IAS CHEMISTRY OPTIONAL SYLLABUS

For a UPSC CSE aspirant, the optional subject is also an important subject. In the UPSC mains exam, optional marks have two papers, Paper 1 and Paper 2. Each paper is of 250 marks which makes a total of 500 marks. The UPSC optional subject list contains 48 subjects in total, one of which is Chemistry.

  • It is a highly specialized subject and the syllabus is suitable for candidates who have studied Chemistry at the graduate level.
  • The syllabus mainly focuses on the atomic structure and atomic structure, states of matter, different kinds of reactions, etc.

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SYLLABUS OF PAPER 1

  1. ATOMIC STRUCTURE:
  • Quantum theory
  • Quantum numbers
  • Heisenberg’s uncertainty principle
  • Schrodinger wave equation (time-independent).
  • Interpretation of wave function
  • Particle in a one-dimensional box
  • Hydrogen atom wave functions
  • Shapes of s, p, and d orbitals.

2. CHEMICAL BONDING:

  • Ionic bond, characteristics of ionic compounds, factors affecting the stability 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 homonuclear molecules: H+2, H2 to Ne2, NO, CO, HF, CN, CN-, BeH2, and CO2.
  • Comparison of valence bond and molecular orbital theories, bond order, bond strength, and bond length.

3. SOLID STATE;

  • Crystal systems and crystal classes (crystallographic groups). Designation of crystal faces, lattice structures, and unit cells.
  • Laws of rational indices.
  • X-ray diffraction by crystals.
  • Bragg’s law.
  • Close packing, radius ratio rules, calculation of some limiting radius ratio values.
  • Structures of NaCl, ZnS, CsCl, CaF2, CdI2 and rutile.
  • Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors, imperfections in crystals.

4. GASEOUS STATE AND TRANSPORT PHENOMENON:

  • Equation of state for real gases
  • Intermolecular interactions as well as a critical phenomenon.
  • Liquefaction of gases
  • Maxwell’s distribution of speeds
  • Intermolecular collisions, collisions on the wall, and effusion.
  • The viscosity of ideal gases, and thermal conductivity.

5. THERMODYNAMICS AND STATISTICAL THERMODYNAMICS:

  • Thermodynamic systems, states, and processes, work, heat, and internal energy; first law of thermodynamics, work done on the systems and heat absorbed in different types of processes; calorimetry, energy and enthalpy changes in various processes and their temperature dependence.
  • The second law of thermodynamics; entropy as a state function, entropy changes in various process, entropy–reversibility and irreversibility, Free energy functions; criteria for equilibrium, the relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem
  • Third law of thermodynamics.
  • Micro and macro states; canonical ensemble and canonical partition function; electronic, rotational, and vibrational partition functions and thermodynamic quantities; chemical equilibrium in ideal gas reactions.

6. PHASE EQUILIBRIA AND SOLUTIONS:

  • Clausius-Clapeyron equation
  • Phase diagram and equilibrium 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.

7. 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 batteries, and fuel cells.
  • Processes at electrodes; double layer at the interface; the rate of charge transfer, current density; overpotential; electroanalytical techniques–voltammetry, polarography, amperometry, cyclic-voltammetry, ion-selective electrodes, and their use.

8. CHEMICAL KINETICS:

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

9. PHOTOCHEMISTRY:

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

10. SURFACE PHENOMENA AND CATALYSIS:

  • Adsorption from gases and solutions on solid adsorbents
  • Adsorption isotherms–Langmuir and B.E.T. isotherms
  • Determination of surface area, characteristics, and mechanism of reaction on heterogeneous catalysts.

11. BIO-INORGANIC CHEMISTRY:

  • Metal ions in biological systems and their role in ion transport across the membranes (molecular mechanism)
  • Ionophores, photosynthesis–PSI, PSII; nitrogen fixation, oxygen uptake proteins, cytochrome, and ferredoxins.

12. COORDINATION CHEMISTRY:

  • Introduction to theories of 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.
  • 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-planer complexes; thermodynamic and kinetic stability of complexes.
  • Synthesis and structures 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.

13. MAIN GROUP CHEMISTRY:

  • Borazines, Boranes, phosphazenes, and cyclic phosphazene, silicones, and silicates.
  • Interhalogens compounds, Sulphur- nitrogen compounds, noble gas compounds.

14. GENERAL CHEMISTRY OF F- BLOCK ELEMENTS:

  • Lanthanides, and Actinides, oxidation states, separation, spectral and magnetic properties, lanthanide contraction.

15. LIQUID STATE:

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

SYLLABUS FOR PAPER 2

1. DELOCALISED COVALENT BONDING:

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

(2)

(2.1) Reaction mechanisms: General methods (both kinetic and non-kinetic) of study of mechanism or organic reactions and examples–use of cross-over experiment, isotopes, intermediate trapping, stereochemistry; energy diagrams of simple organic reactions–transition states and intermediates; the energy of activation; thermodynamic control and kinetic control of reactions.

(2.2) Reactive intermediates: Generation, stability, geometry, and reactions of carbanium and carbonium ions, carbanions, free radicals, carbenes, nitrenes, and benzynes.

(2.3) Substitution reactions: SN1, SN2, SNi, SN1’, SN2’, SNi’, and SRN1 mechanisms, electrophilic and nucleophilic reactions of the aromatic compounds including simple heterocyclic compounds–pyrrole, thiophene, indole, and neighboring group participation.

(2.4) Elimination reactions: E1, E2, and E1cb mechanisms, pyrolytic syn elimination–acetate pyrolysis, orientation in E2 reactions–Saytzeff and Hoffmann, Chagaev, and Cope eliminations.

(2.5) Addition reactions: Electrophilic addition to C C and C=C; nucleophilic addition to C=O, C=N, conjugated olefins, and carbonyl.

(2.6) Rearrangements: Pinacol-pinacolune, Hoffmann, Beckmann, Baeyer–Villiger, Fries, Favorskii, Claisen, Cope, Stevens, and Wagner-Meerwein rearrangements, all class XII important named 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, polyvinyl chloride, polystyrene, nylon, Teflon, natural, and synthetic rubber.
  • Structure of RNA, DNA, and proteins.

(5) Synthetic uses of reagents:

  • OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, 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:

  • Principles of spectroscopy and applications in structure elucidation:
    • Rotational spectra: diatomic molecules; isotopic substitution and rotational constants.
    • Electronic spectra: Singlet and triplet states. N–>* and –>* transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules.
    • Vibrational spectra: diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
    • Mass spectra: Parent peak, base peak, Daugther peak, metastable peak, fragmentation of simple organic molecules;– cleavage, McLafferty rearrangement.
    • Nuclear magnetic resonance: Isochronous and isochronous protons; chemical shift and coupling constants; Application of 1H NMR to simple organic molecules.
    • Electron spin resonance: Inorganic complexes and free radicals
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