PRELIMINARY
1.1 Atomic structure : Schrodinger wave equation, significance of y and y2 quantum numbers and their significance, radial and angular probability, shapes of orbitals, relative energies of atomic orbitals as a function of atomic number. Electronic configurations of elements; Aufbau principle, Hunds multiplicity rule, Pauliexclusion principle.1.2 Chemical periodicity : Periodic classification of elements, salient characteristics of s,p,d and f block elements. Periodic trends of atomic radii, ionic radii, ionisation potential, electron affinity and electronegativity in the periodic table.
1.3 Chemical bonding : Types of bonding, overlap of atomic orbitals, sigma and pi bonds, hydrogen and metallic bonds. Shapes of molecules, bond order, bond length, V.S.E.P.R. theory and bond angles. The concept of hybridization and shapes of molecules and ions.
1.4 Oxidation states and oxidation number : Oxidation and reduction, oxidation numbers, common redox reactions, ionic equations. Balancing of equations for oxidation and reduction reactions.
1.5 Acids and bases : Bronsted and Lewis theories of acids and bases. Hard and soft acids and bases. HSAB principle, relative strengths of acids and bases and the effect of substituents and solvents on their strength.
1.6 Chemistry of elements :
(i) Hydrogen: Its unique position in the periodic table, isotopes, ortho and para hydrogen, industrial production, heavy water.
(ii) Chemistry of s and p block elements : electronic configuration, general characteristics properties, inert pair effect, allotropy and catenation. Special emphasis on solutions of alkali and alkaline earth metals in liquid ammonia. Preparation, properties and structures of boric acid, borates, boron nitrides, borohydride (diborane), carboranes, oxides and oxyacids of nitrogen, phosphorous, sulphur and chlorine; interhalogen compounds, polyhalide ions, pseudohalogens, fluorocarbons and basic properties of halogens. Chemical reactivity of noble gases, preparation, structure and bonding of noble gas compounds.
(iii) Chemistry of d block elements: Transition metals including lanthanides, general characteristic properties, oxidation states, magnetic behaviour, colour. First row transition metals and general properties of their compounds (oxides, halides and sulphides); lanthanide contraction.
1.7 Extraction of metals : Principles of extraction of metals as illustrated by sodium, magnesium, aluminium, iron, nickel, copper, silver and gold.
1.8 Nuclear Chemistry : Nuclear reactions; mass defect and binding energy, nuclear fission and fusion. Nuclear reactors; radioisotopes and their applications.
1.9 Coordination compounds : Nomenclature, isomerism and theories of coordination compounds and their role in nature and medicine.
1.10 Pollution and its control : Air pollution, types of air pollutants; control of air and water pollution; radioactive pollution.
Section-B (Organic Chemistry)
2.1 Bonding and shapes of organic molecules : Electronegativity, electron displacements-inductive, mesomeric and hyperconjugative effects; bond polarity and bond polarizability, dipole moments of organic molecules; hydrogen bond; effects of solvent and structure on dissociation constants of acids and bases; bond formation, fission of covalent bonds : homolysis and heterolysis; reaction intermediates-carbocations, carbanions, free radicals and carbenes; generation, geometry and stability; nucleophiles and electrophiles.
2.2 Chemistry of aliphatic compounds: Nomenclature; alkenes-synthesis, reactions (free radical halogenation) -- reactivity and selectivity, sulphonation-detergents; cycloalkanes-Baeyers strain theory; alkenes and alkynes-synthesis, electrohilic addition reactions, Markownikovs rule, peroxide effects, 1- 3-dipolar addtion; nucleophilic addition to electron-deficient alkenes; polymerisation; relative acidity; synthesis and reactions of alkyl halides, alkanols, alkanals, alkanones, alkanoic acids, esters, amides, nitriles, amines, acid anhydrides, a, ß-unsaturated ketones, ethers and nitro compounds.
