UPSC – Chemistry Syllabus

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 : 

(i) 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. 

(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-planar 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 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. (i) 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. 

(ii) Reactive intermediates : Generation, geometry, stability and reactions of carboniumions  and carbanions, free radicals, carbenes, benzynes and nitrenes. 

 (iii) Substitution reactions :—S_N 1, S_N 2, and S_N i, 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—acetate pyrolysis, Chugaev and Cope  eliminations. 

(v) Addition reactions :—Electrophilic addition to C=C and C≡C; nucleophilic addition to  C=O, 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 polymerspolyethylene, polystyrene,  polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber. 

(ii) Biopolymers: 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 : 

(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* andπ→π* transitions; application to  conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer  spectra. 

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

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