UPSC has a long list of optional subjects out of which you can select any subject of your choice. Here we are giving an outline of syllabus of  Chemistry.

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UPSC Chemistry Optional

UPSC Mains Syllabus Chemistry

PAPER – I

Atomic Structure:

Heisenberg’s uncertainty principle, Interpretation of wave function, Schrodinger wave equation (time independent); particle in one-dimensional box, quantum numbers, Shapes of s, p and d orbitals,hydrogen atom wave functions;.

Chemical Bonding:

Ionic bond, characteristics of ionic compounds, Born-Haber cycle ,lattice energy, covalent bond and characteristics, study of  polarities of bonds in molecules and their dipole moments; concept of resonance and resonance energy; Valence bond theory, Molecular orbital theory (LCAO method); bonding in H2+, H2, He2+ to Ne2, NO,HF, CO and CN–; Comparison of valence bond and molecular orbital theories,bond strength and bond length, bond order..

Solid State:

Crystal systems; Designation of crystal faces, lattice structures and unit cell; X-ray diffraction by crystals, Bragg’s law; Close packing, radius ratio rules, calculation of some limiting radius ratio values; Structures of NaCl, CsCl, CaF2 and ZnS; impurity defects, Stoichiometric and non-stoichiometric defects, semiconductors.

The Gaseous State and Transport Phenomenon:

Equation of state of  real gases, intermolecular interactions and critical phenomena and liquefaction of gases, collisions on the wall and effusion; intermolecular collisions, Maxwell’s distribution of speeds, Thermal conductivity and viscosity of ideal gases.

Liquid State:

Kelvin equation; wetting and contact angle, Surface energy and surface tension, interfacial tension and capillary action.

Thermodynamics:

Work, heat and internal energy; first and second law of thermodynamics. entropy as a state function, entropy–reversibility and irreversibility ,entropy changes in various processes, , 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 in equilibrium constant and thermodynamic quantities, introductory idea of third law of thermodynamics, Nernst heat theorem.

Phase Equilibria and Solutions:

Clausius-Clapeyron equation; phase equilibria in binary systems, the phase diagram for a pure substance, partially miscible liquids–upper and lower critical solution temperatures; partial molar quantities, their determinations and significance; excess thermodynamic functions and their determination.

Electrochemistry:

Debye-Huckel theory of strong electrolytes,  Limiting Law of Debye-Huckel for transport properties and various equilibrium. Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. of cells and its applications batteries and fuel cells. Processes at electrodes; double layer at the interface; current density, rate of charge transfer, overpotential; electro-analytical techniques: amperometry, Polarography, ion selective electrodes and their uses.

Chemical Kinetics:

Integral and Differential rate equations for zeroth, first, second and fractional order reactions; Rate equations involving reverse, consecutive, parallel and chain reactions; branching chain and explosions; effect of temperature and pressure on rate constant; Collisions and transition state theories, Study of fast reactions by stop-flow and relaxation methods.

 Photochemistry:

Absorption of light; decay of excited state by different routes; photochemical reactions between halogens and hydrogen and their quantum yields.

Surface Phenomena and Catalysis:

Gases and Absorption and solutions on solid adsorbents, Langmuir and B.E.T. adsorption isotherms; characteristics and mechanism of reaction on heterogeneous catalysts, determination of surface area.

Bio-inorganic Chemistry:

Metal ions in biological systems and their role in ion transport across the membranes (molecular mechanism), oxygen uptake proteins, ferredoxins and cytochromes.

Coordination Compounds:

(i) Bonding theories of metal complexes; Crystal field theory and its modifications; Valence bond theory, applications of theories in the explanation of magnetism and electronic spectra of metal complexes.

(ii) Isomerism in coordination compounds; IUPAC nomenclature of coordination compounds; chelate effect and polynuclear complexes; stereochemistry of complexes with 4 and 6 coordination numbers; trans effect and its theories; thermodynamic and kinetic stability of complexes, kinetics of substitution reactions in square-planer complexes.

