CHEMISTRY SYLLABUS FOR UPSC IAS CIVIL SERVICES MAINS EXAMINATION

CHEMISTRY SYLLABUS FOR UPSC IAS CIVIL SERVICES MAINS EXAMINATION

                             PAPER-FIRST

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,
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 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, α and β ; 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 determination.
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.

                        PAPER-SECOND

1. Delocalised Covalent Bonding :
Aromaticity, anti-aromaticity; annulenes, azulenes,
tropolones, fulvenes, sydnones.
2. (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 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.
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. (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, 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:
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→π∗ and
π→π∗ 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.