IAS CHEMISTRY OPTIONAL SYLLABUS

For a UPSC CSE aspirant, the optional subject is also an important subject. In the UPSC mains exam, optional marks have two papers, Paper 1 and Paper 2. Each paper is of 250 marks which makes a total of 500 marks. The UPSC optional subject list contains 48 subjects in total, one of which is Chemistry.

It is a highly specialized subject and the syllabus is suitable for candidates who have studied Chemistry at the graduate level.
The syllabus mainly focuses on the atomic structure and atomic structure, states of matter, different kinds of reactions, etc.

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SYLLABUS OF PAPER 1

ATOMIC STRUCTURE:

Quantum theory
Quantum numbers
Heisenberg’s uncertainty principle
Schrodinger wave equation (time-independent).
Interpretation of wave function
Particle in a one-dimensional box
Hydrogen atom wave functions
Shapes of s, p, and d orbitals.

2. CHEMICAL BONDING:

Ionic bond, characteristics of ionic compounds, factors affecting the stability 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 homonuclear molecules: H+2, H2 to Ne2, NO, CO, HF, CN, CN-, BeH2, and CO2.
Comparison of valence bond and molecular orbital theories, bond order, bond strength, and bond length.

3. SOLID STATE;

Crystal systems and crystal classes (crystallographic groups). Designation of crystal faces, lattice structures, and unit cells.
Laws of rational indices.
X-ray diffraction by crystals.
Bragg’s law.
Close packing, radius ratio rules, calculation of some limiting radius ratio values.
Structures of NaCl, ZnS, CsCl, CaF2, CdI2 and rutile.
Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors, imperfections in crystals.

4. GASEOUS STATE AND TRANSPORT PHENOMENON:

Equation of state for real gases
Intermolecular interactions as well as a critical phenomenon.
Liquefaction of gases
Maxwell’s distribution of speeds
Intermolecular collisions, collisions on the wall, and effusion.
The viscosity of ideal gases, and thermal conductivity.

5. THERMODYNAMICS AND STATISTICAL THERMODYNAMICS:

Thermodynamic systems, states, and processes, work, heat, and internal energy; first law of thermodynamics, work done on the systems and heat absorbed in different types of processes; calorimetry, energy and enthalpy changes in various processes and their temperature dependence.
The second law of thermodynamics; entropy as a state function, entropy changes in various process, entropy–reversibility and irreversibility, Free energy functions; criteria for equilibrium, the relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem
Third law of thermodynamics.
Micro and macro states; canonical ensemble and canonical partition function; electronic, rotational, and vibrational partition functions and thermodynamic quantities; chemical equilibrium in ideal gas reactions.

6. PHASE EQUILIBRIA AND SOLUTIONS:

Clausius-Clapeyron equation
Phase diagram and equilibrium 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.

7. 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 batteries, and fuel cells.
Processes at electrodes; double layer at the interface; the rate of charge transfer, current density; overpotential; electroanalytical techniques–voltammetry, polarography, amperometry, cyclic-voltammetry, ion-selective electrodes, and their use.

8. CHEMICAL KINETICS:

Differential and integral rate equations for zeroth, first, second, and fractional order reactions.
Rate equations involving parallel, reverse, consecutive, and chain reactions; effect of temperature and pressure on rate constant.
Study of fast reactions by stop-flow and relaxation methods.
Collisions and transition state theories.

9. PHOTOCHEMISTRY:

Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.

10. SURFACE PHENOMENA AND CATALYSIS:

Adsorption from gases and solutions on solid adsorbents
Adsorption isotherms–Langmuir and B.E.T. isotherms
Determination of surface area, characteristics, and mechanism of reaction on heterogeneous catalysts.

11. BIO-INORGANIC CHEMISTRY:

Metal ions in biological systems and their role in ion transport across the membranes (molecular mechanism)
Ionophores, photosynthesis–PSI, PSII; nitrogen fixation, oxygen uptake proteins, cytochrome, and ferredoxins.

12. COORDINATION CHEMISTRY:

Introduction to theories of bonding in transition 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.
Synthesis and structures 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-metal bonds and metal atom clusters.

13. MAIN GROUP CHEMISTRY:

Borazines, Boranes, phosphazenes, and cyclic phosphazene, silicones, and silicates.
Interhalogens compounds, Sulphur- nitrogen compounds, noble gas compounds.

14. GENERAL CHEMISTRY OF F- BLOCK ELEMENTS:

Lanthanides, and Actinides, oxidation states, separation, spectral and magnetic properties, lanthanide contraction.

15. LIQUID STATE:

Kelvin equation
Surface tension and surface energy, wetting and contact angle, interfacial tension, and capillary action.

SYLLABUS FOR PAPER 2

1. DELOCALISED COVALENT BONDING:

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

(2)

(2.1) Reaction mechanisms: General methods (both kinetic and non-kinetic) of study of mechanism or organic reactions and examples–use of cross-over experiment, isotopes, intermediate trapping, stereochemistry; energy diagrams of simple organic reactions–transition states and intermediates; the energy of activation; thermodynamic control and kinetic control of reactions.

(2.2) Reactive intermediates: Generation, stability, geometry, and reactions of carbanium and carbonium ions, carbanions, free radicals, carbenes, nitrenes, and benzynes.

(2.3) Substitution reactions: SN1, SN2, SNi, SN1’, SN2’, SNi’, and SRN1 mechanisms, electrophilic and nucleophilic reactions of the aromatic compounds including simple heterocyclic compounds–pyrrole, thiophene, indole, and neighboring group participation.

(2.4) Elimination reactions: E1, E2, and E1cb mechanisms, pyrolytic syn elimination–acetate pyrolysis, orientation in E2 reactions–Saytzeff and Hoffmann, Chagaev, and Cope eliminations.

(2.5) Addition reactions: Electrophilic addition to C C and C=C; nucleophilic addition to C=O, C=N, conjugated olefins, and carbonyl.

(2.6) Rearrangements: Pinacol-pinacolune, Hoffmann, Beckmann, Baeyer–Villiger, Fries, Favorskii, Claisen, Cope, Stevens, and Wagner-Meerwein rearrangements, all class XII important named 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) PREPARATION AND PROPERTIES OF POLYMERS:

Organic polymers polyethylene, polyvinyl chloride, polystyrene, nylon, Teflon, natural, and synthetic rubber.
Structure of RNA, DNA, and proteins.

(5) Synthetic uses of reagents:

OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, 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:

Principles of spectroscopy and applications in structure elucidation:
- Rotational spectra: diatomic molecules; isotopic substitution and rotational constants.
- Electronic spectra: Singlet and triplet states. N–>* and –>* transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules.
- Vibrational spectra: diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
- Mass spectra: Parent peak, base peak, Daugther peak, metastable peak, fragmentation of simple organic molecules;– cleavage, McLafferty rearrangement.
- Nuclear magnetic resonance: Isochronous and isochronous protons; chemical shift and coupling constants; Application of 1H NMR to simple organic molecules.
- Electron spin resonance: Inorganic complexes and free radicals