A C H I E V E R S C I R C L E

CSIR-UGC National Eligibility Test (NET) for Junior Research Fellowship and Lecturer-ship.

Syllabus CHEMICAL SCIENCES

Section- I
INORGANIC CHEMISTRY:
1) Chemical Periodicity
Atomic and ionic radii, ionization energy, electron affinity and electronegativity definition,

methods of determination or evaluation, trends in periodic table and applications in predicting and explaining the chemical behaviour. Classification of elements on the basis of electronic configuration. Modern IUPAC Periodic table. General characteristic of s, p, d and f block elements.
Position of hydrogen and noble gases in the periodic table, Effective nuclear charges, screening

effects, Slaters rules, scales of electronegativity, diagonal relationship and Inert pair effect. 2) Structure and bonding in homo- and heteronuclear molecules, including shapes of molecules (VSEPR Theory)
Covalent Bond Valence bond theory and its limitations, directional characteristics of covalent

bond, various types of hybridization and shapes of simple inorganic molecules and ions,Valence shell electron pair repulsion (VSEPR) theory to NH3, H3O+, SF4, CIF3, ICI2- and H2O. LCAO-MO theory for homonuclear and heteronuclear diatomic molecules; orbital symmetry and overlap; Walsh diagrams multicenter bonding in electron deficient molecules, bond strength and bond energy, percentage ionic character from dipole moment and electronegativity difference.
Ionic Solids Ionic structures, radius ratio effect and coordination number, limitation of radius

ratio rule, lattice defects, semiconductors, lattice energy and Born-Haber cycle, solvation energy and solubility of ionic solids, polarizing power and polarisability of ions, Fajans rule, Metallic

bond-free electron theory, valence bond and band theories, conductors, semiconductors and insulators, Weak Interactions Hydrogen bonding, vander-Waals forces.

PHYSICAL CHEMISTRY:
1) Chemical thermodynamics: Laws, state and path functions and their applications. Thermodynamic description of various types of processes, Carnots theorem and its consequences. Carnots cycle- detailed mathematical treatment and various graphical representations.
Concept of entropy, reversible and irreversible processes, Clausius inequality, Free energies,

Criteria of spontaneity, Maxwells relations Gibbs-Helmholtz equations; spontaneity and equilibria.

Joule-Thomson experiment concept of Joule Thomson co-efficient, concept of inversion

temperature, comparison with isoentropic process, temperature and pressure dependence of thermodynamic quantities. Fundamental equations for open systems, Partial molar quantities and chemical potential, GibbsDuhem equation, Real gases and fugacity.
Chemical equilibrium: thermodynamic conditions for equilibrium, Vant Hoffs reaction

isotherm kp , kc and kx .Vant Hoffs reaction isobar and isochors- effect of temperature on Le Chatelier principle.
Thermodynamics of ideal and non-ideal solutions. Activity of ideal, regular and ionic solutions. Strong electrolytes, Debye-Huckel limiting law and its extensions, activity coefficients and ionic

strength, Applications of Debye-Huckel Theory, Nernst heat theorem, Colligative properties: Thermodyanamic derivation and their interrelationships, abnormal colligative properties. Elementary description of phase transitions; phase equilibria and phase rule; Clausius Clapyeron equation, concept of triple point, phase diagrams of one component system. Duhem-Margules equations, Henry's law, Konowaloff's rule, fractional distillation, phase diagrams, azeotrope, eutectic, partial miscibility and critical solution temperature and various other binary and multicomponent systems and excess thermodynamic properties. Ionic equilibrium- pH and buffer solutions, hydrolysis, solubility product.

ORGANIC CHEMISTRY:
1) Principles of stereochemistry:
A) Acyclic stereochemistry:

Optical isomerism in compounds containing one and two asymmetric centers, designation of absolute configuration. symmetry elements, molecular chirality. Configuration: stereogenic units i) stereocentres: systems involving 1, 2, 3centres, stereogenicity, chirotopicity. pseudoasymmetric (D/L and R/S descriptor, threo/erythro and syn/anti nomenclatures (for aldols). Optical activity of chiral compounds: specific rotation, optical purity (enantiomeric excess), racemic compounds, racemisation (through cationic and anionic and radical intermediates), resolution of acids, bases and alcohols via diastereomeric salt formation. Topicity of ligands and faces.

B) Conformational analysis of cyclohexane, mono and disubstituted cyclohexane:

Symmetry properties and optical activity. Conformation & reactivity in cyclohexane system: elimination (E2), rearrangement, nucleophilic substitution (SN1, SN2, NGP), oxidation of cyclohexanol, esterification, saponification, lactonisation.
C) Enantioselcetive synthesis with chiral non racemic reagents and catalysts:

Hydroboration with chiral boranes (IPCBH2), (IPC)2BH, Carbonyl group reduction with chiral complex hydride (BINAL-H, Chiral oxazaborolidines), Chiral organometal complex (-) DAIB; 3exodimethylamino isoborneol. Enantioselective epoxidation of alkene: Sharpless epoxidation, enantioselective hydrogenation with[Rh(DIPAMP)]+. Diastereoselective synthesis: Aldol reactions (Chiral enolate & Achiral Aldehyde and Achiral enolate and chiral aldehyde). Optical Activity in absence of chiral carbon: biphenyls and Allenes and Atropisomerism.
D) Applications of Stereoselectivity, Diastereoselectivity and asymmetric induction

2) Aromaticity: Mono and bicyclic aromatic hydrocarbons. Frost diagram, Huckels rules for aromaticity & antiaromaticity; homoaromaticity. Benzenoid and non-benzenoid compounds-genarations and reactions. delocalization of electrons, Hckels rule, criteria for aromaticity, examples of neutral and charged aromatic systems: annulenes: NMR as a tool for aromaticity, anti and homo-aromatic systems. 3) Organic reactive intermediates:
A) Carbocations (cabenium and carbonium ions), carbanions, carbon radicals:

