Contents
Chemistry Optional-Syllabus as per UPSC official syllabus
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; Thermodynamic
equation 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 their quantum yields.
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.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.
Suggestive books for chemistry optional
- A guide to mechanism in organic chemistry – Peter Sykes
- A textbook of environmental chemistry and pollution – S.S. Dara.
- A textbook of organic chemistry – Bahl & Ba
- A textbook of physical chemistry (Vol. – IV) – K.L. Kapoor
- Advance physical chemistry – Gurdeep Raj
- Advance physical chemistry – Gurdeep Raj
- Advanced Inorganic Chemistry – J.D. Lee
- An advanced inorganic chemistry – J.D. Lee
- Extradition of metals, Principle of inorganic chemistry – Puri, Sharma, Jauhar.
- Organic Chemistry Reactions and reagents – O.P. Agarwal
- Principle of physical chemistry – Puri, Sharma & Pathway
- Principles of Physical Chemistry – Puri, Sharma & Pathway
