1.1 Atomic
structure : Schrodinger wave equation, significance of yand
y2quantum numbers and their significance, radial and angular
probability, shapes of orbitals, relative energies of atomic orbitals as a
function of atomic number. Electronic configurations of elements; Aufbau
principle, Hunds multiplicity rule, Pauli
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exclusion principle.
1.2 Chemical periodicity :
Periodic classification of elements, salient characteristics of s,p,d and f
block elements. Periodic trends of atomic radii, ionic radii, ionisation
potential, electron affinity and electronegativity in the periodic table.
1.3 Chemical bonding : Types
of bonding, overlap of atomic orbitals, sigma and pi bonds, hydrogen and
metallic bonds. Shapes of molecules, bond order, bond length, V.S.E.P.R. theory
and bond angles. The concept of hybridization and shapes of molecules and ions.
1.4 Oxidation states and
oxidation number : Oxidation and reduction, oxidation numbers, common redox
reactions, ionic equations. Balancing of equations for oxidation and reduction
reactions.
1.5 Acids and bases :
Bronsted and Lewis theories of acids and bases. Hard and soft acids and bases.
HSAB principle, relative strengths of acids and bases and the effect of
substituents and solvents on their strength.
1.6 Chemistry of elements :
(i) Hydrogen: Its unique
position in the periodic table, isotopes, ortho and para hydrogen, industrial
production, heavy water.
(ii) Chemistry of s and p block
elements : electronic configuration, general characteristics properties,
inert pair effect, allotropy and catenation. Special emphasis on solutions of
alkali and alkaline earth metals in liquid ammonia. Preparation, properties and
structures of boric acid, borates, boron nitrides, borohydride (diborane),
carboranes, oxides and oxyacids of nitrogen, phosphorous, sulphur and chlorine;
interhalogen compounds, polyhalide ions, pseudohalogens, fluorocarbons and basic
properties of halogens. Chemical reactivity of noble gases, preparation,
structure and bonding of noble gas compounds.
(iii) Chemistry of d block
elements: Transition metals including lanthanides, general characteristic
properties, oxidation states, magnetic behaviour, colour. First row transition
metals and general properties of their compounds (oxides, halides and sulphides);
lanthanide contraction.
1.7 Extraction of metals :
Principles of extraction of metals as illustrated by sodium, magnesium,
aluminium, iron, nickel, copper, silver and gold.
1.8 Nuclear Chemistry :
Nuclear reactions; mass defect and binding energy, nuclear fission and fusion.
Nuclear reactors; radioisotopes and their applications.
1.9 Coordination compounds :
Nomenclature, isomerism and theories of coordination compounds and their role in
nature and medicine.
1.10 Pollution and its control
: Air pollution, types of air pollutants; control of air and water
pollution; radioactive pollution.
Section-B
(Organic Chemistry)
2.1 Bonding and shapes of organic
molecules : Electronegativity, electron displacements-inductive, mesomeric
and hyperconjugative effects; bond polarity and bond polarizability, dipole
moments of organic molecules; hydrogen bond; effects of solvent and structure on
dissociation constants of acids and bases; bond formation, fission of covalent
bonds : homolysis and heterolysis; reaction intermediates-carbocations,
carbanions, free radicals and carbenes; generation, geometry and stability;
nucleophiles and electrophiles.
2.2 Chemistry of aliphatic
compounds: Nomenclature; alkenes-synthesis, reactions (free radical
halogenation) -- reactivity and selectivity, sulphonation-detergents;
cycloalkanes-Baeyers strain theory; alkenes and alkynes-synthesis, electrohilic
addition reactions, Markownikovs rule, peroxide effects, 1- 3-dipolar addtion;
nucleophilic addition to electron-deficient alkenes; polymerisation; relative
acidity; synthesis and reactions of alkyl halides, alkanols, alkanals, alkanones,
alkanoic acids, esters, amides, nitriles, amines, acid anhydrides, a,
�-unsaturated ketones, ethers and nitro compounds.