2.3 Stereochemistry of carbon compounds : Elements of symmetry, chiral and achiral compounds. Fischer projection formulae; optical isomerism of lactic and tartaric acids, enantiomerism and diastereoisomerism; configuration (relative and absolute); conformations of alkanes upto four carbons, cyclohexane and dimethylcyclo-hexanes-their potential energy. D, L-and R, S-notations of compounds containing chiral centres; projection formulae-Fischer, Newman and sawhorse-of compounds containing two adjacent chiral centres; meso and dl-isomers, erythro and threo isomers; racemization and resolution; examples of homotopic, enantiotopic and diasteretopic atoms and groups in organic compounds, geometrical isomers; E and Z notations. Stereochemistry of SN1, SN2, E1 and E2 reactions.
2.4 Organometallic compounds : Preparation and synthetic uses of Grignard reagents, alkyl lithium compounds.
2.5 Active methylene compounds : Diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate-applications in organic synthesis; tautomerism (keto-enol).
2.6 Chemistry of aromatic compounds : Aromaticity; Huckels rule; electrophilic aromatic substitution-nitration, sulphonation, halogenation (nuclear and side chain), Friedel-Crafts alkylation and acylation, substituents effect; chemistry and reactivity of aromatic halides, phenols, nitro-, diazo, diazonium and sulphonic acid derivatives, benzyne reactions.
2.7 Chemistry of biomolecules : (i) Carobhydrates : Classification, reactions, structure of glucose, D, L-configuration, osazone formation; fructose and sucrose; step-up step-down of aldoses and ketoses, and ther interconversions, (ii) Amino acdis : Essential amino acids; zwitterions, isoelectric point, polypeptides; proteins; methods of synthesis of a-amino acids. (iii) Elementary idea of oils, fats, soaps and detergents.
2.8 Basic principles and applications of UV, visible, IR and NMR spectroscopy of simple organic molecules.
Section-C (Physical Chemistry)
3.1 Gaseous state : Deviation of real gases from the equation of state for an ideal gas, van der Waals and Virial equation of state, critical phenomena, principle of corresponding states, equation for reduced state. Liquification of gases, distribution of molecular speed, collisions between molecules in a gas; mean free path, speicific heat of gases
3.2 Thermodynamics : (i) First law and its applications: Thermodynamic systems, states and processes, work, heat and internal energy, zeroth law of thermodynamics, various types of work done on a system in reversible and irreversible processes. Calorimetry and thermochemistry, enthalpy and enthalpy changes in various physical and chemical processes, Joule-Thomson effect, inversion temperautre. Heat capacities and temperature dependence of enthalpy and energy changes.
(ii) Second law and its applications : Spontaneity of a process, entropy and entropy changes in various processes, free energy functions, criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities.
3.3 Phase rule and its applications : Equilibrium bewteen liquid, solid and vapours of a pure substance, Clausius-Clapeyron equation and its applications. Number of components, phases and degrees of freedom; phase rule and its applications; simple systems with one (water and sulphur) and two components (lead-silver, salt hydrates). Distribution law, its modifications, limitations and applications.
3.4 Solutions : Solubility and its temperature dependence, partially miscible liquids, upper and lower critical solution temperatres, vapour pressures of liquids over their mixtures, Raoults and Henrys laws, fractional and steam distillations.
3.5 Colligative Properties : Dilute solutions and colligative properties, determination of molecular weights using colligative properties.
3.6 Electrochemistry : Ions in solutions, ionic equilibria, dissociation constants of acids and bases, hydrolysis, pH and buffers, theory of indicators and acid-base titrations. Conductivity of ionic solutions, its variation with concentration, Ostwalds dilution law, Kohlrausch law and its application. Transport number and its determination. Faradays laws of electrolysis, galvanic cells and measurements of their e.m.f., cell reactions, standard cell, standard reduction potential, Nernst equation, relation between thermodynamic quantities and cell e.m.f., fuel cells, potentiometric titrations.
3.7 Chemical kinetics : Rate of chemical reaction and its dependence on concentrations of the reactants, rate constant and order of reaction and their experimental determination; differential and integral rate equations for first and second order reaction, half-life periods; temperature dependence of rate constant and Arrhenius parameters; elementary ideas regarding collision and transition state theory.
3.8 Photochemistry : Absorption of light, laws of photochemistry, quantum yield, the excited state and its decay by radiative, nonradiative and chemical pathways; simple photochemical reactions.
