Civil Service Exam Preliminary – IAS Exam 2014 Syllabus for Chemistry
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. 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. 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. The Gaseous State and Transport Phenomenon :
Equation of state for real gases, inter-molecular 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. Liquid State :
Kelvin equation; Surface tension and surface energy, wetting and contact angle, interfacial tension and capillary action.
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 ά 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. 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. 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; over-potential; electro-analytical 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.
10. Photochemistry :
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 – nitrogen compounds, noble gas compounds.
15. General Chemistry of ‘f’ Block Elements :
Lanthanides and actinides; separation, oxidation states, magnetic and spectral properties; lanthanide contraction.
Paper – 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 compounds–pyrrole, furan, thiophene and indole.
- Elimination Reactions : E1, E2 and E1 cb mechanisms; orientation in E2 reactions–Saytzeff and Hoffmann; pyrolytic syn elimination – 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, 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.
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.
- Preparation and Properties of Polymers : Organic polymers–polyethy-lene, 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.
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 :
- 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→π* and ππ*→ transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-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.