Genaration,stability and reactivity of Carbocations, carbanions, carbon radicals. Generation of radical intermediates and its (a) addition to alkenes, alkynes (inter & intramolecular) for C-C bond formation and Baldwins rules (b) fragmentation and rearrangements. Name reactions involving radical intermediates such as Barton deoxygenation and decarboxylation, McMurry coupling etc.
B) Chemistry of Carbenes :

Structure using orbital picture, generation of carbenes,electrophilic/nucleophilic behaviour, stability, addition and insertion reactions, rearrangement reactions of carbenes,
C) Benzynes and Nitrenes:

Intermediate-formation and applications of Benzynes, Structure of nitrene, generation and reactions of nitrene and related electron deficient nitrogen intermediates, Curtius, Hoffmann, Schmidt, Beckmann rearrangement reactions.

Section- II
INORGANIC CHEMISTRY:
3) Concepts of acids and bases, Hard-Soft acid base concept, Nonaqueous solvents.
Acid-Base Equilibria: General concept of acid-base equilibria in water and in non-aqueous

solvent, Definition of pH and pH scale (Sorenson and operational definitions), and its significance, relative strength of acids, Pauling rules, Amphoterism, Lux-Flood concept, Lewis concept, Superacids, Hard and Soft Acids and Bases (HSAB) :Classification of acids and bases

as hard and soft. Pearsons HSAB concept, acid-base strength and hardness and softness, definition of hardness and softness from FMO approach, Symbiosis, theoretical basis of hardness and softness, electronegativity and hardness.
Hammett acidity function, pH calculation for aqueous solutions of very weak acid and very

weak base, salts of weak acid and weak bases, mixture of weak acid and its salts, mixture of weak base and its salts, hydrolysis of salts.
Buffer Solutions and Titrations: Theory of buffer solution, dilution and salts effects on the pH

of a buffer, Buffer index, Criteria and expression of maximum buffer capacity, Application buffers, Preparation of buffer solutions of known ionic strength (Typical examples). Practical limitations in use of buffers, Metal ion buffers and their applications, Biological buffers and their applications, Acid-base neutralisation curves; indicator, choice of indicators.
Non-aqueous Solvents: Reactions in non-aqueous solvents with reference to liquid NH3 and

liquid SO2 and HF. 4) Nuclear chemistry: nuclear reactions , fission and fusion, radioanalytical techniques and activation analysis.
Nuclear Chemistry: General characteristics of radioactive decay, parent-daughter decay growth relationships Decay kinetics, artificial transmutation and artificial radioactivity, Nuclear stability and nuclear binding energy, packing fraction, Nuclear forces: meson exchange theory. Nuclear models (elementary idea), magic numbers; fission, fusion and spallation, Bohrs compound nucleus theory of nuclear reaction, Szilard-Chalmers reactions. Radio chemical methods: Principles of determination of age of rocks and minerals, radio carbon dating principles, Isotope dilution and neutron activation analysis. NuclearReactors: Classification of reactors, reactor power, nuclear waste Management, Hazards of radiation and safety measures.

PHYSICAL CHEMISTRY:
2) Chemical kinetics and photochemistry:
Empirical rate laws and temperature dependence, complex reactions: Mechanism of Composite

Reactions - types of composite mechanisms, rate equationsfor composite mechanisms, simultaneous and consecutive reactions, steady state treatment, rate-determining steps, microscopic reversibility, dynamic chain (H2-Br2 reaction, decomposition of ethane and acetaldehyde) and oscillatory reactions (Belousov-Zhabotinskii reaction), branching chain: H2+O2 reaction. Theories of Reaction Rates: Potential energy surfaces-adiabatic and non-adiabatic curve crossing Processes- transition state theory- activation/thermodynamic parameters. Various theories of Unimolecular reactions (Lindemann- Christiansen hypothesis; Hinshelwood, RRK and RRKM theories; non RRKM behavior) Elementary Reactions in Solutions: Influence of solvent properties on rate. Different types of molecular interactions in solution. Diffusion and activation controlled reactions. Kinetics of Unimolecular and bimolecular reactions. Salt effects; homogeneous and heterogenous catalysis: enzyme kinetics; Bimolecular surface reactions - reaction between a gas molecule and an adsorbed molecule, reaction between two

adsorbed molecules including the basic concepts of adsorption isotherms (Langmuir and Freundlich, Gibbs and BET), inhibition and activation energy of such reactions. Catalytic activity at surfaces (volcano curve), transition state theory of surface reactions: rates of chemisorption and desorption, unimolecular and bimolecular surface reaction, comparison of homogeneous and heterogeneous reaction rates, surface heterogeneity, lateral interaction photophysical & photochemical reactions, Laws of photochemistry and quantum yield, Lambert Beers law and applications, FrankCondon principle- Potential energy curves, Jablonski diagrams, Fluoroscene and phosphorescence and non-radiative decay, photochemical dissociations and pre-dissociation.
Resonance energy transfer rates-Fluorescence quenching kinetics in solution and gas phase. Fast

Reaction Kinetics: Relaxation methods, Stopped flow method, Laser Flash Photolysis, flow tube methods, and Laser based experimental techniques. Experimental set up for Unimolecular decomposition studies. State to state dynamics. Molecular beam studies.

ORGANIC CHEMISTRY:
4)
IUPAC nomenclature stereoisomers: of organic molecules including regioand

Basic reaction mechanisms:

A) Sustitution at sp3 centre: Mechanism: SN1, SN2, SN2, SNi mechanisms, effect of solvent,

substrate structure, leaving group, nucleophiles including ambident nucleophiles (cyanide & nitrite) substitution involving NGP;
B) Elimination: Mechanisms: E1, E2 and E1cB; reactivity, orientation (Saytzeff/Hofmann) and

stereoselectivity; Pyrolytic syn-elimination, Competition between substitution and elimination reactions.

