Everything You Need To Know About Upsc Chemistry Optional Syllabus

UPSC Chemistry Optional Syllabus for CSE Mains 2024

Chemistry Syllabus for UPSC Mains Exam 2024


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Syllabus of Chemistry Optional Paper‐I 

  • 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.
  • 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.

    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.
  • 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.
  • Liquid State :
    • Kelvin equation;
    • Surface tension and surface enercy, wetting and contact angle, interfacial tension and capillary action.
  • 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.
  • 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.
  • 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.
  • 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.
  • Photochemistry:
    • Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.


  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.
  • 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.
  • Coordination Chemistry :
    1. Bonding in transition 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.
    2. 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.
    3. EAN rule, Synthesis structure and reactivity of metal carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl compounds.
    4. 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.
  • Main Group Chemistry:
    • Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds;
    • Sulphur—nitrogen compounds, noble gas compounds.

General Chemistry of ‘f’ Block Element: Lanthanides and actinides: separation, oxidation states, magnetic and spectral properties; lanthanide contraction.


Syllabus of Chemistry Optional Paper‐II


  1. Delocalised Covalent Bonding : Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
  2. Reactions:
      1. 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.
      2. Reactive intermediates : Generation, geometry, stability and reactions of carboniumions and carbanions, free radicals, carbenes, benzynes and nitrenes.
      3. Substitution reactions :—SN 1, SN 2, and SN i, mechanisms ; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds—pyrrole, furan, thiophene and indole.
      4. Elimination reactions :—E1, E2 and E1cb mechanisms; orientation in E2 reactions—Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Cope eliminations.
      5. Addition reactions :—Electrophilic addition to C=C and CC; nucleophilic addition to C=O, CN, conjugated olefins and carbonyls.
      6. Reactions and Rearrangements :—
        • 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.
  • 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.
  • Polymers
    1. Preparation and Properties of Polymers: Organic polymerspolyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.
    2. Biopolymers: Structure of proteins, DNA and RNA.

Synthetic Uses of Reagents: OsO4, HlO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, MCPBA.

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

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.

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