in favour of conjugate mechanism; anation reactions; reactions without metal ligand bond cleavage. III Reaction Mechanism of Transition Metal Complexes-II 12 hrs Mechanism of substitution in square planar complexes, trans effect, theories of trans effect and its uses, factors affecting substitution reactions in square planar complexes, cis effect, cis-trans isomerization. Redox Reactions : classification, mechanism of one electron transfer reaction – outer sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions. IV Molecular Orbital Theory-I ( σ-bonding) 12 hrs Pre requisite: Crystal field theory. Ligand field theory; introduction to the molecular orbital diagrams of some simple polyatomic molecules like BeH 2, H2O; complexes involving only σ bonding, LCAO’s approximation; σ-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes. V Molecular Orbital Theory-II ( π-bonding) 12 hrs π-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes; effect of pi-bonding ( π- type ligands); experimental evidences for pi-bonding (crystallography, Infra red spectroscopy); angular overlap model – principles, angular overlap and geometry. Text/References: 1. Mechanism of Inorganic Redox Reactions, Second Edition; F. Basalo and R.G. Pearson; Wiley Eastern Pvt. Ltd., New Delhi, 1973. 2. Inorganic Chemistry; Third Edition; D.F. Shriver and P.W. Atkins; Oxford University Press, New York, 1999. 3. Inorganic Chemistry, Principles of Structure and Reactivity; Fourth Edition; J.E. Hueey, E.A. Keiter and R.L. Keiter; Addison-Wesley Publishing Company, New York, 1993. 4. Advanced Inorganic Chemistry, Fifth Edition; F.A. Cotton and G. Wilkinson; John Wiley and Sons, USA, New York, 1988. 5. Inorganic Chemistry; Third Edition; Gary L. Miessler and Donald A. Tarr; Pearson Education Inc. Singapore, 2005. 6. Coordination Compounds; S.F.A Kettle; Thomson Nelson and Sons Limited, 1975. Semester I Paper II CHY- 122 Basics of Organic Chemistry 60 Hrs (4 hrs/week) Objectives: To learn the basics of organic chemistry and the three dimensional concepts of molecules, elements of symmetry and stereochemistry. I Nature of Bonding in Organic Molecules 12 hrs Pre requisite: Delocalized chemical bond – conjugation, cross conjugation, resonance and field effects. hyperconjugation, tautomerism. Aromaticity in benzenoid and non-benzenoid compounds, alternant and non- alternant hydrocarbons, Huckel’s rule and Möbius system, energy level of π molecular orbitals in simple systems (ethylene, 1, 3 butadiene, benzene and allylic system), annulenes, fullerenes, antiaromaticity, homoaromaticity, PMO approach, steric inhibition to resonance. Bonds weaker than covalent – addition compounds, phase transfer catalysis and crown ether complexes, cryptands, inclusion compounds, cyclodextrins, catenanes, rotaxanes and Kekulene. II Reaction Mechanism: Structure and Reactivity 16 hrs Structure and Reactivity: Concept of linear free energy relationship-Hammett and Taft equations, application of the above in determination of organic reaction mechanisms. Hammond’s postulates, Nucleophilicity, HSAB principle, Curtin- Hammett principle Pre requisite : Types of reactions, types of mechanisms, general principles for the determination of reaction mechanism. Organic Reaction Dynamics and Reactive Intermediates: general methods for the determination of reaction mechanism – product analysis, determination of presence of intermediates, study of catalysis, isotopic labelling, stereochemical evidences, kinetic evidences and isotope effects. Methods of generation, structure and reactivity of classical and non-classical carbocations, phenonium ions, norbornyl system, carbanions, radical-anions and radical-cations, arynes, carbenes and nitrenes. III Molecular Rearrangements 12 hrs General mechanistic consideration – nature of migration, migratory aptitude. A detailed study of the following rearrangements: Pinacol-pinacolone rearrangement, Wagner-Meerwein rearrangement, Damjanov