Chemistry: Chemistry Syllabus For UPSC Main Examination
Chemistry: Chemistry Syllabus For UPSC Main Examination
Paper-I
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.
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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; Nerns theat 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.
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.
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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), oxygenuptake 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.
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Paper-II
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.
(v) Addition Reactions: Electrophilic addition to C=C and C=C; nucleophilic addition to C=0, C=N,
conjugated olefins and carbonyls.
3. Pericyclic Reactions: Classification and examples; Woodward Hoffmann rules - electro cyclic
reactions, cycloaddition reactions [2+2 and 4+2] and sigma tropic shifts [1, 3; 3, 3 and 1, 5] FMO
approach.
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4. (i) Preparation and Properties of Polymers: Organic polymers-polyethylene, polystyrene,
polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.
5. Synthetic Uses of Reagents: OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3,
LiAlH4, NaBH4, n-BuLi and MCPBA.
(iii) Electronic: Singlet and triplet states; N→π* and ππ*→ 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.