CHEMISTRY
PAPER-I
1. Atomic structure
Quantum theory, Heisenberg's uncertainty principle, Schrödinger
wave equation (timeindependent). 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: H+2,
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. 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.
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