2.3 Stereochemistry of carbon
compounds : Elements of symmetry, chiral and achiral compounds. Fischer
projection formulae; optical isomerism of lactic and tartaric acids,
enantiomerism and diastereoisomerism; configuration (relative and absolute);
conformations of alkanes upto four carbons, cyclohexane and dimethylcyclo-hexanes-their
potential energy. D, L-and R, S-notations
of compounds containing chiral centres; projection formulae-Fischer, Newman and
sawhorse-of compounds containing two adjacent chiral centres; meso and
dl-isomers, erythro and threo isomers; racemization and resolution; examples of
homotopic, enantiotopic and diasteretopic atoms and groups in organic compounds,
geometrical isomers; Eand Znotations.
Stereochemistry of SN1, SN2, E1 and E2 reactions.
2.4 Organometallic compounds
: Preparation and synthetic uses of Grignard reagents, alkyl lithium compounds.
2.5 Active methylene compounds
: Diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate-applications in
organic synthesis; tautomerism (keto-enol).
2.6 Chemistry of aromatic
compounds : Aromaticity; Huckels rule; electrophilic aromatic
substitution-nitration, sulphonation, halogenation (nuclear and side chain),
Friedel-Crafts alkylation and acylation, substituents effect; chemistry and
reactivity of aromatic halides, phenols, nitro-, diazo, diazonium and sulphonic
acid derivatives, benzyne reactions.
2.7 Chemistry of biomolecules :
(i) Carobhydrates : Classification, reactions, structure of
glucose, D, L-configuration, osazone formation; fructose and sucrose; step-up
step-down of aldoses and ketoses, and ther interconversions, (ii) Amino acdis :
Essential amino acids; zwitterions, isoelectric point, polypeptides; proteins;
methods of synthesis of a-amino acids. (iii) Elementary idea of oils, fats,
soaps and detergents.
2.8 Basic principles and
applications of UV, visible, IR and NMR spectroscopy of simple organic
molecules.
Section-C
Physical Chemistry)
3.1 Gaseous state : Deviation
of real gases from the equation of state for an ideal gas, van der Waals and
Virial equation of state, critical phenomena, principle of corresponding states,
equation for reduced state. Liquification of gases, distribution of molecular
speed, collisions between molecules in a gas; mean free path, speicific heat of
gases
3.2 Thermodynamics : (i)
First law and its applications: Thermodynamic systems, states and processes,
work, heat and internal energy, zeroth law of thermodynamics, various types of
work done on a system in reversible and irreversible processes. Calorimetry and
thermochemistry, enthalpy and enthalpy changes in various physical and chemical
processes, Joule-Thomson effect, inversion temperautre. Heat capacities and
temperature dependence of enthalpy and energy changes.
(ii) Second law and its
applications : Spontaneity of a process, entropy and entropy changes in
various processes, free energy functions, criteria for equilibrium, relation
between equilibrium constant and thermodynamic quantities.
3.3 Phase rule and its
applications : Equilibrium bewteen liquid, solid and vapours of a pure
substance, Clausius-Clapeyron equation and its applications. Number of
components, phases and degrees of freedom; phase rule and its applications;
simple systems with one (water and sulphur) and two components (lead-silver,
salt hydrates). Distribution law, its modifications, limitations and
applications.
3.4 Solutions : Solubility
and its temperature dependence, partially miscible liquids, upper and lower
critical solution temperatres, vapour pressures of liquids over their mixtures,
Raoults and Henrys laws, fractional and steam distillations.
3.5 Colligative Properties :
Dilute solutions and colligative properties, determination of molecular weights
using colligative properties.
3.6 Electrochemistry : Ions
in solutions, ionic equilibria, dissociation constants of acids and bases,
hydrolysis, pH and buffers, theory of indicators and acid-base titrations.
