Civil Service Exam Syllabus (Preliminary) – Chemistry
Section-A
(Inorganic 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 ofvalence bond and molecular orbital theories,bond order, bond strength and bond length.
3. Solid State:
Crystal systems; Designation of crystalfaces, 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 surfaceenergy, 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 á and â; 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; overpotential; 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 stopflow 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:
(i) 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.
(ii)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.
2. (i) 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.
(ii) Reactive Intermediates:Generation,geometry, stability and reactions of carbonium ions and carbanions, free radicals,carbenes, benzynes and nitrenes.
(iii) 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.
(iv) Elimination Reactions:E1, E2 andE1cb mechanisms; orientation in E2 reactions–Saytzeff and Hoffmann; pyrolytic synelimination – Chugaev and Cope eliminations.
(v) Addition Reactions:Electrophilic addition to C=C and C=C; nucleophilic addition to C=0, C=N, conjugated olefins and carbonyls.
(vi) Reactions and Rearrangements:
(a) Pinacol-pinacolone, Hoffmann,Beckmann,Baeyer–Villiger, Favorskii, Fries,Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.
(b) 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. (i) Preparation and Properties of Polymers:Organic polymers–polyethy-lene,polystyrene, polyvinyl chloride, teflon, nylon,terylene, synthetic and natural rubber.
(ii) 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:
(i) Rotational: Diatomic molecules; isotopic substitution and rotational constants.
(ii) Vibrational: Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
(iii) Electronic: Singlet and triplet states;n Ý p* and p p*Ý transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules; Charge transfer spectra.
(iv) Nuclear Magnetic Resonance (1HNMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
(v) Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.
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