C) Reaction kinetics: Elucidation of reaction mechanism, Transition state theory, rate constant

and free energy of activation,free energy profiles for one step and two step reactions, catalyzed reactions, kinetic control and thermodynamic control of reactions, isotope effect , primary kinetic isotopic effect (kH/kD), principle of microscopic reversibility, Hammond postulate. 5) Common named reactions and rearrangements: Reformatsky reaction, E. Clarke reaction, Vilsmeier-Haack reaction, Reimer-Tiemann reaction, Kolbe-Schmidt reaction, Tischenko reaction, Acyloin condensations, Shapiro reaction, Julia olefination,aldol condensation, benzoin condensation, Bouveault-Blanc reduction, Clemmensen Reduction, Wagner-Meerwein rearrangement, pinacol rearrangement, dienone-phenol; Wolff rearrangement in Arndt-Eistert synthesis, benzil-benzilic acid rearrangement, Beckmann rearrangement, Schmidt rearrangement, Hofmann rearrangement, Lossen rearrangement, Curtius rearrangement, Baeyer-Villiger oxidation, hydroperoxide rearrangement, Dakin reaction, Fries rearrangement, Claisen rearrangemen, Hofmann-Martius rearrangement, Fischer-Hepp rearrangement, N-azo to C-azo rearrangement, Bamberger rearrangement, Orton rearrangement, benzidine rearrangement.

SECTION III:
INORGANIC CHEMISTRY
5) Main group elements and their compounds: Allotropy, synthesis, structure and bonding, industrial importance of the compounds.
s Block Elements: General trends in Physical and Chemical properties of the Elements and their important classes of Compounds. Lithium and Beryllium: Anomalous behaviour and diagonal relationship. Hydrides: Classification and general properties. Noble gases, Clathrates: Types, preparation and stability. Fluorides and Oxides of Xenon: Preparation, properties, structure and bonding (VB and MO treatment). p Block Elements: Comparative study (including diagonal relationship and anomalous behaviour) of groups (13 -17). Boron Hydrides: Introduction, Nomenclature, Preparation. Properties, Structure and bonding in diborane, borazine : structure, bonding and reactions, boric acid, borax, boron nitrides, silanes, silicon halides, silicic acids, silicones, silicates. Carbides. Nitrogen Compounds: Hydrazine, Hydroxylamine, Oxides and Oxyacids of nitrogen (Properties, Structure-bonding & Uses), nitrides, condensed phosphates, phophonitrilic compounds. Thionic acids, sodium thiosulphate, polysulphides, hydrogen peroxide, ozone, Oxygen fluorides, Oxides and Oxyacids of Sulphur (Properties, Structure-bonding), Structure-bonding (SN)x with x = 2, 4. Halogens: General properties, Oxides and Oxyacids of Cl, Br and I, Interhalogens; Polyhalides and Pseudohalogens, basic properties of halogens, fluorocarbons, noble gases (isolation properties and structure of compounds of noble gases)

6) Inner transition elements: spectral and magnetic properties, redox chemistry, analytical applications.
Chemistry of Lanthanide and Actinide Elements Lanthanoids: Electronic structure, oxidation states, Magnetic properties & Complexing behaviour. Ionic radii and Lanthanide contraction: Cause and Consequences of lanthanide Contraction Separation of lanthanoids: Ion-exchange methods; occurrence and isolation, lanthanide compounds. Actinoids: Introduction, Electronic configuration, Oxidation states, Magnetic properties & Comparison with lanthanoids. Redox Chemistry (General):

 Solubility product principle, common ion effect and their applications to the precipitation and separation of common metallic ions as hydroxides, sulfides, phosphates, carbonates, sulfates and halides. Ion-electron method of balancing equation of redox reaction. Elementary idea on standard redox potentials with sign conventions, Nernst equation (without derivation). Influence of complex formation, precipitation and change of pH on redox potentials; formal potential. Feasibility of a redox titration, redox potential at the equivalence point, redox indicators. Redox potential diagram (Latimer and Frost diagrams) of common elements and their applications. Disproportionation and comproportionation reactions (typical examples).

PHYSICAL CHEMISTRY:
3) Basic Quantum mechanics: Basic principles of quantum mechanics: Postulates; operator algebra: wave functions and probabilities, operators, matrix representations, commutation relationships. Hermitian operators, Commutators and results of measurements in Quantum Mechanics. Eigenfunctions and eigenvalues of operators and superposition principle. States as probability distributions and expectation values. The expansion of arbitrary states in terms of complete set. Angular momentum, commutation relationships, basis functions and representation of angular momentum operators. Exactly-solvable systems: particle-in-a-box: 1D,2D and 3D, harmonic oscillator: solutions of Hermite equation in detail(Solution of differential equations by power series method) and the introduction of the parity operator, particlein-a-ring and on a sphere (rigid rotor model): the solutions of Legendre and Laguerre differential equations, Spherical Harmonics and hence the prediction of the shape of orbitals and solution of the Schrodinger equation for the hydrogen atom, radial and angular probability distributions, atomic orbitals.

