DEPARTMENT OF CHEMISTRY
UNIVERSITY OF ALLAHABAD
ALLAHABAD
M.Sc. (Previous & Final)
Syllabus & Instruction Manual
Syllabus for M.Sc. (Previous)
FIRST PAPER
INORGANIC CHEMISTRY
1. Molecular Symmetry—Symmetry elements and operations, multiplication of symmetry operations,
symmetry groups, symmetry considerations in H2O, CO2, NH3, H2O2, BCI3, SiF4, XeF4, PCI5.
2. Chemical Bonding—Molecular orbital theory for polyatomic molecules multicenter bonding, bonding in
election deficient molecules. Weak interactions-hydrogen bonding, van-der Waals forces : dipole-dipole,
dipole induced dipole and London dispersion forces.
3. Solid State—Theory of metals-free electron, valence bond and molecular orbital theories. Conductors,
insulators and semi-conductors. Super conductivity. Alloys and intermetallic compounds. Hume-Rothery
rules. Lattice defects in ionic crystals-stoichiometric and non-stoichiometric defects.
Section B
4. Coordination Chemistry—Theories of the co-ordinate linkage : Valence bond, crystal field, igand field
and molecular orbital theories. Crystal field splittings of d-orbitals in octahedral, trigonal bipyramidal,
sqarue pyramidal, tetragonal and square planar fileds. Crystal field stabilization energy (CFSE). M.O.
energy level diagram for octabedral and tetrahedral complexes (with s bonding only). Spectrochmical
series. Electronic absorption spectra of transition metal complexes. Orgel diagrams for d1, d4, d6 and d9
configurations with D ground state. Jahn-Teller effect. Stabilization of less familiar oxidation states of
transition metals via coordination.
5. Stability of Metal Complexes in Solution—Stepwise and overall stability constants. Thermodynamic
correlations. Determination of stability constants job’s method of continuous variation and mole ratio
method. Factors affecting the stability constants-Chelation and its importance.
6. Metal Corbonyls and Nitrosyls—Mononuclear and polynuclear corbonyls and their structures. Nature
of M-C-O bonding. Preparation of metal corbonyls and their reactions. Metal nitrosyls-bonding and
structure. Metal carbonyl-nitrosyl complexes.
Section - C
7. Soft and Hard Acids and Bases—Pearson’s concept. SHAB priciple and its applications.
8. Inorganic Spectroscopy—(i) Number of microstates and term symbols for gaseous free atoms and
ions. Spin-orbit coupling in free ion terms. Hunds rules. Splitting of spectroscopic terms of p2 and d2
configurations.
(ii) Principles of Electronic Spectroscopy-Franck-Condon principle, selection rules, band intensities and
vibronic coupling Band width. Different types of electronic transitions and molar absorption coefficient.
9. Chemistry of f-Block Elements—Comparative study of lanthanides and actinides with special
reference to electronic structure. Oxidatin state, coordination number, structure, stereochemistry and
magnetic and spectral properties. General chemistry of actinides including E.M.F. diagrams. Extraction
and metallurgy of thorium and uranium. Tehcnical productin of plutonium. Separation of transamericium
elements.
SECOND PAPER
ORGANIC CHEMISTRY
120 Hrs (4Hrs/week)
Nature of Bonding in Organic Molecules
10 Hrs
Cross conjugation, Steric inhibition of resonance, bonding in fullerenes. Aromaticity in benzenoid and non
benzenoid compounds, alternant and non-alternant hydrocarbons, Huckels rule, energy level of pmolecular orbitals, annulenes, anti-aromaticity, homo-aromaticity, PMO approach.
Stereochemistry
15 Hrs
Conformational analysis of cycloalkanes-disubstituted cyclohexanes, decalins effect of conformation on
reactivity, conformation of sugars.
Elements of symmetry, chirality, molecules with more than one chiral center, threo and erythro isomers,
methods of resolution, optical purity, enantiotopic and diasterotopic atoms, group and faces,
stereospecific and stereoselective synthesis, Asymmetric synthesis. Optical activity in the absence of
chiral carbon (biphenyls, allenes and spiranes), chirality due to helical shape.
