UPSC Mains Exam Syllabus - Chemistry Optional
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 in H2
+, H2, He2
Ne2, NO, CO, HF, and CN–; Comparison of
valence bond and molecular orbital theories,
bond order, bond strength and bond
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
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
Second law of thermodynamics; entropy
as a state function, entropy changes in various
processes, entropy–reversibility and
irreversibility, Free energy functions; Thermodynamic quation 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.
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
amperometry, ion selective electrodes and
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.
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
(iii) EAN rule, Synthesis structure and reactivity
of metal carbonyls; carboxylate
anions, carbonyl hydrides and metal nitrosyl
(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 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 and
E1cb 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
(vi) Reactions and Rearrangements:
Pinacol-pinacolone, Hoffmann, Beckmann,
Baeyer–Villiger, Favorskii, Fries,
Claisen, Cope, Stevens and Wagner-
(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,
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
4. (i) Preparation and Properties of Polymers:
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
Photochemical reactions of simple organic
compounds, excited and ground states,
singlet and triplet states, Norrish-Type I and
Type II reactions.
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
Charge transfer spectra.
(iv) Nuclear Magnetic Resonance (1H
NMR): Basic principle; chemical shift and
spin-spin interaction and coupling constants.
(v) Mass Spectrometry: Parent peak, base
peak, metastable peak, McLafferty rearrangement.