ORGANIC CHEMISTRY:
6) Organic transformations and reagents: Functional group interconversion including oxidations and reductions; Common catalysts and reagents (organic, inorganic, organometallic and enzymatic).
Chemo, regio and stereo-selectivet ransformations: [Stereoselective synthesis of tri- and tetra-

substituted olefins;Claisen rearrangement and its variants, aza-Cope rearrangement (Overman rearrangement), ene reaction (metallo-ene; Coniaene); Prins reaction]. Modern Synthetic Methodology in Organic Chemistry:

A)

Oxidation: Metal based and non-metal based oxidations of (a) alcohols to carbonyls (Chromium, Manganese, aluminium, silver, ruthenium. DMSO, hypervalent iodine and TEMPO based reagents). (b) phenols (Fremys salt, silver carbonate) (c) alkenes to epoxides (peroxides/per acids based),

Sharpless asymmetric epoxidation, Jacobsen epoxidation, Shi epoxidation.(d) alkenes to diols (Manganese, Osmium based), Sharpless asymmetric dihydroxylation, Prevost reaction and Woodward modification, (e) alkenes to carbonyls with bond cleavage (Manganese, Osmium, Ruthenium and lead based, ozonolysis) (f) alkenes to alcohols/carbonyls without bond cleavage (hydroboration-oxidation, Wacker oxidation, selenium, chromium based allylic oxidation) (g) ketones to ester/lactones (BaeyerVilliger). Reduction: (a) Catalytic hydrogenation (Heterogeneous: Palladium/Platinum/Rhodium/Nickel etc; Homogeneous: Wilkinson). Noyori asymmetric hydrogenation. (b) Metal based reductions using Li/Na/Ca in liquid ammonia, Sodium, Magnesium, Zinc, Titanium and Samarium (Birch, Pinacol formation, McMurry, Acyloin formation, dehalgenation and deoxygenations) (c) Hydride transfer reagents from Group III and Group IV in reductions. (i) NaBH4 triacetoxyborohydride, L-selectride, Kselectride, Luche reduction; LiAlH4, DIBAL-H, and Red-Al,;Trialkylsilanes and Trialkylstannane, Meerwein-Pondorff-Verley reduction) (ii) Stereo/enantioselectiviey reductions (Chiral Boranes, CoreyBakshi-Shibata). B) Concepts in organic synthesis:

a) Retrosynthesis: Retrosynthetic Analysis: Basic principles and terminology of retrosynthesis, synthesis of aromatic compounds, one group and two group C-X disconnections, one group C-C and two group C-C disconnections, amine and alkene synthesis, important strategies of retrosynthesis, functional group transposition, important functional group interconversions,disconnection,synthons,linear and convergent synthesis, umpolung of reactivity. b) Protecting groups: Protection and deprotection of hydroxy, carboxyl, carbonyl, carboxy amino groups and carbon-carbon multiple bonds; chemo- and regioselective protection and deprotection; illustration of protection and deprotection in synthesis. C) Modern Synthetic Methods:

Baylis-Hillman reaction, Henry reaction, Nef reaction, Kulinkovich reaction, Ritter reaction, Sakurai reaction, Tishchenko reaction and Ugi reaction. Brook rearrangement; Tebbeolefination. Metal mediated C-C and C-X coupling reactions: Heck, Stille, Suzuki, Negishi and Sonogashira, NozakiHiyama, Buchwald-Hartwig, Ullmann coupling reactions, directed orthometalation. D) Construction of Ring Systems:

Different approaches towards the synthesis of three, four, five and six-membered rings; photochemical approaches for the synthesis of four membered rings, oxetanes and cyclobutanes. Diels-Alder reaction (inter- and intramolecular), ketene cycloaddition (inter- and intramolecular), Pauson-Khand reaction, Bergman cyclization; Nazarov cyclization, cation-olefin cyclization and radical-olefin cyclization, inter-conversion of ring systems (contraction and expansion); construction of macrocyclic rings, ring closing metathesis. E) Organometallics: Review of formalisms such as oxidation state, 18-electron rule, classes of ligands, structure and bonding. Review of reaction mechanisms, ligand substitution, oxidative addition, reductive elimination, migratory insertion, hydride elimination, transmetallation, nucelophilic and electrophilic attack on the ligands coordinated to metals.

 Organo zinc and copper reagents, preparation using transmetallation, functionalized zinc and copper reagents, synthetic applications in conjugate addition and allylic and propargylic substitution reactions. Organo tin reagents, hydrostannation reaction and synthetic utility of vinylstannanes and allylstannanes in addition and substitution reactions. Organoboron and aluminium reagents, alkyl and aryl derivatives, synthesis and examples of applications in C-C bond forming reactions. Organotitanium and zirconium reagents, metallocene complexes in C-C bond forming reactions. Addition to enynes and diynes, hydrozirconation, metallocycle formation and their synthetic utility. Metal (W, Cr, Rh, Ru, Mo) carbene complexes, Fischer, Schrock and Grubbs type carbene complexes, comparison of their stability and reactivity, reactions of Fischer carbene complexes and their synthetic utility, Dtz reaction, simple and cross metathesis reactions, ring opening, ring closing metathesis in organic synthesis, examples from macrocycles synthesis. Copper and rhodium based carbene and nitrene complexes, cyclopropanation, Rh catalysed C-H insertion and aziridination reactions including asymmetric version. Introduction to N-heterocyclic carbene metal complexes. Metal (Fe, Cr, Mo, Ni, Co, Rh) carbonyl compounds in organic synthesis. C-C bond forming.Cyclooligomerization of alkenes, enynes and alkynes, Vollhardt reaction.Carbonylation and decarbonylation reactions and hydroformylation reaction.
Metal (Fe, Pd) ene, diene and dienyl complexes, metal complexes as protecting groups,

activation towards nucleophilic addition reaction and rules governing such additions, synthetic utility. allyl palladium, nickel and iron complexes, synthesis and their synthetic utility.Various Wacker type oxidation and cyclization reactions including asymmetric version.
Metal (Co, Zr) alkyne complexes, protection of triple bond, C-C bond forming reactions such as

Pauson-Khand reaction, alkyne cyclotrimerization and oligomerization reaction. Metal (Cr, Fe, Ru) arene complexes, synthesis and structure.Activation of arene nucleus and side chain.Nucleophilic substitution and addition of arene. Metal (Rh, Ir) catalyzed C-H activation reactions and their synthetic utility.