Reaction Mechanism : Structure and Reactivity
12 Hrs.
Types of mechanisms, types of reactions, thermodynamic and kinetic requirements, kinetic and
thermodynamic control, Hammond’s postulate, Curtin-Hammett principle. Potential energy diagrams,
transition states and intermediates, methods of determining mechanisms, isotope effects (Product
analysis : Kinetic and stereo chemical studies).
Generation, structure, stability and reactivity of carbocations, carbanions, free radicals carbenes and
nitrenes.
Effect of structure on reactivity-reasonance and field effects, steric effect, quantitative treatment. The
Hammett equation and linear free energy relationship, substituent and reaction constants. Taft equation.
Aliphatic Nueleophilic Substitution
The SN2, SNI, mixed SNI and SN2 and SET mechanisms.
15 Hrs
The neighbouring group mechanism, neighbouring group participation by P and S bonds, anchimeric
assistance.
Classical and nonclassical carbocations, phenonium ions, norbornyl system, common carbocation
rearrangement. The SNi mechanism.
Nucleophilic substitution at an allylic, aliphatic trigonal and vinylic carbon. Reactivity effects of substrate
structure, attacking nucleophile, leaving group and reaction medium, phase transfer catalysis, ambident
nucleophile and regioselectivity.
Aliphatic Electrophilic Substitution
15 Hrs
Bimolecular mechanisms, - SE2 and SE1. The SE1 mechanism, electrophilic substitution accompanied by
double bond shifts. Effect of substrates, leaving group and the solvent polarity on the reactivity.
Aromatic Electrophilic Substitution
6 Hrs
The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso
attack. Diazonium coupling Vilsmeier reaction, Gatterman-Koch reaction.
Aromatic Nucleophilic Substitution
5 Hrs
The SNAr, SNI benzyne and SRNI mechanisms. Reactivity-effect of substrate structure, leaving group and
attacking nucleophile. The von Richter, Sommelet-Hauser and Smiles rearrangements.
Free Radical Reactions
8 Hrs
Types of free radical reactions, free radical substitution mechanism, mechanism at an aromatic substrate,
neighboring group assistance, reactivity for aliphatic and aromatic substrates at a bridgehead, Reactivity
in the attacking radicals. The effect of solvent on reactivity.
Allylic halogenation (NBS), oxidation of aldehydes to carboxylic acids, auto oxidation, coupling of alkynes
and arylation on aromatic compounds by diazonium salts. Sandmeyer reation. Free radical
rearrangement. Hunsdiecker reaction.
Addition to carbon-carbon Multiple Bonds
7 Hrs
Mechanisitc and sterochemical aspects of addition reaction involving electrophiles, nucleophiles and free
radicals, ragio and chemoselectivity, orientation and reactivity. Addtiion to cyclopropance ring.
Hydrogenation of double and triple bonds, hydrogenation of aromatic rigns, Hydroboration, Michael
reaction, Sharpless asymmetric epoxidation.
Addition to Carbon-Hetero Multiple Bonds
12 Hrs
Mechanism of metal hydride reduction of saturated and unasaturated carbonyl compounds, acids, esters
and nitriles. Addition of Grignard reagents, organozinc and organolithium reagents to carbonyl and
unsaturated carbonyl compounds, Witting reaction. Mechanism of condensation reactiosn involving
enolates-Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions. Hydrolysis of
esters and amides, ammonolysis of estters.
Elimination Reactions
5 Hrs
The E2, E1 and E1cB mechanisms and their spectrum, orientation of the double bond. Reactivity-effects of
substrate structures, attacking base, the leaving group and the medium.
Mechanism and orientation in pyrolytic elimination.
Pericyclic Reactions
Molecular orbital symmetry, Frontier orbitals of etyhylene, 1, 3-butadiene, 1, 3, 5-hexatriene and allyl
system. Classification of pericyclic reactions, Woodward-Hoffmann correlation diagrams. FMO and PMO
approach. Electrocyclic reactions-conrotatory and disrotatory motions, 4n, 4n+2 and allyl systems.
