Punjab Public Service Commission (PPSC)
Mains Examination Syllabus - 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
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 in H2 +, H2 , He2 + to Ne2, NO, CO, HF, and CN-; Comparison of
valence bond and molecular orbital theories, bond order, bond strength and bond
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 and CaF2; Stoichiometric and nonstoichiometric
defects, impurity defects, semi-conductors.
4. The Gaseous State and Transport Phenomenon:
Equation of state for real gases, inter-molecular
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.
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, a and b 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
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
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: 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 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.
Absorption of light; decay of excited state by different
routes; photochemical reactions between hydrogen and halogens and their quantum
11. Surface Phenomena and Catalysis:
Absorption 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 Compounds:
(i) Bonding theories 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-planer 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
unsaturation, oxidative addition reactions, insertion reactions, fluxional
molecules and their characterization; Compounds with metal-metal bonds and metal
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 Elements:
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 control and kinetic control of reactions.
(ii) Reactive Intermediates.—Generation, geometry,
stability and reactions of carbonium ions and carbanions, free radicals,
carbenes, benzynes and nitrenes.
(iii) Substitution Reactions.—SN1, SN2 and SNi
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 Elcb
mechanisms; orientation in E2 reactions— Saytzeff and Hoffmann; pyrolytic syn
elimination – Chugaev and Cope eliminations.
(v) Addition Reactions.—Electrophilic addition to C=C
and C C; nucleophilic addition to C=0, 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
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
polymers–polyethy-lene, polystyrene, polyvinyl chloride, teflon, nylon, terylene,
synthetic and natural rubber.
(ii) Biopolymers.—Structure of proteins, DNA and RNA.
5. Synthetic Uses of Reagents:
OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3,
LIAIH4, NaBH4, n-BuLi and MCPBA.
Photochemical reactions of simple organic compounds, excited
and ground states, singlet and triplet states, Norrish-Type I and Type II
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®p* and
p p*® transitions; 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 spinspin interaction and coupling constants.
(v) Mass Spectrometry.—Parent peak, base peak,
metastable peak, McLafferty rearrangement.
Courtesy : ppsc.gov.in