UPSC Civil Services Mains Exam Optional Subject consists of 2 papers. Each paper is of 250 marks, making a total of 500 marks.
Chemistry Syllabus – Civil Services Mains Exam UPSC
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, the 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.
Work, heat, and internal energy; first law of thermodynamics.
The 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 Cvá and â; J-T effect and inversion temperature; criteria for equilibrium, the relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem, the introductory idea of the 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.
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; the rate of charge transfer, current density; overpotential; electro-analytical 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.
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.
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 the mechanism of organic reactions: isotopic method, cross-over experiment, intermediate trapping, stereochemistry; the 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; neighboring 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.
Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
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 π* and π π* 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.