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SET (Chemical Science) Syllabus

CHEMICAL SCIENCES
The syllabus consists of two papers, as follows :
Paper II and Paper III will be of 75 minutes and 2½ hours duration respectiveoy. Paper II will be
of 100 marks and Paper III will be of 200 marks.

PAPER II
1. Structure and Bonding : Atomic orbitals, electronic configuration of atoms
(L-S coupling) and the periodic properties of elements, ionic radii, ionization potential, electron
affinity, electronegativity, concept of hybridization. Molecular orbitals and electronic
configuration of homonuclear and heteronuclear diatomic molecules. Shapes of polyatomic
molecules. VSEPR theory. Symmetry elements and point groups for simple molecules. Bond
lengths, bond angles, bond order and bond energies. Resonance. Types of chemical bond
(weak and strong). Intermolecular forces. Types of solids, lattice energy.

2. Acids and Bases : Bronsted and Lewis acids and bases. pH and pKa, acid-base concept in non-
aqueous media, SHAB concept, Buffer solutions.

3. Redox Reactions : Oxidation numbers, Redox potentials, Electrochemical series, Redox
indicators.

4. Introductory Energetics and Dynamics of Chemical Reactions : Law of conservation of energy.
Energy and enthalpy of reactions. Entropy, free energy, relationship between free energy change
and equilibrium. Rates of chemical reactions (first-and second-order reactions). Arrhenius
equation and Concept of transition state. Mechanisms, including S
N
1 and S
N
2 reactions, electron
transfer reactions, catalysis Colligative properties of solutions.

5. Aspects of s, p, d, f Block Elements : General characteristics of each block. Chemical principles
involved in extraction and purification of common metals. Coordination chemistry, Structural
aspects, isomerism, octahedral and tetrahedral crystal-field spliting of d-orbitals. CFSE,
magnetism and colour of transition metal ions. Sandwich compounds metal carbonyls and
metal clusters. Rare gas compounds, non-stoichiometric oxides. Radioactivity and transmutation
of elements.

6. IUPAC Nomenclature of Simple Organic and Inorganic Compounds.

7. Concept of Chirality : Recognition of symmetry elements and chiral structures,
R-S nomenclature, diastereoisomerism in acyclic and cyclic-systems, E-Z isomerism.
Conformational analysis of simple cyclic (chair and boat cyclohexanes) and acyclic systems,
Interconverison of Fischer, Newman and Sawhorse projections.

8. Common Organic Reactions and Mechanisms : Reactive intermediates. Formation and stability of
carbonium ions, carbenes, nitrenes, radicals and arynes. Nucleophilic, electrophilic, radical substitution,
addition and elimination reactions. Familiar name reactions : Aldol, Perkin, Stobbe,

Dieckmann condensations ; Hofmann, Schmidt, Lossen, Curtius, Beckmann and Fries
rearrangements, Reimer-Tiemann, Reformatsky and Grignard reactions. Diels-Alder reaction,
Claisen rearrangement, Friedel-Crafts reaction, Witting reaction. Routine functional group
transformations and inter-convertions of simple functionalities. Hydroboration, Oppenauer oxidation,
Clemmensen, Wolf-Kishner, Meerwein-Ponndorf Verley and Birch reductions.

9. Elementary principles and applications of electronic, vibrational, NMR, EPR, Mossbauer and mass
spectral techniques to simple structural problems.

10. Data Analysis : Types of erros, propogation of errors, accuracy and precision, least-square analysis,
average standard diviation.

PAPER III
1. Quantum Chemistry, Planck’s quantum theory, wave-particle duality, Uncertainty Principle,
operators and commutation relations, postulates of quantum mechanics and Schrodinger
equation, free particle, pastick in a box, degeneracy, harmonic oscillator, rigid rotator and the
hydrogen atom. Angular momentum including spin coupling of angular momenta including
spin-orbit coupling.

2. The variation method and pertubation theory : Application to the helium, atom, antisymmetry
and Exclusion Principle, Slater determinantal wave functions. Term symobols and spectroscopic
states.

3. Born-Oppenheimer approximation, Hydrogen molecule ion : LCAO-MO and VB treatments
of the hydrogen molecule, electron density, forces and their role in chemical binding.
Hybridisation and valence MO, of H
2
O, NH
3
and CH
4
. Huckel pi-electron theory and its
applications to ethylene, butadiene and benzene, idea of self-consistent fields.

4. Group theoretical representations and quantum mechanics : Vanishing of intergrals,
spectroscopic selection rules for vibrational, electronic, vibronic and Raman spectroscopy. MO
treatment of large molecules with symmetry.

5. Spectroscopy : Theoretical treatment of rotational, vibrational and electronic spectroscopy.
Principles of magnetic resonance, Mossbauer and Photoelectron spectroscopy.

