UPSC Civil Services Examination Syllabus of “Chemistry” Preliminary and Mains Exam.

Optional Subject Papers I & II Candidates may choose any optional subject from amongst the list of subjects given in Para 2 (Group 1). However, if a candidate has graduated in any of the literatures of languages indicated in Group-2, with the literature as the main subject, then the candidate can also opt for that particular literature subject as an optional subject.

Syllabus of Chemistry

Paper-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 IH2+, H2, He2 ± to Nee, 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 NaC1, ZnS, CsCI 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 Cva and a; 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.

• 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 solutiontemperatures; partial molar quantities, their significance and determination; excess thermodynamic functions and their determination.

8. Electrochemistry:

Debye-Heckel 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 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. 4 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.

MN 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-met 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-2

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:

SN 1 , 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:

El, E2 and E I cb mechanisms; orientation in E2 reactions—Saytzeff and Hoffmann; pyrolytic syn elimination — 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; Fische 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 sigtnatropic 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: 0s04, HI04, Cr03, Pb(OAc)4, Se02, NBS, B2H6, Na-Liquid NH3, LiAIH4, 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 -?A* and A A*- transitions; application to conjugated double bonds and conjugated carbonyls—Woodward-Fieser rules; Charge transfer spectra.
• Nuclear Magnetic Resonance (‘H NMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
• Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.