UPSC Civil Services (Mains)

1. 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. 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. 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. 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. 5
   Liquid state

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

6. 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; Nernst heat theorem, introductory idea of third law of thermodynamics.

7. 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. 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 uses.

9. 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. 10
    Photochemistry

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

11. 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. 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. 13
    Coordination chemistry

    (i) Bonding in transition 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-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. 14
    Main group chemistry

    Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, interhalogen compounds; sulphur–nitrogen compounds, noble gas compounds.

15. 15
    General chemistry of 'f' block elements

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

The wording follows the UPSC examination notification, with misprints corrected. Check the current notification on upsc.gov.in before your exam.