SECTION IV:
INORGANIC CHEMISTRY
7) Transition elements and coordination compounds: structure, bonding theories, spectral and magnetic properties, reaction mechanisms.
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 behavior, spectral properties and stereochemistry.

Metal-ligand Bonding in Transition Metal Complexes:

Limitations of valence bond theory, an elementary idea of crystal-field theory, crystal field splitting in octahedral, tetrahedral and square planar complexes, CFSE for d1 to d10 systems, pairing energy, low-spin and high-spin complexes and magnetic properties; LFT, and molecular orbital (MO) theory of selected octahedral and tetrahedral complexes; Factors affecting the crystal-field parameters ,Jahn-Teller distortions; experimental evidence for metal-ligand orbital overlap; ligand, JT-distorted octahedral, square planar, square pyramidal, trigonal bipyramidal, and tetrahedral complexes; Magnetic Properties of Transition Metal Complexes:

Types of magnetic behaviour, methods of determining magnetic susceptibility, spin-only formula. L-S coupling, correlation of s and eff values, orbital contribution to magnetic moments, quenching of magnetic moment: super exchange and antiferromagnetic interactions (elementary idea with examples only), application of magnetic moment data for 3d-metal complexes. Electron Spectra of Transition Metal Complexes: Types of electronic transitions, selection rules for dd transitions, spectroscopic ground states, spectrochemical series. Orgel-energy level diagrams for d1 to d9 states, discussion of the electronicspectrum of complexes. colors, intensities and origin of spectra, interpretation, term symbols and splitting of terms in free atoms, selection rules for electronic transitions, Tanabe-Sugano diagram, calculation of Dq, B, C, Nephelauxetic ratio, Charge transfer spectra. Thermodynamic and Kinetic Aspects of Metal Complexes:

A brief outline of thermodynamic stability of metal complexes and factors affecting the stability, IrvingWilliam series, chelate and macrocyclic effect,substitution reactions of square planar complexes, Trans Effect. Kinetics and Mechanism of Substitution Reactions:

Nature of substitution reactions; prediction of reactivity of octahedral, tetrahedral and square-planar complexes in terms of crystal field activation energy and structure preference energy; rates of reactions; acid hydrolysis, base hydrolysis and anation reactions.

8) Organometallic compounds: synthesis, bonding and structure, and reactivity; Organometallics in homogeneous catalysis and Cages and metal clusters. Organometallic Chemistry
Introduction: Historical background of organometallics, Definition, nomenclature and classification of organometallic compounds. Structure and bonding in mono and polynuclear metal carbonyls; substituted metal carbonyls and related compounds; synthesis and reactivity of metal carbonyls; vibrational spectra of metal carbonyls; dinitrogen and dioxygen as ligands in organometallic compounds. Valence electron count (16/18 electron rules) and its applications to carbonyls (including carbonyl hydrides and carbonylates), nitrosyls, cyanides, and nature of bonding involved therein. Metal-olefin complexes: Zeises salt (preparation, structure and bonding), Ferrocene (preparation, structure and reactions). Hapticity() of organometallic ligands, Cages and metal clusters, fluxional molecules, isolobal analogy.

Organometallic in Catalysis Substitution, oxidative addition, reductive elimination, insertion and deinsertion Catalysis - Hydrogenation, Hydroformylation, polymerization of olefins (Ziegler-Natta catalyst) Environmental Chemistry Monsanto process, Wacker process,

PHYSICAL CHEMISTRY:
4) Molecular spectroscopy:
Time-dependent states and spectroscopy:

Absorption and emission of radiation. Selection rules. Line shapes and widths. Fourier transform spectroscopy.
Rotation and Vibration of Diatomic Molecules:

o Rigid Rotor and harmonic oscillator wave functions and energies. o Selection rules from the concept of T.M.I. on the basis of time-dependent perturbation theory. o A review of MW and IR spectroscopy: The rigid diatomic rotor, energy Eigen values and Eigen states, selection rules, intensity of rotational transitions, the role of rotational level degeneracy, the role of nuclear spin in determining allowed rotational energy levels. o Classification of polyatomic rotors and the non-rigid rotor. o Vibrational spectroscopy, harmonic and anharmonic oscillators, Morse potential, mechanical and electrical anharmonicity, selection rules. o The determination of anharmoncity constant and equilibrium vibrational frequency from fundamental and overtones. o Normal modes of vibration, G and F matrices, internal and symmetry coordinates. o Roto-vibronic spectrum of diatomic molecules: branching of the spectral lines. o Raman Effect: Rotational and vibration-rotational transitions. o Vibration of polyatomic moleculesnormal coordinates. o Polarization of Raman lines. o Resonance Raman and CARS spectroscopy.
Electronic spectroscopy:

Electronic spectroscopy of diatomic molecules. Franck-Condon factor. Dissociation and predissociation. Rotational fine structure. Lasers and laser spectroscopy.
Magnetic Resonance:

Review of angular momentum. Commutation relations. Basic principles and relaxation times. Magnetic resonance spectrum of hydrogen. First-order hyperfine energies.NMR in liquids: Chemical shifts and spin-spin couplings First order Spectra: A2X, AX and AMX systems. Second order spectra: AB system. Equivalent nuclei: A2B2 system. 5) Solid state: Elementary ideas of crystallography: basic laws, crystal lattices, various crystal systems: ionic and covalent crystals, Braggs law and applications and band structure of solids, heat capacities of solids: Einstiens theory and Debye T3 law. 6) Polymers and colloids: Properties of colloids: optical, kinetic and electrical, electrokinetic phenomena: charge and stability of colloids, mechanism of coagulation. Colloidal electrolytes and their properties: micelles with various external effects on micellization, CMC, entropy effect, MAM and PPM concepts, micro-emulsions,

reverse micelles and proteins, polymer: : definition, types of polymers, Molecular mass number and mass average molecular mass, determination of molecular mass by Osmometry, viscosity, light scattering and size exclusion chromatography and the kinetics of polymerization.