Cycloadditions-antrafacial and suprafacial additions. 4n and 4n+2 systems, 2+2 addition of ketenes, 1, 3
dipolor cycloadditions and cheleotropic reactions.
THIRD PAPER
PHYSICAL CHEMISTRY
Section - A
Molecular Spectra—Basic concepts of molecular spectroscopy
Characterization of electromagnetic radiations Regions of the Sectrum.
Classification
of
spectra.
Rotation Spectra—Rigid and non-rigid rotation spectra-selection rule Centrifugal distortion. Isotopic Shift.
Spectra of polyatomic molecules. Rotational function. Experimental techniques.
Vibration Rotation Spectra—Simple harmonic oscillator. Vibrational energy. Anharmonicity. Principle of
vibration-rotation spectra. Selection rule. PQR branches. Vibration in polyatomic molecules. Effect of
nuclear spin. Isotopic shift. Group frequency. Experimental techniques.
Quantum Chemistry
Origin of quantum theory. Black body radiation. Wien and Rayleigh Jeans laws. Planck’s law and energy
of harmonic oscillator.
Postulates of quantum mechanics. Three dimensional time independent schrodinger wave equation
Eigen functions and eigen values particle. Normalization and orthogonality conditions. One dimensional
harmonic oscillator. Tunnel effect. Eigen function and eigen valud of H-atom. (Solutions not required).
Shapes of s, p and d orbitals.
Approximate Methods—Variation principle and its applications to ground state H-atom. Radial and
angular distribution curves for H-atom.
Section B
Thermodynamics
Nernst heat theorem and its application to non-condensed systems. Statements of the third law of
thermodynamics. Derivation of unattainability of absolute zero. The relationship between entropy constant
and Nernst chemical constant. Determination of entropy from the third law using the correction due to gas
imperfections. Consequences of the third law (o-, p- hydrogen and liquid He-II) Verification of the third
law. Applications of the third law.
Statistical Mechanics
Quantum states and complexions. The combinatory rule. System with definite total energy. Degeneracy
of energy levels Probability and most probable distribution. Indistinguishability. Maxwell-Boltzmann
statistics, partition function. Translational, rotational, vibrational and electronic partition functions. Internal
energy and heat capacity in terms of partition function.
Chemical Kinetics
Thermodynamic formulation of rate constant. Comparison of collision of absolute reaction rate theories.
Calculations of transmission coefficient. Transition srtate theory in solution. Primary and secondary salt
effets in the light of mechanistic tests. The theory of absolute reactions between atoms and reactions
between molecules in terms of partiion function. Influence of ionic strength and deielectric constant.
Explosive reactions. Acid-base catalysis with special reference to protolytic and prototropic mechanisms.
Section C
Chemistry of Macromolecules
Introduction to type of polymers. Step polymerization. Kinetics of step polymerization. Statistical approach
to Gelation. Molecular weight distribution in linear polycondenstion (Derivation of size distribution).
Molecular weight averages. Methods of determining the molecular weight by osmotic pressure, light
scattering, sedimentation and viscosity methods.
Electrolytes
Limitation of Arrhenius theory of electrolytic dissociation. Role of solvent and inter-ionic forces. Activities
and activity coefficients. Determination of activity coefficient. Debye-Huckel theory of the structure of
dilute ionic solution. Charge density and electrical potential. Properties of ionic cloud. Activity coefficient
from Debye-Huckel theory. Limiting law and its verification. Thermodynamic properties of electrolytic
solutions and Debye-Hyckel theory. Weak electrolytes and Debye-Huckel theory to more concentrated
solutions. Partial molar quantities of electrolytic solutions. Determination of partial molar volume.
Solid State
The Crystal system. Properties of Crystals. Basic laws regarding the forms of crystals. The structure of
crystal. Crystal lattices. Symmetry. Lattices and unit cells. Miller indices. X-ray diffraction studies of
crystals. The Laue and Bragg methods of crystal analysis. X-ray analysis of NaCI. Determination of
Avogadrao number from X-ray analysis.
FOURTH PAPER
ANALYTICAL CHEMISTRY
Time : 3 Hrs.
