2013 paper 2 Question 1b

upsc previous year question paper analysis and solution.

CHEMISTRY
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 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, semiconductors.
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, 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.
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.
51
Government strives to have a workforce which reflects gender balance and women candidates are encouraged to apply.
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