Chemistry

CHEMISTRY

PAPER-I

1. Atomic structure

Quantum theory, Heisenberg's uncertainity principle, Schrodinger wave equation (time independent).

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: H+2, H2 to Ne2, NO, CO, HF, CN, CN-, BeH2 and CO2. Comparision 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. Bragg's 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, liquifictaion of gases and critical phenomena, Maxwell's 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�voltametry, polarography, amperometry, 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 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 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.