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Chemistry Optional Syllabus for Civil Service Examination

Chemistry is one of the optional subjects in the Civil Service Mains Examination. Chemistry optional has two papers (Paper I and Paper II). Each paper carries 250 which makes the total of 500. This UPSC optional paper is highly specialised and the syllabus is suitable for a candidate who took Chemistry as their main in their graduation. The syllabus for chemistry options mainly focuses on the atomic structure, states of matter, different kinds of reactions etc. It should be noted that the topics covered in this paper have a small overlap with the physics syllabus for the UPSC Optional paper. This optional paper is ideal for candidates who have done the job roles of a chemist, chemical engineer, doctor or allied medical professional and HAZMAT specialist. 

 

UPSC Syllabus for 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 bonds and their 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 
    • 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, semi-conductors

 

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 energy
  • wetting and contact angle
  • Interfacial tension and capillary action

 

6. Thermodynamics

 

  • Work, heat and internal energy
  • The 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 the 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.

 

8. Electrochemistry

 

  • Debye-Huckel theory of strong electrolytes 
  • 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 ferredoxins

 

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 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-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 characterisation
  • 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

 

UPSC Syllabus for Chemistry Optional: Paper II

 

1.Delocalised Covalent Bonding

 

  • Aromaticity, anti-aromaticity
  • Annulenes, azulenes, tropolones, fulvenes, sydnones.

 

2. (i) Reaction mechanisms

 

  • General methods of study of mechanisms or organic reactions
    • both kinetic and non-kinetic
  • Isotopies, 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 carbenium ions 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 
    • Cope eliminations

 

(v) Addition reactions

  • Electrophilic addition to C=C and C C
  • Nucleophilic addition to C=O, CN, conjugated olefins and carbonyls

 

(vi) Reactions and Rearrangements

  • 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 Reformatsky reactions.

 

3. Pericyclic reactions

 

  • classification and examples
    • Woodward-Hoffmann rules-electrocyclic reactions, cycloaddition reactions [2+2 and 4+2] 
    • Sigmatropic shifts [1, 3; 3, 3 and 1, 5]
    • FMO approach

 

4. (i) Preparation and Properties of Polymers

 

  • Organic polymers polyethylene, polystyrene, polyvinyl chloride, Teflon, nylon, terylene, synthetic and natural rubber.

 

(ii) Biopolymers

  • Structure of proteins, DNA and RNA

 

5. Synthetic Uses of Reagents

 

  • Os04, H104, Cr03, Pb(OAc)4, Se02, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, МСРВА.

 

  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

 

  • Principles 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

 

The chemistry optional subject requires a higher level of proficiency. Thus, the preparation must start at the earliest. It is recommended that the candidate should solve the questions that appeared in the previous year. In addition, the candidates must attend the mock test during their preparation. This would help them to secure higher scores in the UPSC CSE examination.