UPSC CHEMISTRY - Chanakya Mandal Pariwar



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,

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, A, G, Cp and Cv, and ; 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

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


1. Delocalised covalent bonding :

Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.


(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
(v) Addition reactions :—Electrophilic addition to C=C and C C; nucleophilic addition to
C=O, C N, conjugated olefins and carbonyls.
(vi) Reactions and Rearrangements :

(a) Pinacol-pinacolone, Hoffmann, Beckmann, BaeyerVilliger, 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


(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,

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 and transitions; application to
conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer
(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