UPSC Chemistry Optional Syllabus for CSE Mains 2024
Chemistry Syllabus for UPSC Mains Exam 2024
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Syllabus of Chemistry Optional Paper‐I
- Atomic Structure :
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- 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.
- Chemical bonding :
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- 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.
Solid State :
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- 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.
- The Gaseous State and Transport Phenomenon :
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- 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.
- Liquid State :
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- Kelvin equation;
- Surface tension and surface enercy, wetting and contact angle, interfacial tension and capillary action.
- Thermodynamics :
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- 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.
- Phase Equilibria and Solutions :
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- 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.
- Electrochemistry :
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- 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.
- Chemical Kinetics:
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- 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.
- Photochemistry:
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- Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.
Surface Phenomena and Catalysis:
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- 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.
- Bio‐inorganic Chemistry:
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- Metal ions in biological systems and their role in ion-transport across the membranes (molecular mechanism), oxygen-uptake proteins, cytochromes and ferrodoxins.
- Coordination Chemistry :
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- Bonding in transition 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-planar complexes; thermodynamic and kinetic stability of complexes.
- EAN 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—metal bonds and metal atom clusters.
- Main Group Chemistry:
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- Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds;
- Sulphur—nitrogen compounds, noble gas compounds.
General Chemistry of ‘f’ Block Element: Lanthanides and actinides: separation, oxidation states, magnetic and spectral properties; lanthanide contraction.
Syllabus of Chemistry Optional Paper‐II
- Delocalised Covalent Bonding : Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
- Reactions:
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- 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.
- Reactive intermediates : Generation, geometry, stability and reactions of carboniumions and carbanions, free radicals, carbenes, benzynes and nitrenes.
- 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.
- Elimination reactions :—E1, E2 and E1cb mechanisms; orientation in E2 reactions—Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Cope eliminations.
- Addition reactions :—Electrophilic addition to C=C and CC; nucleophilic addition to C=O, CN, conjugated olefins and carbonyls.
- Reactions and Rearrangements :—
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- Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner—Meerwein rearrangements.
- 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.
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- 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.
- Polymers
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- Preparation and Properties of Polymers: Organic polymerspolyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.
- Biopolymers: Structure of proteins, DNA and RNA.
Synthetic Uses of Reagents: OsO4, HlO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, MCPBA.
Photochemistry :—Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
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 and transitions; application to conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer spectra.
Nuclear Magnetic Resonance (1HNMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
Mass Spectrometry :—Parent peak, base peak, metastable peak, McLafferty rearrangement.
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