6. Thermodynamics : First law of thermodynamics, relation between C
p
and C
v
; enthalpies of
physical and chemical changes, temperature depednence of enthaplies. Second law of
thermodynamics, entropy, Gibs-Helmholtz equation. Third law of thermodynamics and
calculation of entropy.

7. Chemical Equilibrium : Free energy and entropy of mixing, partial molar quantities, Gibbs-
Duhem equation. Equilibrium constant, temperature dependence of equilibrium constant, phase
diagram of one and two-component systems, phase rule.

8. Ideal and Non-ideal Solutions : Excess functions, activities, concept of hydration number,
activities in electrolytic solutions, mean ionic activity coefficient. Debye-Huckel treatment of
dilute electrolyte solutions.

9. Equilibria in Electrochemical Cells : Cell reactions, Nernst equation, application of cell
EMF measurements.

10. Surface Phenomena : Surface tension, adsorption on solids, electrical phenomena at interfaces
including electrokinetic micelles and reverse micelles; solutions. Applications of photoelectron
spectroscopy, ESCA and Auger spectroscopy to the study of surfaces.

11. Statistical Thermodynamic probability and entropy : Maxwell-Boltzmann distribution of
velocities, average, most probable and root-mean-square velocities. Maxwell-Boltzmann, Bose-
Einstein and Fermi-Dirac statistics. Partition function, rotational, translational, vibrational and
electronic partition functions for diatomic molecules, calculations of thermodynamic functions
and equilibrium constants. Theories of specific heat for solids.

12. Non-equilibrium Thermodynamics : Postulates and methodologies, linear laws, Gibbs
equation, Onsager reciprocal theory.

13. Reaction Kinetics : Methods of determining rate laws, Mechanisms of photo-chemical,
chain and oscillatory reactions. Collision theory of reaction rates, steric factor, treatment of
unimolecular reactions. Theory of absolute reaction rates, comparison of result with Eyring
and Arrhenius equations, ionic reactions, salt effect. Homogeneous catalysis and Michaelis-
Menten Kinetics; heterogeneous catalysis.

14. Fast Reactions : Study of kinetics by stop-flow technique, relaxation method, flash photolysis
and magnetic resonance method.

15. Macromolecules : Number-average and weight-average molecular weights. Determination of
molecular weights. Kinetics of polymerisation. Stereochemistry and mechanism of
polymerisation.

16 Solids : Dislocations in solids, Schottky and Frenkel defects. Electrical properties. Insulators
and semiconductors, band theory of solids, solid-state reactions.

17. Nuclear Chemistry : Radioactive decay and equilibrium. Nuclear reactions, Q value, cross-
sections, types of reactions. Chemical effects of nuclear transformations, fission and fusion,
fission products and fission yields. Radioactive techniques, tracer techniques, neutron activation
analysis, counting techniques such as G.M., ionization and proportional counters.

18. Chemistry of Non-transition Elements : General discussion on the properties of the non-
transition elements, special features of individual elements, synthesis, properties and structure
of their halides and oxides, polymorphism of carbon, phosphorus and sulphur. Synthesis,
properties and structure of boranes, carboranes, borazines, silicates, carbides, silicones,
phosphazenes, sulphur, oxyacids of nitrogen, phophorus, sulphur and halogens. Interhalogens,
pseudohalides and noble gas compounds.

19. Chemistry of Transition Elements : Coordination chemistry of transition metalions. Stability
constants of complexes and their determination, stabilization of unusual oxidation states.
Stereochemistry of coordination compounds. Ligand field theory, spliting of
d-orbitals in low symmetry environments. Jahn-Teller effect, interpretation of electronic spectra
including charge transfer spectra, spectrochemical series, nephelauxetic series. Dia-para-ferro
and antiferromagentism, quenching of orbital angular moments, spin orbit coupling. Inorganic
reaction mechanisms, substitution reactions, trans-effect and electron transfer reactions,
photochemical reactions of chromium and ruthenium complexes. Fluxional molecules. Iso and
heteropolyacids, metal clusters. Spin crossover in coordination compounds.

20. Chemistry of Lanthanides and Acitindes : Spectral and magnetic properties, use of lanthanide
compounds as shift reagents.

21. Organometallic Chemistry of Transition Elements : Synthesis, structure and bonding,
organometallic reagents in organic synthesis and in homogeneous catalytic reactions
(hydrogenation, hydroformylationn, isomerisation and polymerisation), pi-metal complexes,
activation of small molecules by coordination.

22. Topics in Analytical Chemistry : Adsorption, partition, exclusion, electrochromatography.
Solvent extraction and ion exchange methods. Application of atomic and molecular absorption
and emmision spectroscopy in quantitative analysis. Light scattering techniques including
nephelometry and Raman spectroscopy. Electroanalytical techniques, voltametry, cyclic
voltametry, polarography, amperometry, coulometry and conductometry. Ion-selective electrodes.
Anodic stripping voltametry, TGA, DTA, DSC and on-line analysers.