ORGANIC CHEMISTRY:
7) Asymmetric synthesis: Chiral auxiliaries, methods of asymmetric induction- substrate, reagent and catalyst controlled reactions; determination of enantiomeric anddiastereomeric excess; enantio-discrimination. Resolution optical and kinetic. 8) Pericyclic reactions: Electrocyclisation, cycloaddition, sigmatropic rearrangements and other related concerted reactions: Molecular orbital symmetry, Frontier orbitals of ethylene 1,3 butadiene, 1,3,5, hexatriene and allyl system, classification of pericyclic reactions, Woodward- Hoffmann correlation diagrams. FMO and PMO approach. Electrocyclicreactions: Conrotatory and disrotatory motion, 4n, 4n+2 and allyl systems. Cycloadditions: antarafacial and suprafacial addition, 4n and 4n+2 systems, 2+2 addition of ketenes, 1,3 dipolar cycloadditions. Sigmatropic rearrangements suprafacial and antarafacial shifts of H, sigmatropic shifts involving carbon moieties, 3,3 and 5,5 sigmatropic rearrangements. Enereaction; pericyclic reactions in organic synthesis such as Claisen, Cope, Diels-Alder and Ene reactions (with stereochemical aspects), introductory dipolar cycloaddition. 9) Principles and applications of photochemical reactions in organic chemistry: A) Introduction and Basic Principles of Photochemistry:

Absorption of light by organic molecules, properties of excited states, mechanism of excited state processes and methods of preparative photochemistry.

B) Photochemistry of alkenes and related compounds: Isomerization, Di--methane rearrangement and cycloadditions. C) Photochemistry of carbonyl compounds: Norrish type-I cleavage of acyclic, cyclic and , and , unsaturated carbonyl compounds, Norrish type-II cleavage. Hydrogen abstraction: Intramolecular and intermolecular hydrogen abstraction, photoenolization. Photocyclo-addition of ketones with unsaturated compounds: PaternoBuchi reaction, photodimerisation of , - unsaturated ketones, rearrangement of enones and dienones, Photo-Fries rearrangement.

Section- V
INORGANIC CHEMISTRY
9) Analytical Chemistry Separation, Spectroscopic, Electro and thermoanalytical methods

Statistical tests and error analysis: Accuracy, precision, classification of errors, minimization of errors, significant figures and computation, mean deviation and standard deviation, Gaussian distribution, mean value statistics. Qualitative Analysis: Underlying principles Common-ion effect, Solubility product, Relation between Solubility and Solubility product. Analysis of Inorganic Mixtures Group reagents, Selective precipitation of cations; Precipitation of Sulphides and metal hydroxides. Reactions involved in Separation and identification of cations and anions. Polarography: Origin of polargraphy, Current-voltage relationship, Theory of polarographic waves (DC and sampled DC (tast) polarograms), Instrumentation, Ilkovic equation, Qualitative and quantitative applications. Spectroscopic Techniques: Theory, Instrumentation and applications of X-rays (emission, absorption, diffraction and fluorescence methods), Atomic absorption Spectroscopy, Atomic fluorescence spectrometry, Atomic emission spectrometry Spectroscopy: UV-visible molecular absorption spectrometry (instrumentation and application), Molecular luminescence spectroscopy (fluorescence, phosphorescence, chemiluminescence). Separation Methods: Principle of chromatography, Classifications of chromatography, Techniques of planar and column chromatography, Gas chromatography, High-performance liquid chromatography Thermal Analysis: Theory, methodology and applications of thermogravimetric analysis (TGA), Differential Thermal Analysis (DTA), and Differential scanning calorimetry (DSC). Principles, techniques and applications of thermometric titration methods.

PHYSICAL CHEMISTRY
7) Electrochemistry:

Conductance: Electrical conductance specific and equivalent conductance for strong and weak electrolytes and effect of dilution, concept of infinite dilution, mobility of ions, conductometric titrations, Kohlrauschs law independent migration and applications, Waldens rule and its applications, Transport numbers dependence and determination. Electrochemical cell: Types of cells with examples and cell reactions , application of Nernst equation, G,H and S of a cell reaction and its application in various types of potentiometric titrationsdetermination of solubility product and other examples, glass electrode and pH determination. Concentration cells with and without transport, liquid junction potential and its elimination, polarography. 8) Kinetic theory of gases: Maxwell-Boltzmann distribution law detailed treatment. Collision of gas molecules, collision diameter; collision number and mean free path; frequency of binary collisions; wall collision and rate of effusion. Equipartition principle. Fundamental concepts for real gases Vanderwaals equation. Deviation from ideal behaviour; Compressibility factor; Amagats curves and Boyle temperature. Andrews experimental curves. Vanderwaals interpretation of these curves. Principle of continuity of states. Critical constants in terms of Van der Walls equation; Reduced equation of state-law of corresponding states. Virial equation of state, the rules of Cailletet and Mathias.

ORGANIC CHEMISTRY
10) Synthesis and reactivity of common heterocyclic compounds having one or two heteroatoms (O,N,S) Structure, preparation and reactions of: a) heterocyclic analogues of cyclopropane, cyclobutane, cyclopentadiene and benzene containing one or more heteroatoms (azeridine, oxirane, thiirane, oxaziridine, azetidine, azetidinone, oxetane, oxetanone, thietane, pyrrole, furan, thiophene, 1,2- and 1,3-azoles, triazoles, pyridine, pyryliums, diazines, triazine and their oxy-derivatives); b) fused heterocycles containing one or more heteroatoms (indoles, benzofurans, benzothiophene, benzanellated azoles, quinolines, isoquinolines, benzopyrones). Heterocycles in natural products, medicine and materials. Heterocyclic compounds: reactivity, orientation and important reactions of furan, pyrrole, pyridine, indole, synthesis (including retrosynthetic approach) pyrrole: Knorr pyrrole synthesis and Hantzsch synthesis. Hantzsch pyridine synthesis. Indole: Fischer, Madelung and Reissert synthesis, Skaurp quinoline and Bischler-Napieralski Synthesis of isoquinoline.

