(iii)
Electronic: Singlet and triplet states; n
p*
and p
p*
transitions; application to conjugated double bonds and conjugated
carbonyls–Woodward-Fieser rules; Charge transfer spectra.| CHEMISTRY -
Optional of Part B - Main Examination of Civil Services Exam |
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PAPER
- I
1.
Atomic Structure:
Heisenberg's
uncertainty 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, 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 H2+,
H2, He2+ to Ne2, NO, CO, HF, and CN–;
Comparison of valence bond and molecular orbital theories, bond order, bond
strength and bond length.
3.
Solid State:
Crystal
systems; Designation of crystal faces, lattice structures and unit cell; Bragg's
law; X-ray diffraction by crystals; Close packing, radius ratio rules,
calculation of some limiting radius ratio values; Structures of NaCl, ZnS, CsCl
and CaF2; Stoichiometric and nonstoichiometric defects, impurity
defects, semi-conductors.
4.
The Gaseous State and Transport Phenomenon:
Equation
of state for real gases, intermolecular interactions and critical phenomena and
liquefaction of gases, Maxwell's distribution of speeds, intermolecular
collisions, collisions on the wall and effusion; Thermal conductivity and
viscosity of ideal gases.
5.
Liquid State:
Kelvin
equation; Surface tension and surface energy, wetting and contact angle,
interfacial tension and capillary action.
6.
Thermodynamics:
Work,
heat and internal energy; first law of thermodynamics.
Second
law of thermodynamics; entropy as a state function, entropy changes in various
processes, entropy–reversibility and irreversibility, Free energy functions;
Thermodynamic equation of state; Maxwell relations; Temperature, volume and
pressure dependence of U, H, A, G, Cp and Cv, α and
β; J-T effect and inversion temperature; criteria for equilibrium, relation
between equilibrium constant and thermodynamic quantities; Nernst heat theorem,
introductory idea of third law of thermodynamics.
7.
Phase Equilibria and Solutions:
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.
8.
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: Polarography, amperometry,
ion selective electrodes and their uses.
9.
Chemical Kinetics:
Differential
and integral rate equations for zeroth, first, second and fractional order
reactions; Rate equations involving reverse, parallel, consecutive and chain
reactions; branching chain and explosions; effect of temperature and pressure on
rate constant; Study of fast reactions by stop-flow and relaxation methods;
Collisions and transition state theories.
10.
Photochemistry:
Absorption
of light; decay of excited state by different routes; photochemical reactions
between hydrogen and halogens and their quantum yields.
11.
Surface Phenomena and Catalysis:
Absorption
from gases and solutions on solid adsorbents, Langmuir and B.E.T. adsorption
isotherms; determination of surface area, characteristics and mechanism of
reaction on heterogeneous catalysts.
12.
Bio-inorganic Chemistry:
Metal
ions in biological systems and their role in ion transport across the membranes
(molecular mechanism), oxygen-uptake proteins, cytochromes and ferredoxins.
13.
Coordination Compounds:
(i)
Bonding theories of metal complexes; Valence bond theory, crystal field theory
and its modifications; applications of theories in the explanation of magnetism
and electronic spectra of metal complexes.
(ii)
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.
(iii)
EAN rule, Synthesis structure and reactivity
of metal carbonyls; carboxylate anions, carbonyl hydrides and metal
nitrosyl compounds.
(iv)
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.
14.
Main Group Chemistry:
Boranes,
borazines, phosphazenes and cyclic phosphazene, silicates and silicones,
Interhalogen compounds; Sulphur – nitrogen compounds, noble gas compounds.
15.
General Chemistry of ‘f’ Block Elements:
Lanthanides
and actinides; separation, oxidation states, magnetic and spectral properties;
lanthanide contraction.
PAPER
- II
1.
Delocalised Covalent Bonding:
Aromaticity,
anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
2.
(i) Reaction Mechanisms: General methods (both kinetic and
non-kinetic) of study of mechanism of organic reactions: isotopic method,
cross-over experiment, intermediate trapping, stereochemistry; energy of
activation; thermodynamic control and kinetic control of reactions.
(ii)
Reactive Intermediates: Generation, geometry, stability and reactions of
carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.
(iii)
Substitution Reactions: SN1, SN2 and SNi
mechanisms; neighbouring group participation; electrophilic and nucleophilic
reactions of aromatic compounds including heterocyclic compounds–pyrrole,
furan, thiophene and indole.
(iv)
Elimination Reactions: E1, E2 and E1cb mechanisms; orientation in E2
reactions–Saytzeff and Hoffmann; pyrolytic syn elimination – Chugaev
and Cope eliminations.
(v)
Addition Reactions: Electrophilic addition to C=C and C≡C;
nucleophilic addition to C=0, C≡N, conjugated olefins and
carbonyls.
(vi)
Reactions and Rearrangements: (a) Pinacol-pinacolone, Hoffmann, Beckmann,
Baeyer–Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein
rearrangements.
(b)
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.
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.
(i)
Preparation and Properties of Polymers: Organic
polymers–polyethylene, polystyrene, polyvinyl chloride, teflon, nylon,
terylene, synthetic and natural rubber.
(ii)
Biopolymers: Structure of proteins, DNA and RNA.
5.
Synthetic Uses of Reagents:
OsO4,
HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6,
Na-Liquid NH3, LiAlH4, NaBH4, n-BuLi
and MCPBA.
6.
Photochemistry:
Photochemical
reactions of simple organic compounds, excited and ground states, singlet and
triplet states, Norrish-Type I and Type II reactions.
7.
Spectroscopy:
Principle and applications in structure elucidation:
(i)
Rotational: Diatomic molecules; isotopic substitution and rotational
constants.
(ii)
Vibrational: Diatomic molecules, linear triatomic molecules, specific
frequencies of functional groups in polyatomic molecules.
(iii)
Electronic: Singlet and triplet states; n
p*
and p
p*
transitions; application to conjugated double bonds and conjugated
carbonyls–Woodward-Fieser rules; Charge transfer spectra.
(iv)
Nuclear Magnetic Resonance (1H NMR): Basic
principle; chemical shift and spin-spin interaction and coupling constants.
(v)
Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty
rearrangement.