Max. Marks : 75
Section A
1. Data Handling : Significant Figures, Rounding off figures. Accuracy and Precision; Standard Deviation;
Fitting data to a straight line. Errors Determinate and indeterminate errors, error curves, propagation of
errors.
2. Hydrogen ion exponent, Buffer solutions; Pseudobuffers.
3. Principles of volumetric methods
chelatometric titrations. Theory of indicators.
: Acid-base redox, precipitation, complexometric and
4. Principles and scope of gravimetric methods : Precipitation equilibria, condition for analytical
precipitation-coprecipitation and post precipitation.
5. Organic reagents in inorganic analysis : Dimethylgyoxime, Cupferron, Cupron, Salicyladoxime, anitroso, b-hapthol, Anthranilic acid, Acetyle acetone. Spot tests for common cations; Ringoven method.
Section B
1. Principles of spectrochemcial analysis : Beer-Lambert’s law, deviation from law and its applications.
Photoelecrtric colorimeters and spectrophotmeters : Instrumentation and applications.
2. Potentiometric, Conductometric, Amperometric titrations and Coulometric titrations and their
applications.
3. Distribution law Principles and applications of solvent extraction technique.
4. Chromatrography : Adsorption, Partition and Ion-exchange chromatography-theory and application in
analytical chemistry.
5. Measurements and significance of dissolved oxygen (DO). Biological oxygen Demand (BOD) and
Chemical Oxygen Demand (COD).
Section C
1. Gas Analysis : Sampling, gas volumetric methods of analysis determination of H2O2, evaluation of
pyrolusite determination of available chlorine in bleaching powder. Sources and sampling of polluted
water and air.
2. Semimicro determination of carbon, hydrogen, sulphur and nitrogen in organic compounds.
3. Methods of determination of functional groups : Carboxyl including amides and esters, O-acetly, Nacetly, C-methyl, N-methly, alkoxyl and hydroxy.
4. Spot test identification of functional groups : Hydroxyl, carboxylic, nitro, nitroso, azo and amino.
5. Analysis of oils and fats.
CHEMISTRY PRACTICAL
Time 18 Hrs. (3 Days)
Max Marks 150
1. Qualitative analysis of inorganic mixture for seven radicals only (including interfering radicals,
insolubles, and two rare elements.
21 Marks
2. Quantitative separation and estimation of individual metal component from binary mixture solution
(either both component gravimetricaslly or one component gravimetrically and other one volumetrically).
(15 + 14) = 29 marks
1. Qualitative Analysis
25 Marks
Separation, purification and identification of compounds of binary mixture (two solids or one liquid and
one solid) using TLC, the column chromatography and chemical tests. I.R. spectra to be used or
functional group identification.
2. Organic synthesis
Acylation : Acetylation of cholestral and separation of cholesteryl acetate by column chromatography.
Oxidation : Adipic acid by chromic acid, oxidation of cyclohexanol.
Aldol condensation : Dibenzal acetone from benzaldehyde.
Sandmeyer reaction : p-Chloro toluene from p-toluidine.
Cannizzaro reaction : p-Chlorobenzaldehyde as substrate.
Friedel Crafts reaction : B-Benzoyl propionic acid from succinic anhydride and benzene.
Aromatic electrophilie substitutions : Synihesis of p-bromoanline.
Rearrangement : Synthesis of benzilic acid by benzil-benzilic acid rearrangement. Pinacolpinacolone rearrangement in Benzpinacol.
The product may be characterized by spectral technique.
3. Quantitative Analysis
Estimation of amines/phenols using bromate bromide solution.
Determination of Iodine and Saponification values of an oil sample.
4. Analytical Experiments :
(i) Compelxometric (EDTA) titrations
(ii) Estimation of sulphur in an Organic Compound.
(iii) Estimation of nitrogen in an Organic Compounds.
(iv) Estimation of saponification value of an ester.
(v) Estimation of iodine value of a fat or an oil.
(vi) Colorimetric determination of copper, iron and phosphate.
40 marks
15 marks
5. Physical Experiments :
(i) Determination of specific rotation of dextrose, and the concentration of unknown dextrose solution
(20% to 2.5%).