3.9 Catalysis : Homogeneous and heterogeneous catalysis and their characteristics, mechanism of heterogeneous catalysis; enzyme catalysed reactions (Michaelis-Menten mechanism).
3.10 Colloids : The colloidal state, preparation and purification of colloids and their characteristics properties; lyophilic and lyophobic colloids and coagulation; protection of colloids; gels, emulsions, surfactants and micelles.
Mains
1. Atomic structure
Quantum theory, Heisenbergs uncertainity principle, Schrodinger wave equation (time independent). Interpretation of wave function, particle in one-dimensional box, quantum numbers, hydrogen atom wave functions. Shapes of s, p and d orbitals.
2. Chemical bonding
Ionic bond, characteristics of ionic compounds, factors affecting stability of ionic compounds, lattice energy, Born-Haber cycle; covalent bond and its general characteristics, polarities of bonds in molecules and their dipole moments. Valence bond theory, concept of resonance and resonance energy. Molecular orbital theory (LCAO method); bonding in homonuclear molecules: H2+, H2 to Ne2, NO, CO, HF, CN, CN–, BeH2 and CO2. Comparison of valence bond and molecular oribtal theories, bond order, bond strength and bond length.
3. Solid State
Forms of solids, law of constancy of interfacial angles, crystal systems and crystal classes (crystallographic groups). Designation of crystal faces, lattice structures and unit cell. Laws of rational indices. Braggs law. X-ray diffraction by crystals. Close packing, radious ratio rules, calculation of some limiting radius ratio values. Structures of NaCl, ZnS, CsCl, CaF2, CdI2 and rutile. Imperfections in crystals, stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors. Elementary study of liquid crystals.
4. The gaseous state
Equation of state for real gases, intermolecular interactions, liquefictaion of gases and critical phenomena, Maxwells distribution of speeds, intermolecular collisions, collisions on the wall and effusion.
5. Thermodynamics and statistical thermodynamics
Thermodynamic systems, states and processes, work, heat and internal energy; first law of thermodynamics, work done on the systems and heat absorbed in different types of processes; calorimetry, energy and enthalpy changes in various processes and their temperature dependence.
Second law of thermodynamics; entropy as a state function, entropy changes in various process, entropy–reversibility and irreversibility, Free energy functions; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem and third law of thermodynamics.
Micro and macro states; canonical ensemble and canonical partition function; electronic, rotational and vibrational partition functions and thermodynamic quantities; chemical equilibrium in ideal gas reactions.
6. Phase equilibria and solutions
Phase equilibria in pure substances; Clausius-Clapeyron equation; phase diagram for a pure substance; phase equilibria in binary systems, partially miscible liquids–upper and lower critical solution temperatures; partial molar quantities, their significance and determination; excess thermodynamic functions and their determination.
7. Electrochemistry
Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law for various equilibrium and transport properties.
Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. of cells and its applications fuel cells and batteries.
Processes at electrodes; double layer at the interface; rate of charge transfer, current density; overpotential; electroanalytical techniques–voltameter, polarography, ampero-metry, cyclic-voltametry, ion selective electrodes and their use.
8. Chemical kinetics
Concentration dependence of rate of reaction; defferential and integral rate equations for zeroth, first, second and fractional order reactions. Rate equations involving reverse, parallel, consecutive and chain reactions; effect of temperature and pressure on rate constant. Study of fast reactions by stop-flow and relaxation methods. Collisions and transition state theories.
9. Photochemistry
Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogn and halogens and their quantum yields.
10. Surface phenomena and catalysis
Absorption from gases and solutions on solid adsorbents, adsorption isotherms,–Langmuir and B.E.T. isotherms; determination of surface area, characteristics and mechanism of reaction on heterogeneous catalysts.
11. Bio-inorganic chemistry
Metal ions in biological systems and their role in ion-transport across the membranes (molecular mechanism), ionophores, photosynthesis–PSI, PSII; nitrogen fixation, oxygen-uptake proteins, cytochromes and ferredoxins.