(iii) EAN rule, Synthesis structure and reactivity of metal carbonyls; carbonyl hydrides, carboxylate anions and metal nitrosyl compounds.

(iv) Complexes with aromatic systems, structure,  synthesis, bonding in metal olefin complexes, cyclopentadienyl complexes and alkyne complexes; coordinative unsaturation, insertion reactions, oxidative addition reactions,  fluxional molecules and their characterization; Compounds with metal- metal atom clusters and metal bonds.

Main Group Chemistry:

Borazines, Boranes, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds; noble gas compounds, Sulphur – nitrogen compounds.

General Chemistry of ‘f’ Block Elements:

Lanthanides and actinides; oxidation states, separation, magnetic and spectral properties; lanthanide contraction.


UPSC Mains Syllabus Chemistry

PAPER – II

Delocalised Covalent Bonding:

Aromaticity, anti-aromaticity; azulenes, annulenes, tropolones, fulvenes, sydnones.

(i) Reaction Mechanisms:

General methods (both non-kinetic and kinetic) of the study of mechanism of organic reactions:

isotopic method, intermediate trapping, cross-over experiment, the energy of activation; stereochemistry; kinetic control and thermodynamic control of reactions.

(ii) Reactive Intermediates: Geometry, Generation, stability and reactions of carbonium ions and carbanions, carbenes, free radicals, benzynes and nitrenes.

(iii) Substitution Reactions: SN1 and SN2  along with  SN1 mechanisms; neighbouring group participation;  nucleophilic and electrophilic reactions of aromatic compounds including heterocyclic compounds– furan, pyrrole, thiophene and indole.

(iv) Elimination Reactions: E1, E2 and E1cb mechanisms; orientation in E2 reactions–Saytzeff and Hoffmann;  Chugaev and Cope eliminations, pyrolytic syn elimination.

(v) Addition Reactions: Electrophilic addition to C=C and C=C; conjugated olefins and carbonyls, nucleophilic addition to C=0, C=N.

(vi) Reactions and Rearrangements:

(a) Pinacol-pinacolone, Hoffmann, Beckmann, Favorskii, Fries, Baeyer–Villiger, Claisen, Cope, Stevens and Wagner- Meerwein rearrangements.

(b) Aldol condensation, Claisen condensation, Knoevenagel, Witting, Dieckmann, Perkin, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin condensations; Skraup synthesis, Fischer indole synthesis, Bischler-Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactions.

Pericyclic Reactions:

Classification and examples; Woodward- Hoffmann rules – electrocyclic reactions, and sigmatropic shifts [1, 3; 3, 3 and 1, 5] ,cycloaddition reactions [2+2 and 4+2] FMO approach.

(i) Preparation and Properties of Polymers: Polystyrene, polyvinyl chloride, Organic polymers–polyethylene, terylene, Teflon, nylonsynthetic and natural rubber.

(ii) Biopolymers: Structure of proteins, DNA and RNA.

Synthetic Uses of Reagents:

OsO4, HIO4, CrO3, SeO2, Pb(OAc)4, NBS, B2H6, Na-Liquid NH3, NaBH4, LiAlH4, n-BuLi and MCPBA.

Photochemistry:

Photochemical reactions of simple organic compounds, singlet and triplet states,  excited and ground states, Norrish-Type I and Type II reactions.

Spectroscopy:

Principle and applications used in structure elucidation:

(i) Rotational: Diatomic molecules; rotational constants and isotopic substitution.

(ii) Vibrational: Linear triatomic molecules, Diatomic molecules, specific frequencies of functional groups in polyatomic molecules.

(iii) Electronic: Singlet and triplet states; N→π* and ππ*→ transitions; application to conjugated double bonds and conjugated carbonyls, Charge transfer spectra, Woodward-Fieser rules;

(iv) Nuclear Magnetic Resonance (1H NMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.

(v) Mass Spectrometry: Parent peak, metastable peak, base peak, McLafferty rearrangement.

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