CHEMISTRY Optional Subject in UPSC

 CHEMISTRY

Paper-I

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 H2 +, H2 He2 + to Ne2, NO, CO, HF, 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, 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; 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 enercy, 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; Thermodynamicequation of state; Maxwell relations; Temperature, volume and pressure dependence of U, H, -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; electroanalytical techniques : amperometry, ion selective electrodes

and their use.

 

 

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

 

11. Surface Phenomena and Catalysis:

Adsorption 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 ferrodoxins.

 

 

13. Coordination Chemistry :

(i) Bonding in transition of metal complexes. Valence bond theory, crystal field theory and

its modifications; applications of theories in the explanation of magnetism and elctronic

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-planar complexes; thermodynamic and kinetic stability of complexes.

 

(iii) EAN rule, Synthesis structure and reactivity of metal carbonyls; carboxylate anions,

carbonyl hydrides and metal nitrosyl compounds.

 

(iv) 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 Element:

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

mechanisms or organic reactions : isotopies, mathod 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

carboniumions and carbanions, free radicals, carbenes, benzynes and nitrenes.

 

 

(iii) Substitution reactions :—SN 1, SN 2, and SN i, mechanisms ; neighbouring group

participation; electrophilic and nucleophilic reactions of aromatic compounds

including heterocyclic compounds—pyrrole, furan, thiophene and indole.

 

 

(iv) Elimination reactions :—E1, E2 and E1cb mechanisms; orientation in E2

reactions—Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev

and Cope eliminations.

 

 

(v) Addition reactions :—

ed 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 polymerspolyethylene, polystyrene,

polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.

 

 

(ii) Biopolymers: Structure of proteins, DNA and RNA.

 

 

5. Synthetic Uses of Reagents:

OsO4, HlO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, 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:

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

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.