UPSC Optional Subject Syllabus: Chemistry Notes - 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, concept of resonance and resonance energy; Molecular orbital theory (LCAO method); bonding H₂ +, H₂ He₂ + to Ne₂, NO, CO, HF, 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, 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 enercy, 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, ??and?? ; 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 : amperometry, ion selective electrodes and their use. 

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:

• Adsorption 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 ferrodoxins. 

13. Coordination Chemistry 

• Bonding in transition of metal complexes. Valence bond theory, crystal field theory and its modifications; applications of theories in the explanation of magnetism and elctronic spectra of metal complexes.
• 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-planar complexes; thermodynamic and kinetic stability of complexes.
• EAN rule, Synthesis structure and reactivity of metal carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl compounds.
• 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 Element: 

• 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. 

• Reaction mechanisms: General methods (both kinetic and non-kinetic) of study of mechanisms or organic reactions : isotopies, mathod cross-over experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions. 
• Reactive intermediates: Generation, geometry, stability and reactions of carboniumions and carbanions, free radicals, carbenes, benzynes and nitrenes. 
• Substitution reactions : S_N1, S_N2, and S_N i, mechanisms ; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds—pyrrole, furan, thiophene and indole.
• Elimination reactions : E1, E2 and E1cb mechanisms; orientation in E2 reactions—Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Cope eliminations. 
• Addition reactions: Electrophilic addition to C=C and C?C; nucleophilic addition to C=O, C?N, conjugated olefins and carbonyls. 
• Reactions and Rearrangements: (a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner—Meerwein rearrangements.
• 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. 

• Preparation and Properties of Polymers: Organic polymers polyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber. 
• Biopolymer: Structure of proteins, DNA and RNA.

5. Synthetic Uses of Reagents

• OsO₄, HlO₄, CrO₃, Pb(OAc)₄, SeO₂, NBS, B₂H₆, Na-Liquid NH₃, LiAIH₄,  NaBH₄, n-BuLi, 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
• Rotational: Diatomic molecules; isotopic substitution and rotational constants. 
• Vibrational: Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules. 
• Electronic: Singlet and triplet states. n??? and ???? transitions; application to conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer spectra. 
• Nuclear Magnetic Resonance (1HNMR): Basic principle; chemical shift and spin-spin interaction and coupling constants. 
• Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.