Civil Service Mains Optional Chemistry

CHEMISTRY


PAPER - I

1. Atomic Structure:
Heisenberg’s uncertainty principle,
Schrodinger wave equation (time indepen-dent); Interpretation of wave function, par-ticle 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 com-pounds, lattice energy, Born-Haber cycle;
covalent bond and its general characteris-tics, polarities of bonds in molecules and
their dipole moments; Valence bond
theory, concept of resonance and reso-nance energy; Molecular orbital theory
(LCAO method); bonding in H
2
+, H
2
, He
2
+
to
Ne2, NO, CO, HF, and CN
–
; Comparison of
valence bond and molecular orbital theo-ries, 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, calcula-tion of some limiting radius ratio values;
Structures of NaCl, ZnS, CsCl and CaF
2
;
Stoichiometric and nonstoichiometric de-fects, impurity defects, semi-conductors.

4. The Gaseous State and Transport Phe-nomenon:
Equation of state for real gases, inter-mo-lecular interactions and critical pheno-mena and liquefaction of gases, Maxwell’s
distribution of speeds, intermolecular col-lisions, collisions on the wall and effusion;
Thermal conductivity and viscosity of ideal
gases.

5. Liquid State:
Kelvin equation; Surface tension and sur-face energy, 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 vari-ous processes, entropy–reversibility and
irreversibility, Free energy functions; Ther-modynamic equation of state; Maxwell re-lations; Temperature, volume and pressure
dependence of U, H, A, G, C
p and C
v
á and
â; J-T effect and inversion temperature;
criteria for equilibrium, relation between
equilibrium constant and thermodynamic
quantities; Nernst heat theorem, introduc-tory idea of third law of thermodynamics.

7. Phase Equilibria and Solutions:
Clausius-Clapeyron equation; phase dia-gram for a pure substance; phase equilib-ria in binary systems, partially miscible liq-uids–upper and lower critical solution tem-peratures; partial molar quantities, their sig-nificance and determination; excess ther-modynamic functions and their determina-tion.

8. Electrochemistry:
Debye-Huckel theory of strong electrolytes
and Debye-Huckel limiting Law for vari-ous equilibrium and transport properties.
Galvanic cells, concentration cells; elec-trochemical 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, cur-rent density; overpotential; electro-analyti-cal techniques: Polarography,
amperometry, ion selective electrodes and
their uses.

9. Chemical Kinetics:
Differential and integral rate equations for
zeroth, first, second and fractional order
reactions; Rate equations involving re-verse, parallel, consecutive and chain re-actions; 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 react-ions between hydrogen and halogens and
their quantum yields.

11. Surface Phenomena and Catalysis:
Absorption from gases and solutions on
solid adsorbents, Langmuir and B.E.T. ad-sorption isotherms; determination of sur-face 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 Compounds:
(i) Bonding theories of metal complexes;
Valence bond theory, crystal field theory
and its modifications; applications of theo-ries in the explanation of magnetism and
electronic spectra of metal complexes.
(ii) Isomerism in coordination compounds;
IUPAC nomenclature of coordination com-pounds; stereochemistry of complexes
with 4 and 6 coordination numbers; che-late effect and polynuclear complexes;
trans effect and its theories; kinetics of sub-stitution reactions in square-planer com-plexes; thermodynamic and kinetic stabil-ity of complexes.
(iii) EAN rule, Synthesis structure and re-activity of metal carbonyls; carboxylate
anions, carbonyl hydrides and metal ni-trosyl compounds.
(iv) Complexes with aromatic systems, syn-thesis, structure and bonding in metal ole-fin 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 clus-ters.

14. Main Group Chemistry:
Boranes, borazines, phosphazenes and
cyclic phosphazene, silicates and sili-cones, Interhalogen compounds; Sulphur
– nitrogen compounds, noble gas com-pounds.

15. General Chemistry of ‘f’ Block Ele-ments:
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.

2.  (i)  Reaction Mechanisms:General
methods (both kinetic and non-kinetic) of
study of mechanism of organic reactions:
isotopic method, cross-over experiment,
intermediate trapping, stereochemistry;
energy of activation; thermodynamic con-trol and kinetic control of reactions.
(ii)  Reactive Intermediates:Generation,
geometry, stability and reactions of car-bonium ions and carbanions, free radicals,
carbenes, benzynes and nitrenes.
(iii)Substitution Reactions:SN1, S
N
2 and
S
N
i mechanisms; neighbouring group par-ticipation; electrophilic and nucleophilic
reactions of aromatic compounds includ-ing heterocyclic compounds–pyrrole, fu-ran, thiophene and indole.
(iv)  Elimination Reactions:E1, E2 and
E1cb mechanisms; orientation in E2 reac-tions–Saytzeff and Hoffmann; pyrolytic  syn
elimination – Chugaev and Cope elimina-tions.
(v) Addition Reactions: Electrophilic ad-dition to C=C and C=C; nucleophilic  addi-tion to C=0, C=N,  conjugated olefins and
carbonyls.
(vi)Reactions and Rearrangements:(a)
Pinacol-pinacolone, Hoffmann, Beck-mann, Baeyer–Villiger, Favorskii, Fries,
Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.
(b) Aldol condensation, Claisen conden-sation, Dieckmann, Perkin, Knoevenagel,
Witting, Clemmensen, Wolff-Kishner,
Cannizzaro and von Richter reactions;
Stobbe, benzoin and acyloin condensat-ions; Fischer indole synthesis, Skraup syn-thesis, 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
30 www.employmentnews.gov.in Employment News 11 - 17 February 2012
sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO
approach.

4. (i)Preparation and Properties of Poly-mers:  Organic polymers–polyethy-lene,
polystyrene, polyvinyl chloride, teflon, ny-lon, terylene, synthetic and natural rubber.
(ii)  Biopolymers:Structure of proteins,
DNA and RNA.
5. Synthetic Uses of Reagents:
OsO
4
, HIO
4
, CrO
3
, Pb(OAc)
4
, SeO
2
, NBS,
B
2H6, Na-Liquid NH
3, LiAlH
4,NaBH4,
n-BuLi
and 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 elu-cidation:
(i)Rotational: Diatomic molecules; isoto-pic substitution and rotational constants.
(ii) Vibrational: Diatomic molecules, linear
triatomic molecules, specific frequencies
of functional groups in polyatomic mol-ecules.
(iii)  Electronic:Singlet and triplet states;
n Ý  π* and  π  π*Ýtransitions; application to
conjugated double bonds and conjugated
carbonyls–Woodward-Fieser rules;
Charge transfer spectra.
(iv)Nuclear Magnetic Resonance (
1H
NMR):  Basic principle; chemical shift and
spin-spin interaction and coupling con-stants.
(v)  Mass Spectrometry:Parent peak, base
peak, metastable peak, McLafferty rear-rangement