Conductivity of ionic solutions, its variation with concentration, Ostwalds
dilution law, Kohlrausch law and its application. Transport number and its
determination. Faradays laws of electrolysis, galvanic cells and measurements
of their e.m.f., cell reactions, standard cell, standard reduction potential,
Nernst equation, relation between thermodynamic quantities and cell e.m.f., fuel
cells, potentiometric titrations.
3.7 Chemical kinetics : Rate
of chemical reaction and its dependence on concentrations of the reactants, rate
constant and order of reaction and their experimental determination;
differential and integral rate equations for first and second order reaction,
half-life periods; temperature dependence of rate constant and Arrhenius
parameters; elementary ideas regarding collision and transition state theory.
3.8 Photochemistry :
Absorption of light, laws of photochemistry, quantum yield, the excited state
and its decay by radiative, nonradiative and chemical pathways; simple
photochemical reactions.
3.9 Catalysis :
Homogeneous and heterogeneous catalysis and their characteristics,
mechanism of heterogeneous catalysis; enzyme catalysed reactions (Michaelis-Menten
mechanism).
3.10 Colloids : The
colloidal state, preparation and purification of colloids and their
characteristics properties; lyophilic and lyophobic colloids and coagulation;
protection of colloids; gels, emulsions, surfactants and micelles.
Mains
1. Atomic structure
Quantum theory, Heisenbergs
uncertainity 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, factors affecting stability 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 homonuclear molecules: H2+, H2 to Ne2, NO, CO, HF, CN, CN�,
BeH2 and CO2. Comparison of valence bond and molecular oribtal theories, bond
order, bond strength and bond length.
3. Solid State
Forms of solids, law of constancy
of interfacial angles, crystal systems and crystal classes (crystallographic
groups). Designation of crystal faces, lattice structures and unit cell. Laws of
rational indices. Braggs law. X-ray diffraction by crystals. Close packing,
radious ratio rules, calculation of some limiting radius ratio values.
Structures of NaCl, ZnS, CsCl, CaF2, CdI2 and rutile. Imperfections in crystals,
stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors.
Elementary study of liquid crystals.
4. The gaseous state
Equation of state for real gases,
intermolecular interactions, liquefictaion of gases and critical phenomena,
Maxwells distribution of speeds, intermolecular collisions, collisions on the
wall and effusion.
5. Thermodynamics and statistical thermodynamics
Thermodynamic systems, states and
processes, work, heat and internal energy; first law of thermodynamics, work
done on the systems and heat absorbed in different types of processes;
calorimetry, energy and enthalpy changes in various processes and their
temperature dependence.
Second law of thermodynamics;
entropy as a state function, entropy changes in various process,
entropy�reversibility and irreversibility, Free energy functions; criteria for
equilibrium, relation between equilibrium constant and thermodynamic quantities;
Nernst heat theorem and third law of thermodynamics.
Micro and macro states; canonical
ensemble and canonical partition function; electronic, rotational and
vibrational partition functions and thermodynamic quantities; chemical
equilibrium in ideal gas reactions.
6. Phase equilibria and solutions
Phase equilibria in pure
substances; 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.
7. 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�voltameter, polarography, ampero-metry,
cyclic-voltametry, ion selective electrodes and their use.
8. Chemical kinetics
Concentration dependence of rate
of reaction; defferential and integral rate equations for zeroth, first, second
and fractional order reactions. Rate equations involving reverse, parallel,
consecutive and chain reactions; effect of temperature and pressure on rate
constant. Study of fast reactions by stop-flow and relaxation methods.
Collisions and transition state theories.
9. Photochemistry
Absorption of light; decay of
excited state by different routes; photochemical reactions between hydrogn and
halogens and their quantum yields.
10. Surface phenomena and catalysis
Absorption from gases and
solutions on solid adsorbents, adsorption isotherms,�Langmuir and B.E.T.
isotherms; determination of surface area, characteristics and mechanism of
reaction on heterogeneous catalysts.
