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UPSC Mains 2023: Paper II
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Optional Subject Chemistry

 

 

 

 

   Chemistry Optional 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.

  1. 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.

  1. 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 Government strives to have a workforce which reflects gender balance and women candidates are encouraged to apply. nonstoichiometric defects, impurity defects, semi-conductors.

  1. 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.

  1. Liquid State:

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

  1. 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.

  1. 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.

  1. 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.

  1. 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.

  1. Photochemistry:

Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields. Surface Phenomena and Catalysis: Government strives to have a workforce which reflects gender balance and women candidates are encouraged to apply. 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.

  1. 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.

  1. 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.

  1. Main Group Chemistry:

Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds; Sulphur—nitrogen compounds, noble gas compounds.

  1. 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.

  1. (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. Government strives to have a workforce which reflects gender balance and women candidates are encouraged to apply.

(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 :—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, 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.

  1. 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.
  1. (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.

  1. Synthetic Uses of Reagents: OsO4, HlO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, MCPBA.
  1. Photochemistry :—Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
  1. 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 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.

 

 

 

Chemistry Optional Strategy

Preparing for the Chemistry Optional subject in the UPSC Civil Services examination requires a comprehensive strategy along with the right set of reference books. Here's a guideline covering reference books, study strategy, mapping, and answer writing:

Reference Books for Chemistry Optional:

  1. Physical Chemistry:
    • Atkins' Physical Chemistry by Peter Atkins
    • Physical Chemistry by P.W. Atkins and Julio de Paula
  2. Inorganic Chemistry:
    • Concise Inorganic Chemistry by J.D. Lee
    • Inorganic Chemistry by James E. Huheey
  3. Organic Chemistry:
    • Organic Chemistry by Morrison and Boyd
    • Organic Chemistry by Solomons and Fryhle
  4. Analytical Chemistry:
    • Quantitative Analysis by R.A. Day Jr. and A.L. Underwood
    • Vogel's Textbook of Quantitative Chemical Analysis by Arthur I. Vogel

Study Strategy:

  1. Understanding the Syllabus:
    • Familiarize yourself with the UPSC Chemistry Optional syllabus. Understand the weightage of different topics and subtopics to prioritize your preparation.
  2. Conceptual Clarity:
    • Develop a clear understanding of fundamental concepts, principles, and theories across all branches of chemistry.
    • Focus on understanding the underlying principles and mechanisms behind chemical reactions and phenomena.
  3. Thematic Study:
    • Organize your study material thematically to facilitate a deeper understanding and analysis.
    • Identify recurring themes and patterns across different topics in chemistry.
  4. Practice Numerical Problems:
    • Practice solving numerical problems and numerical-based questions regularly to strengthen your problem-solving skills in physical and analytical chemistry.

Mapping:

  1. Concept Maps:
    • Create concept maps to visualize the interrelationships between different concepts, reactions, and principles in chemistry.
    • Use concept maps to organize your notes and revise key concepts effectively.
  2. Reaction Mechanisms:
    • Develop a clear understanding of reaction mechanisms in organic and inorganic chemistry.
    • Create flowcharts or diagrams to illustrate reaction pathways and mechanisms.

Answer Writing:

  1. Practice Previous Year Papers:
    • Solve previous years' question papers to familiarize yourself with the exam pattern and types of questions asked.
    • Analyze the structure and presentation of answers in previous years' papers to understand the expectations of the examiner.
  2. Structuring Answers:
    • Structure your answers logically with clear introductions, well-organized body paragraphs, and concise conclusions.
    • Use diagrams, equations, and chemical structures wherever applicable to enhance the clarity and understanding of your answers.
  3. Time Management:
    • Allocate specific time limits for each question during practice sessions to improve time management skills.
    • Prioritize questions based on marks allotted and complexity of the topic.
  4. Seek Feedback:
    • Seek feedback from mentors, peers, or subject matter experts on your answer writing practice to identify areas of improvement and refine your approach.

By following these strategies and dedicating consistent effort to practice and improvement, you can enhance your performance in the Chemistry Optional subject of the UPSC Civil Services examination.