12. Coordination chemistry
(a) Electronic configurations; introduction to theories of bonding in transition metal complexes. Valence bond theory, crystal field theory and its modifications; applications of theories in the explanation of magnetism and electronic spactra of metal complexes.
(b) Isomerism in coordination compounds. IUPAC nomenclature of coordination compounds; stereochemistry of complexes with 4 and 6 coordination numbers; chelate effect and polynuclear complexes; trans effect and its theories; kinetics of substitution reactions in square-planer complexes; thermodynamic and kinetic stability of complexes.
(c) Synthesis and structures of metal carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl compounds.
(d) Complexes with aromatic systems, synthesis, structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadienyl complexes; coordinative unsaturation, oxidative addition reactions, insertion reactions, fluxional molecules and their characterization. Compounds with metal-metal bonds and metal atom clusters.
13. General chemistry of ‘f’ block elements
Lanthanides and actinides; separation, oxidation states, magnetic and spectral properties; lanthanide contraction.
14. Non-Aqueous Solvents
Reactions in liquid NH3, HF, SO2 and H2 SO4. Failure of solvent system concept, coordination model of non-aqueous solvents. Some highly acidic media, fluorosulphuric acid and super acids.
Paper-II
1. Delocalised covalent bonding : Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, kekulene, fulvenes, sydnones.
2(a) Reaction mechanisms : General methods (both kinetic and non-kinetic) of study of mechanism or organic reactions illustrated by examples–use of isotopes, cross-over experiment, intermediate trapping, stereochemistry; energy diagrams of simple organic reactions–transition states and intermediates; energy of activation; thermodynamic control and kinetic control of reactions.
(b) Reactive intermediates : Generation, geometry, stability and reactions of carbonium and carbonium ions, carbanions, free radicals, carbenes, benzynes and niternes.
(c) Substitution reactions : SN1, SN2, SNi, SN1/, SN2/, SNi/ and SRN1 mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compound including simple heterocyclic compounds–pyrrole, furan thiophene, indole.
(d) Elimination reactions : E1, E2 and E1cb mechanism; orientation in E2 reactions–Saytzeff and Hoffmann; pyrolytic syn elimination–acetate pyrolysis, Chugaev and Cope eliminations.
(e) Addition reactions : Electrophilic addition to CºC and C=C; nucleophilic addition to C=O, CºN, conjugated olefins and carbonyls.
(f) Rearrangements : Pinacol-pinacolune, Hoffmann, Beckmann, Baeyer–Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.
3. Pericyclic reactions : Classification and examples; Woodward-Hoffmann rules—clectrocyclic reactions, cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO approach.
4. Chemistry and mechanism of reactions : Aldol condensation (including directed aldol condensation), Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin condensations; Fischer indole synthesis, Skraup synthesis, Bischler-Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactions.
5. Polymeric Systems
(a) Physical chemistry of polymers : Polymer solutions and their thermodynamic properties; number and weight average molecular weights of polymers. Determination of molecular weights by sedimentation, light scattering, osmotic pressure, viscosity, end group analysis methods.
(b) Preparation and properties of polymers : Organic polymers–polyethylene, polystyrene, polyvinyl chloride, Teflon, nylon, terylene, synthetic and natural rubber. Inorganic polymers–phosphonitrilic halides, borazines, silicones and silicates.
(c) Biopolymers : Basic bonding in proteins, DNA and RNA.
6. Synthetic uses of reagents : OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiA1H4 NaBH4 n-BuLi, MCPBA.
7. Photochemist : Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
8. Principles of spectroscopy and applications in structure elucidation
(a) Rotational spectra–diatomic molecules; isotopic substitution and rotational constants.
(b) Vibrational spectra–diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
(c) Electronic spectra : Singlet and triplet states. N–>p* and p–>p* transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules.
(d) Nuclear magnetic resonance : Isochronous and anisochronous protons; chemical shift and coupling constants; Application of H1 NMR to simple organic molecules.
(e) Mass spectra : Parent peak, base peak, daugther peak, metastable peak, fragmentation of simple organic molecules; a cleavage, McLafferty rearrangement.
(f) Electron spin resonance : Inorganic complexes and free radicals.
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