23. Bioiorganic Chemistry : Molecular mechanism of ion transport across membranes, ionophores.
Photosynthesis-PS-I, PS-II, nitrogen fixation, oxygen uptake proteins, cytochromes and
ferrodoxions.

24. Aromaticity : Huckel’s rule and concept of aromaticity : annulenes and heteroannulenes,
fullerenes. (C
60
)

25. Stereochemistry and Conformational Analysis : Newer methods of assymetric synthesis
(including enzymatic and catalytic nexus), enantio-and diastereo selective synthesis. Effects of
conformation on reactivity in acylic compounds and cyclohexanes.

26. Selective Organic Name Reactions : Favorskii reaction, Strok enamine reaction, Michael
addition, Mannich reaction, Sharpless asymmetric expoxidation, ene reaction, Barton reaction,
Hofmann Loffler-Freytag reaction, Shapiro reaction, Baeyer-Villiger reaction, Chichibabin
reaction.

27. Mechanisms of Organic Reactions : Labelling and kinetic isotope effects, Hamett equation,
σ–δ (sigma-rho) relationship, non-classical carbonium ions, neighbouring group participation.

28. Pericyclic Reactions : Selection rules and stereochemistry of electrocyclic reactions, cycloaddition
and sigmatrophic shifts, Sommelet-Hauser, Cope and Claisen rearrangements.

29. Heterocycles : Synthesis and reactivity of furan, thiophene, pyrrole, pyridine, quinoline,
isoquinoline and indole. Skraup synthesis, Fischer indole synthesis.

30. Reagents in Organic Synthesis : Use of following reagents in organic synthesis and fuctinal
group transformations-Complex metal hydride. Gilman’s reagent, lithium, dimethylcuprate,
lithim, disopropylamide (LDA) dicyclohexylcarbodimide, 1, 3-dithiane (reactivity umpolung).
Trimethy, silyl iodide, tri-n-butyltin hydride, Woodward and Prevost hydroxylation, osmium
tetraoxide, DDQ, selenium dioxide, phase transfer catalysts, crown ethers and Merrifield resin.
Peterson’s synthesis, Wilkinson’s catalyst, Baker’s yeast.

31. Chemistry of Natural Products : Familiarity with methods of structure elucidation and
biosynthesis of alkaloids, terpenoids, steroids, carbohydrates and proteins, Conformations
of proteins and nucleic acids.

32. Bioorganic Chemistry : Elementary structure and function of biopolymers such as proteins
and nucleic acids, Genetic code, Mechanism of enzyme action.

33. Photochemistry : Principles of energy transfer, cis-trans isomerization, Paterno-Buchi reaction,
Norrish Type I and II reactions, photoreduction of ketones, di-pi-methane rearrangement,
photochemistry of arenes.

34. Spectroscopy : Combined applications of mass, UV-VIS, IR and NMR spectroscopy for
structural elucidation of compounds.

SAMPLE QUESTIONS
PAPER II
1. The total number of permitted electrons in a 4f orbital is
(A) 10,
(B) 6,
(C) 14,
(D) 2.
Ans. C

2. Which one of the following is a molecular solid ?
(A) NaCl,
(B) Phosphorus,
(C) Diamond,
(D) Iron.
Ans. B

3. Thr chiral molecules among the following are
( i ) 1, 1-Dimethylcyclopropane.
( ii) cis-1, 2-dimethylcyclopropane.
(iii) trans-1, 2-dimethylcyclopropane.
(A) All three, (B) (ii) and (iii), (C) only (ii), (D) only (iii).
Ans. D

PAPER III
1. The standard heat of hydrogenation of propane in the reaction
CH
2
= CHCH
3
(g) + H
2
(g) = C
3
H
8
(g) is - 124 kJ/mol.
The standard heat of combustion of propane in the reaction
C
3
H
8
(g) + 5O
2
(g) = 3CO
2
(g) + 4H
2
O (1) is - 2220 kJ/mol.
Calculate the standard heat of combustion of propane.
Given : {H
2
(g) + 0.5O
2
(g) = H
2
O(l), AHo = -285.8kJ/mol}
2. Match the following Hammet σ values :
(a) m - Me
( i ) + 0.78
(b) p - Me
(ii) – 0.27
(c) p - NO
2
(iii) + 0.12
(d) p - COCH
3
(iv) – 0.07
(e) m - OMe
(v) + 0.50
(f) p - OMe
(vi) – 0.17
3. (a) Predict whether the following reactions will proceed via inner, sphere or
outer sphere mechanism. Give the products also.
( i ) [Fe (CN)
6
]4 + [Ir Cl
6
]2– →
( ii) [Co (NH
3
)
5
NCS]2+ + [Cr (H
2
O)
6
]2+ →
(b) Name the factors that determine the magnitude of crystal field splitting