Civil Services Examination Chemistry Syllabus

Civil Services Syllabus for Chemistry

Syllabus for Chemistry

Paper I (Maximum Marks 300)

1. Atomic Structure: Shapes of s, p and d orbitals, hydrogen atom wave functions, Heisenberg's uncertainty principle, Schrodinger wave equation (time independent) and interpretation of wave function, particle in one-dimensional box and quantum numbers.

2. Chemical Bonding: Molecular orbital theory (LCAO method), Bonding in H2+, H2, He2+ to Ne2, NO, CO, HF, and CN–, Valence bond theory, concept of resonance and resonance energy, 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 and comparison of valence bond and molecular orbital theories, bond order, bond strength and bond length.

3. Solid State: Close packing, radius ratio rules, calculation of some limiting radius ratio values, crystal systems, structures of NaCl, ZnS, CsCl and CaF2, designation of crystal faces, lattice structures and unit cell, stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors, X-ray diffraction by crystals and Bragg's law.

4. The Gaseous State and Transport Phenomenon: Thermal conductivity and viscosity of ideal gases, 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.

5. Liquid State: Kelvin equation, surface tension and surface energy, wetting and contact angle, interfacial tension and capillary action.

6. Thermodynamics: First law of thermodynamics (work, heat and internal energy), 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, temperature, volume and pressure dependence of U, H, A, G, Cp and Cv, an 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 and Maxwell relations.

7. Phase Equilibria and Solutions: Phase equilibria in binary systems, partially miscible liquids–upper and lower critical solution temperatures, phase diagram for a pure substance, excess thermodynamic functions and their determination, partial molar quantities, their significance and determination and Clausius-Clapeyron equation.

8. Electrochemistry: 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 (polarography, amperometry, ion selective electrodes and their uses) and Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law for various equilibrium and transport properties.

9. Chemical Kinetics: Effect of temperature and pressure on rate constant, study of fast reactions by stop-flow and relaxation methods, collisions and transition state theories, branching chain and explosions, differential and integral rate equations for zeroth, first, second and fractional order reactions and rate equations involving reverse, parallel, consecutive and chain reactions.

10. Photochemistry: Photochemical reactions between hydrogen and halogens and their quantum yields, absorption of light and decay of excited state by different routes.

11. Surface Phenomena and Catalysis: Determination of surface area, absorption from gases and solutions on solid adsorbents, characteristics and mechanism of reaction on heterogeneous catalysts and Langmuir and B.E.T. adsorption isotherms.

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. Coordination Compounds:

  1. Applications of theories in the explanation of magnetism and electronic spectra of metal complexes, bonding theories of metal complexes, Valence bond theory and crystal field theory and its modifications.
  2. IUPAC nomenclature of coordination compounds, Isomerism in coordination compounds, kinetics of substitution reactions in square-planer complexes, thermodynamic and kinetic stability of complexes, stereochemistry of complexes with 4 and 6 coordination numbers, trans effect and its theories, chelate effect and polynuclear complexes.
  3. Synthesis structure and reactivity of metal carbonyls, EAN rule, carbonyl hydrides, metal nitrosyl compounds and carboxylate anions.
  4. Coordinative unsaturation, oxidative addition reactions, insertion reactions, fluxional molecules and their characterization, complexes with aromatic systems, synthesis, structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadienyl complexes and compounds with metal-metal bonds and metal atom clusters.
14. Main Group Chemistry: Sulphur – nitrogen compounds, noble gas compounds, boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, interhalogen compounds.

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

Paper II (Maximum Marks 300)

1. Delocalised Covalent Bonding: Annulenes, azulenes, tropolones, fulvenes, sydnones, aromaticity and anti-aromaticity.

2. Reaction Mechanisms:

  1. Isotopic method, cross-over experiment, intermediate trapping, stereochemistry energy of activation, thermodynamic control and kinetic control of reactions, general methods (both kinetic and non-kinetic) of study of mechanism of organic reactions.
  2. Reactive Intermediates: Generation, geometry, stability and reactions of carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.
  3. Substitution Reactions: SN1, SN2 and SNi 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 – Chugaev and Cope eliminations.
  5. Addition Reactions: Electrophilic addition to C=C and CC, nucleophilic addition to C=0, CN, conjugated olefins and carbonyls.
  6. Reactions and Rearrangements: (i) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer–Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein rearrangements. (ii) 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:

  1. Organic polymers–polyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.
  2. Biopolymers: Structure of proteins, DNA and RNA.
5. Synthetic Uses of Reagents: OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, NaBH4, n-BuLi and 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:

  1. Rotational: Diatomic molecules, isotopic substitution and rotational constants.
  2. Vibrational: Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
  3. Electronic: Singlet and triplet states, n p and p p transitions, application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules, charge transfer spectra.
  4. Nuclear Magnetic Resonance (1H NMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
  5. Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.

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