: Chemistry : Optional Subject of Main Examination
1. . Atomic structure: Quantum theory, Heisenbergs
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 homonuciear molecules: H2+, H2 to NÂ«,, NO, CO HF, CN, BeH2 and CO2.
Comparison of valence bond and molecular orbital theories, bond order, bond
strength and bond length.
3. Solid State: Forms of solids, law of constancy of inters
facial angles, crystal systems and crystal classes (crystallographic groups).
Designation of crvstal faces, lattice structures and unit cell. Laws of rational
indices. Braggs law. X-ray diffraction by crystals. Close packing, radius ratio
rules, calculation of same limiting radius ratio values. Structures of NaCl,
ZnS, CsCl, CaF2, Cdl2 and rutile. Imperfections in crystals, stoichiometric and
non-stoichiometric defects, impurity defects, semiÂ¬conductors. Elementary study
of liquid crystals.
4. The gaseous state: Equation of state for real gases,
intermolecular interactions, liquefication 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; Nemst 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
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- voltametery, polarography,
amperometry, cyctic-voltametry, ion selective electrodes and their use.
8. Chemical kinetics:- Concentration dependence of rate of
reaction; differential and integral rate equations for zeroth, first, second and
fractional order reactions. Rate equation-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 hydrogen and halogens
and their quantum yields.
10. Surface phenomena and catalysis: Adsorption from gages
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 bonds theory, crystal field theory and its
modifications; application of theories in the explanation of magnetism and
electronic spectra of metal complexes.
(b) Isomerism in coordination compounds. IUPAC nomenclature of coordination
compounds; stereochemistry of complexes with 4 and 6 coordination numbers;
chalet effect and polynuclear complexes; trans effect and its theories; kinetics
of substitution reactions in square-planar 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 metai
olefin complexes, alkyne complexes and cyclopentadienyl complexes; coordmative
unsaturation, oxidative addition reactions, insertion reactions, fluxional
molecules and their characterization. Compounds with metal-metal bonds and metal
13. General Chemistry of T 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 H2SO4.
Failure of solvent system concept, coordination model of non-aqueous solvents.
Some highly acidic media, fluorosulphuric acid and super acids.
1. Delocalises 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) Substitutions reactions: SN1, SN2, SNi, SNI, SN2, SNi and
SRN1 mechanisms; neighbouring group participation; electrophilic and
nucleophilic reactions of aromatic compound including simple heterocyclic
compounds-pyrrole, thiophene, indole.
(d) Elimination reactions: El, E2 and Elcb mechanism;
orientation inE2 reactions- Say tzeff and Hoffmann; pyrolytic syn elimination -
acetate pyrolysis, Chugaev and Cope eliminations.
(e) Addition reactions: Electrophilic addition to CÂ«=C and
C=C; nucleophilic addition to C=O, C=N, conjugated olefins and carbonyls.
(f) Rearrangements: Pinacol-pinacolune, Hoffmannn, Beckmann,
Baeyer-Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein
3. Pericyclic reactions: Classification and examples;
Woodward-Hoffmann rules- electrocyclic 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
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, tight 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: Basis bonding in proteins, DNA and RNA.
6. Synthetic uses of reagents: OsO4, HIO4, CrO3, Pb(OAc)4,
SeO0, NBS, B2H6, Na-Liquid NH3, LiAlH4 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
(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^-TI* and
n-~>n* transitions; application to conjugated double bonds and conjugated
(d) Nuclear magnetic resonance: Isochronous and anisochronous
protons; chemical shift arid coupling constants; Application of ^HNMR to simple
(e) Mass spectra: Parent peak, base peak, daughter peak,
metastable peak, fragmentation of simple organic molecules: a cleavage,
(f) Electron spin resonance: Inorganic complexes and free