UPSC Civil Services (Mains) Examination Chemistry Syllabus
UPSC Civil Services (Mains) Examination Syllabus of Chemistry.
Paper ï¿½ I
1. Atomic Structure
- Heisenbergï¿½s uncertainty principle, Schrodinger wave equation (time independent);
- nterpretation 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 in H2+, H2, He2+ to Ne2, NO, CO, HF, and CNï¿½;
- 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; Braggï¿½s 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. The Gaseous State and Transport Phenomenon
- Equation of state for real gases, intermolecular interactions and critical phenomena and liquefaction of gases,
- Maxwellï¿½s 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 energy, wetting and contact angle, interfacial tension and capillary action.
- Work, heat and internal energy; first law of thermodynamics. Second law of thermodynamics; entropy as a state function, entropy changes in various processes, entropyï¿½reversibility and irreversibility,
- Free energy functions; Thermodynamic equation of state; Maxwell relations; Temperature, volume and pressure dependence of U, H, A, G, Cp and Cv;
- 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 liquidsï¿½upper and lower critical solution temperatures;
- partial molar quantities, their significance and determination; excess thermodynamic functions and their determination.
- 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: Polarography, amperometry, ion selective electrodes and their uses.
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.
- 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
- Absorption 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 ferredoxins.
13. Coordination Compounds
- Bonding theories 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.
- 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.
- EAN rule, Synthesis structure and reactivity 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.
14. Main Group Chemistry
- Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds;
- Sulphur ï¿½ nitrogen compounds, noble gas compounds.
- General Chemistry of ï¿½fï¿½ Block Elements:ï¿½Lanthanides and actinides; separation, oxidation states, magnetic and spectral properties; lanthanide contraction.
Paper ï¿½ II
1. Delocalised Covalent Bonding:
Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
- Reaction Mechanisms: General methods (both kinetic and non-kinetic) of study of mechanism of organic reactions: isotopic method, cross-over experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions.
- Reactive Intermediates: Generation, geometry, stability and reactions of carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.
- Substitution Reactions: SN1, SN2 and SNi mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compoundsï¿½pyrrole, furan, thiophene and indole.
- Elimination Reactions: E1, E2 and E1cb mechanisms; orientation in E2 reactionsï¿½Saytzeff and Hoffmann; pyrolytic syn elimination ï¿½ Chugaev and Cope eliminations.
- Addition Reactions: Electrophilic addition to C=C and C?C; nucleophilic addition to C=0, C?N, conjugated olefins and carbonyls.
Reactions and Rearrangements:
- Pinacol-pinacolone, Hoffmann, Beckmann, Baeyerï¿½Villiger, 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.
3. Pericyclic Reactions
- Classification and examples; Woodward-Hoffmann rules ï¿½ electrocyclic reactions, cycloaddition reactions [2+2 and 4+2] and
- sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO approach.
ï¿½4. Preparation and Properties ofï¿½Polymers
- Organic polymersï¿½polyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber
- 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.
- Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
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 p* and p p* transitions; application to conjugated double bonds and conjugated carbonylsï¿½Woodward-Fieser rules; Charge transfer spectra.
- Nuclear Magnetic Resonance (1H NMR): 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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