11) Chemistry of natural products: A) Carbohydrates:

Monosaccharides: Aldoses upto 6 carbons, structure of D-glucose & D-fructose (configuration & conformation), anomeric effect, mutarotation reactions: osazone formation, bromine water oxidation, steppingup (Kiliani method) and steppingdown (Ruffs & Wohls method) of aldoses. Disaccharides: glycosidic linkages, structure of sucrose.
B) Amino acids,Proteins and peptides:

Amino acids: Synthesis: (Strecker, Gabriel, acetamido malonic ester, azlactone); isoelectric point, ninhydrin reaction. Peptides: peptide linkage, syntheses of peptides using N-protection & C-protection,solid phase synthesis; peptide sequence: Cterminal and Nterminal unit determination (Edmann, Sanger & dansyl chloride).
C) Fatty acids: General features. D) Nucleic acids:

Nucleic acids: pyrimidine & purine bases, nucleosides and nucleotides, DNA: Watson-Crick model, complimentary base pairing in DNA.
E) Terpenes:

Camphor, Longifolene, Abietic acid, and Taxol.

F) Steroids:

Cholesterol, Cortisone, and Aldosterone.

G) Alkaloids:

Structure elucidation of alkaloids a general account; Structure, synthesis, and stereochemistry

of Narcotine and Quinine; synthesis and stereochemistry of Morphine, Lysergic acid and Reserpine. Biogenesis of terpenoids and alkaloids.

Section- VI
INORGANIC CHEMISTRY
10) Bioinorganic chemistry:

Essential and trace elements in biological processes, Metal ion transport across biological membrane, Na+-ion pump, ionophores. Biological functions of hemoglobin and myoglobin, cytochromes and ferredoxins. Carbonate bicarbonate buffering system and carbonic anhydrase. Biological nitrogen fixation, Photosynthesis: Photosystem-I and Photosystem-II. Toxic metal ions and their effects, chelation therapy (examples only), Pt and Au complexes as drugs (examples only).

11) Characterisation of inorganic compounds by IR, Raman, NMR, EPR, Mssbauer, UV-Vis, NQR, MS, electron spectroscopy and microscopic techniques. Structural Methods in Inorganic Chemistry NMR Spectroscopy: NMR phenomenon, spin nuclei, (1H, 13C, 31P and 19F), 1H NMR, Zeeman splitting, effect of magnetic field strength on sensitivity and resolution, chemical shift, chemical and magnetic equivalence of spins, spin-spin coupling, structural correlation to coupling constant J, first order patterns. Second order effects, examples of AB, AX and ABX systems, simplification of second order spectrum, selective decoupling, use of chemical shift reagents for stereochemical assignments. 13C NMR, introduction to FT technique, relaxation phenomena, NOE effects, 1H and 13C chemical shifts to structure correlations. Electron Spin Resonance Spectroscopy: Electron paramagnetic resonance (EPR) spectroscopy of inorganic compounds with unpaired electrons - determination of electronic structure, Zeeman splitting, g-values, hyperfine and super hyperfine coupling constants, practical considerations of measurements, and instrumentation. Mssbauer Spectroscopy: Basic principle, conditions for Mossbauer spectroscopy, Spectral parameters (Isomer shift, electric quadrupole interactions, magnetic interactions), temperature dependent effects, structural deductions for iron and tin complexes, miscellaneous applications.

Infrared and Raman Spectroscopy: Infrared and Raman spectroscopy of simple inorganic molecules, predicting number of active modes of vibrations, analysis of representative spectra of metal complexes with various functional groups at the coordination sites; application of isotopic substitution, organic functional group identification through IR spectroscopy. Mass Spectrometry: Mass spectrometry, basic principles, ionization techniques, isotope abundance, molecular ion, fragmentation processes of organic molecules, deduction of structure through mass spectral fragmentation, high resolution MS, soft ionization methods, ESI-MS and MALDI-MS, illustrative examples from macromolecules and supramolecules, studies of inorganic/coordination and organometallic representative compounds.

PHYSICAL CHEMISTRY
9) Statistical Thermodynamics:
Macro and micro states, entropy and thermodyanamic probability Third Law of

Thermodyanamics, concepts of ensembles (micro canonical, canonical and grand canonical), fluctuations and residual entropy.
Boltzmann distribution law, partition functions physical meaning and evaluation of the

absolute value of thermodyanamic state function, applications in their calculations for the model systems. Barometric distribution law and applications, Nernst heat theorem, approach to zero Kelvin and adiabatic demagnetisation. Quantum statistics Bose Einstein and Fermi Dirac statistics fundamental concepts. 10) Advanced quantum mechanics and group theory: Approximation Methods: Stationary perturbation theory for non-degenerate and degenerate systems up to second order in energy with examples. Variation method. Atomic structure and spectroscopy: Zeeman effect and anomalous Zeeman effect in details (behaviour of angular in homogenous magnetic field, Stern-Gerlach experiment, spin-orbit interaction and L-S coupling, effect of magnetic field in presence of spin-orbit interaction), term symbols; manyelectron systems and antisymmetry principle. Group theory: The concept of groups, symmetry operations and symmetry elements in molecules, matrix representations of symmetry operations, point groups, irreducible representations, character tables and selection rules, Great orthogonality theorem.

ORGANIC CHEMISTRY
12) Structure determination of organic compounds by UV-Vis, 1H & 13C NMR and Mass spectroscopic techniques:
A) UV Spectra: Electronic transition (-*, n-*, -* and n-*), relative positions of max

considering conjugative effect, steric effect, solvent effect, red shift (bathochromic shift), blue shift (hypsochromic shift), hyperchromic effect, hypochromic effect (typical examples).