rearrangement, Benzil-benzilic acid rearrangement, Favorskii rearrangement, Arndt-Eistert rearrangement, Neber rearrangement, Beckmann rearrangement, Hofmann rearrangement, Curtius rearrangement, Lossen rearrangement, Schmidt rearrangement, Wolff rearrangement, Baeyer-Villiger oxidation, Shapiro reaction, β-Keto rearrangement, Dienone- phenol rearrangement, Wittig rearrangement. IV Stereochemistry – I 10 hrs Pre requisite : Conformation, configuration, erythro and threo isomers, E,Z, R,S and D,L nomenclature. Optical isomerism, elements of symmetry chirality, enantiomers, diastereomers, R,S nomenclature in cyclic systems, absolute configuration, optical purity resolution, prochirality; enantiotopic and diastereotopic atoms, groups and faces. Pseudoasymmetry: optical activity in the absence of chiral carbons (biphenyls, allenes, spiranes, ansa compounds and cyclophanes), chirality due to helical shape; chirality in the compounds containing N, S and P. V Stereochemistry - II 10 hrs Geometrical isomerism in cyclic and condensed systems (decalins, decalols and decalones), conformational analysis of cycloalkanes (5, 6, 7 membered rings) and decalins, effect of conformation on reactivity, conformations of sugars (glucose,maltose and sucrose), steric strain due to unavoidable crowding. Asymmetric synthesis, Cram’s rule, Prelog’s rule, CD, ORD, octant rule, Cotton effect and their application in determination of absolute and relative configuration and conformation. Self Study - Geometrical isomerism in acyclic systems. Text/References: 1. Advanced Organic Chemistry: Reactions, Mechanisms and Structure; Fourth Edition; Jerry March; John Wiley and Sons Asia Private Limited, New Delhi, 2007 2. Organic Chemistry; Fourth Edition; G. Marc Loudon; Oxford University Press, New York, 2002. 3. Advanced Organic Chemistry Part A & B; Fourth Edition; Francis A. Carey and Richard J. Sundberg; Kluwer Academic/Plenum Publishers, New York, 2000. 4. Stereochemistry: Conformation and Mechanism; Fourth Edition; P.S. Kalsi; New Age International Publishers Pvt Ltd, New Delhi, 1999. 5. Physical Organic Chemistry Vol. I and II; Neil Isaac; Longman. 6. Named Organic Reactions; Thomas Lave and Andreas Plagens; John Wiley and Sons. 7. Advanced Organic Chemistry; Lowry & Richardson; Addison Weiley Publishing Company. Semester I Paper III CHY- 123 Quantum Chemistry and Surface Phenomena 60 Hrs (4 hrs/week) Objectives: To learn chemical bonding and quantum mechanical concepts and surface phenomena including three dimensional concepts of molecules and introduction to group theory. I Introduction to Quantum Mechanical Results 12 hrs Schrodinger equation, postulates of quantum mechanics, operators and commutation relations, discussions of solutions of the Schrodinger equation to some model systems – particle in a box, harmonic oscillator, rigid rotor, hydrogen atom. II Approximate Methods and Angular Momentum 13 hrs The variation theorem, linear variation principle, perturbation theory (first order and non – degenerate), application of variation method and perturbation theory to helium atom, ordinary and generalized angular momentum, eigen functions and eigen values for angular momentum, operator using ladder operators, addition of angular momenta, spin, antisymmetry and Pauli’s exclusion principle. III Molecular Orbital Theory 10 hrs Huckel’s theory of conjugated systems, bond order and charge density calculations, applications to ethylene, butadiene, cyclopropenyl radical and cyclobutadiene. IV Symmetry and Group Theory 12 hrs Symmetry elements and symmetry operations, definitions of group and subgroup, relation between orders of a finite group and its subgroup, conjugacy relation and classes, point group symmetry, schonfiles symbols, representations of group by reducible and irreducible presentations and relation between them (representation for the C n, C nv , D nh etc. groups to be worked out explicitly), character of a representation,