11. Bio-inorganic chemistry
Metal ions in biological systems
and their role in ion-transport across the membranes (molecular mechanism),
ionophores, photosynthesis�PSI, PSII; nitrogen fixation, oxygen-uptake proteins,
cytochromes and ferredoxins.
12. Coordination chemistry
(a) Electronic configurations;
introduction to theories of bonding in transition metal complexes. Valence bond
theory, crystal field theory and its modifications; applications of theories in
the explanation of magnetism and electronic spactra of metal complexes.
(b) 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.
(c) Synthesis and structures of
metal carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl
compounds.
(d) 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.
13. General chemistry of �f� block elements
Lanthanides and actinides;
separation, oxidation states, magnetic and spectral properties; lanthanide
contraction.
14. Non-Aqueous Solvents
Reactions in liquid NH3, HF, SO2
and H2 SO4. Failure of solvent system concept, coordination model of non-aqueous
solvents. Some highly acidic media, fluorosulphuric acid and super acids.
2(a) Reaction mechanisms :
General methods (both kinetic and non-kinetic) of study of mechanism or organic
reactions illustrated by examples�use of isotopes, cross-over experiment,
intermediate trapping, stereochemistry; energy diagrams of simple organic
reactions�transition states and intermediates; energy of activation;
thermodynamic control and kinetic control of reactions.
(b) Reactive intermediates :
Generation, geometry, stability and reactions of carbonium and carbonium ions,
carbanions, free radicals, carbenes, benzynes and niternes.
(c) Substitution reactions :
SN1, SN2, SNi, SN1/, SN2/, SNi/ and SRN1 mechanisms;
neighbouring group participation; electrophilic and nucleophilic reactions of
aromatic compound including simple heterocyclic compounds�pyrrole, furan
thiophene, indole.
(d) Elimination reactions :
E1, E2 and E1cb mechanism; orientation in E2 reactions�Saytzeff and Hoffmann;
pyrolytic syn elimination�acetate pyrolysis, Chugaev and Cope
eliminations.
(e) Addition reactions :
Electrophilic addition to C�C and C=C; nucleophilic addition to C=O, C�N,
conjugated olefins and carbonyls.
3. Pericyclic reactions :
Classification and examples; Woodward-Hoffmann rules�clectrocyclic reactions,
cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1,
5] FMO approach.
4. Chemistry and mechanism of
reactions : Aldol condensation (including directed 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.
5. Polymeric Systems
(a) Physical chemistry of
polymers : Polymer solutions and their thermodynamic properties; number and
weight average molecular weights of polymers. Determination of molecular weights
by sedimentation, light scattering, osmotic pressure, viscosity, end group
analysis methods.
(b) Preparation and properties
of polymers : Organic polymers�polyethylene, polystyrene, polyvinyl
chloride, Teflon, nylon, terylene, synthetic and natural rubber. Inorganic
polymers�phosphonitrilic halides, borazines, silicones and silicates.
(c) Biopolymers : Basic
bonding in proteins, DNA and RNA.
7. Photochemist :
Photochemical reactions of simple organic compounds, excited and ground states,
singlet and triplet states, Norrish-Type I and Type II reactions.
8. Principles of spectroscopy
and applications in structure elucidation
(a) Rotational spectra�diatomic
molecules; isotopic substitution and rotational constants.
(b) Vibrational spectra�diatomic
molecules, linear triatomic molecules, specific frequencies of functional groups
in polyatomic molecules.
(c) Electronic spectra :
Singlet and triplet states. N�>p* and p�>p* transitions; application to
conjugated double bonds and conjugated carbonyls�Woodward-Fieser rules.
(d) Nuclear magnetic resonance
: Isochronous and anisochronous protons; chemical shift and coupling
constants; Application of H1 NMR to simple organic molecules.
(e) Mass spectra : Parent
peak, base peak, daugther peak, metastable peak, fragmentation of simple organic
molecules; a cleavage, McLafferty rearrangement.
(f) Electron spin resonance :
Inorganic complexes and free radicals.
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AKHAND PRATAP SINGH