B) IR Spectra: Modes of molecular vibrations, application of Hookes law, characteristic

stretching frequencies of O-H, N-H, C-H, C-D, C=C, C=N, C=O functions; factors effecting stretching frequencies (H-bonding, mass effect, electronic factors, bond multiplicity, ring size).
C) PMR Spectra: Nuclear spin, NMR active nuclei, principle of proton magnetic resonance,

equivalent and non-equivalent protons, chemical shift ), shielding / deshielding of protons, upfield and down-field shifts. NMR peak area (integration), diamagnetic anisotropy, relative peak positions of different kinds of protons (alkyl halides, olefins, alkynes, aldehyde H), substituted benzenes (toluene, anisole, nitrobenzene, halobenzene, dinitrobenzenes, chloronitrobenzene), first order coupling (splitting of the signals: ordinary ethanol, bromoethane, dibromoethanes), coupling constants.
D) Mass Spectra: Mass spectrometry, basic principles, ionization techniques, isotope abundance,

molecular ion, fragmentation processes of organic molecules, deduction of structure through mass spectral fragmentation, high resolution MS, soft ionization methods, ESI-MS and MALDI-MS, illustrative examples from macromolecules and supramolecules. 13) Medicinal Chemistry:
A) Mechanism of enzyme action: Typical enzyme mechanism for ribonuclease, lysozome, chemical

models and mimics for enzymes, receptors, peptides, carbohydrates and other bioactive molecules. Design, synthesis and evaluation of enzyme inhibitors.
B) Enzyme

catalysed reactions: Carboxylation and decarboxylataion, Isomerization and rearrangement. associated with biological activities, structure-activity relationship, mechanism of drug action.

C) Drug design: Introduction to rational approach to drug design, physical and chemical factors D) Classification of drugs: Based on structure or pharmacological basis with examples.

Antineoplastic agents, cardiovascular drugs, local antiinfective drugs, psychoactive drugs, antibiotics.
E) Synthesis: Synthesis of important drugs. F) Modelling: Molecular modelling, conformational analysis. G) Drugs based on five-membered heterocycles fused to six-membered rings: Acyclovir,

methotrexate.
H) -Lactam antibiotics: Penicillin, cephalosporin. I) J)

Drugs based on heterocycles fused to two benzene rings: Quinacrine, tacrine. Drugs based on six membered heterocycles: Warfarin, quinine, norfloxacin and ciprofloxacin, methylclothiazide, citrine, terfenadine. nizatidine, imolamine, isobuzole.

K) Drugs based on five membered heterocycles: Tolmetin, spiralpril, oxaprozine, sulconazole, L) Illustration

of drug development a) Antibacterials: sulfonamides and penicillins

through

specific

examples:

b) Antivirals: case studies with inhibitors of reverse transcriptase (nucleoside reverse transcriptase- and non-nucleoside reverse transcriptase inhibitors) and protease inhibitors. c) Anticancer agents: antimetabolite-based approaches, those which affect signalling pathways or structural proteins such as tubulin. Drug resistance, Drug synergism and combination therapy.

CSIR- UGC (NET) EXAM FOR AWARD OF JUNIOR RESEARCH FELLOWSHIP AND ELIGIBILITY FOR LECTURERSHIP

CHEMICAL SCIENCES
EXAM SCHEME
TIME: 3 HOURS MAXIMUM MARKS: 200

CSIR-UGC (NET) Exam for Award of Junior Research Fellowship and Eligibility for Lecturership shall be a Single Paper Test having Multiple Choice Questions (MCQs). The question paper is divided in three parts Part 'A' This part shall carry 20 questions pertaining to General Science, Quantitative Reasoning & Analysis and Research Aptitude. The candidates shall be required to answer any 15 questions. Each question shall be of two marks. The total marks allocated to this section shall be 30 out of 200.

Part 'B' This part shall contain 50 Multiple Choice Questions(MCQs) generally covering the topics given in the syllabus. A candidate shall be required to answer any 35 questions. Each question shall be of two marks. The total marks allocated to this section shall be 70 out of 200. Part 'C' This part shall contain 75 questions that are designed to test a candidate's knowledge of scientific concepts and/or application of the scientific concepts. The questions shall be of analytical nature where a candidate is expected to apply the scientific knowledge to arrive at the solution to the given scientific problem. A candidate shall be required to answer any 25 questions. Each question shall be of four marks. The total marks allocated to this section shall be 100 out of 200. There will be negative marking @25% for each wrong answer. To enable the candidates to go through the questions, the question paper booklet shall be distributed 15 minutes before the scheduled time of the exam. The Answer sheet shall be distributed at the scheduled time of the exam.

On completion of the exam i.e. at the scheduled closing time of the exam, the candidates shall be allowed to carry the Question Paper Booklet. No candidate is allowed to carry the Question Paper Booklet in case he/she chooses to leave the test before the scheduled closing time.

Joint CSIR-UGC NET for JRF and Elegibility for Lectureship Notice
It is notified for information of all students that syllabus of Part A of Joint CSIR-UGC Test for Junior Research Fellowship and Eligibility for Lectureship has been revised. The existing syllabus and revised syllabus is as under: Existing Syllabus: General Science, Quantitative Reasoning and Analysis and Research Aptitude. Revised Syllabus: General Aptitude with emphasis On logical reasoning, graphical analysis, analytical and numerical ability, quantitative comparison, series formation, puzzles etc. The number of questions available and to be attempted in this Part A remains the same i.e. there will be 20 questions and the candidates shall be required to answer any 15 questions. Each question will be of two marks.

ALL THE VERY BEST TO YOU FOR YOUR NET EXAM- A C H I E V E R S C I R C L E.