(ii) Determination of molal elevation constant (Kb) of water using urea/sucrose as solute, the
concentration of given unknown urea/sucrose solution (using graphical and direct method), and the
molecular weight of a non-volatile solute.
(iii) Determination of the velocity constant of the reaction between acetone and iodine catalysed by
HCI/H2SO4 and the study of the kinetics of decomposition of sodium thiosulphate by mineral acids (HCI).
(iv) Detemrination of the molecular mass of volatile liquids (and their binary mixtures) by victor Meyer
method (CHCI3/CI2/C6H6 and similar compounds).
(v) Determination of cell constant of a conductivity cell, and the specific conductivity and equivalent
conductitivy of an electrolytic solution at different concentrations (KCI, NaCI, Na2SO4 etc.)
(vi) Determination of the quilibrium constant of the reaction (KI + I2 = KI3) and the formula of the
complex formed between the cupric ion and ammonia by distribution method.
7. Record and viva-voce
(25+15) = 40 marks
Students shall be given six experiments to be completed in 18 hours (3 days) inorganic mixture : 3 hours,
of 21 marks; inorganic quantitative estimations : 6 hours, or 29 marks; organic preparation (of 15 marks)
and identification of an organic compound (of 10 marks); 3 hours, of 25 marks; analytical experiment; 3
hours, of 15 marks; and physical experiment; 3 hours of 20 marks) in the annual practical examination
comparising 40 marks of records and viva-voce.
(Total MM : 150)
Syllabus for M.Sc. Final Chemistry
(Effective from 2000-2001 session)
There are following Four specialized courses :
1. Inorganic Chemistry
2. Organic Chemistry
3. Physical Chemistry
4. Analytical Chemistry
A student can opt for one of the above courses and has to study all the three theory papers of the opted
course along with the Fourth Theory Paper which is Elective. There are at present Five Elective Papers—
A, B, C, D and E. Thus, a student had to study Four theory papers of 75 marks each.
Each specialized course has Practicals of 150 marks. A student is required to get atleast 36 percent
marks in theory and 36 percent marks in practicals in order to get declared as passed.
PHYSICAL CHEMISTRY
FIRST PAPER
(Kinetic Theory of Gases, Liquid State, Electrolytic Solutions and Solid State)
Time : 3 Hrs.
Max Marks : 75
Kinetics Theory of Gases and Transport Properties
Distribution law (Barometric formula). Sedimentation equilibrium. Maxwell’s law of distribution of velocity
and energy. Maxwell’s law and Gaussian density function. R.M.S., mean and most probable velocities.
Collision frequency. Collisin between like and unlike molecules. Triple collision. Viscoisty, thermal
conductivity and diffusion coefficient of gases (quantitative treatement). Mean free path.
LIQUID STATE
Vapour pressure, compressbility viscosity and sound velocity. Internal pressure and its determination.
Significance of internal pressure, solubility parameter and cohesive-energy-density. Free volume of
liquids and its determination. Application of free volume and its relation with energy and heat of
vaporization.
Partition function of a liquid. Equation of state in terms of partition function. Outline of the theory of liquid
state. Simple cell theory (Eyring equation) and cell model theory of Lennard-Jones and Devonshire.
Eyring’s free volume theory of liquid viscosity. Effect of pressure on viscosity.
Thermodynamic functions of ideal and non-ideal liquid mixtures. Partial molar properties of liquid
mixtures. Determination of partial molar volume and partial molar enthalpy.
SOLID STATE
Classification of solids. Bonding in solids, covalent, metallic, ionic and molecular crystals. Lattice energy
of crystals. Cohesive energy. Conduction in solids and superconductance. Electronic structures of solids.
Free electron theory. Fermi-gas theory and band theory of solids. Metals, semi-conductors and insulators.
Intrinsic extrtinsic p-tyipe and n-type semi-conductors.
Dissolution of An Ionic Crystal.—Quatitative treatment of ion-solvent interactions. Born model. Entropy
and enthalpy of interactions.
ELECTROLYTIC SOLUTIONS
The triumph and limitations of Debye-Huckel theory of activity coefficients. Electrical potential and mean
activity coefficient in the case of ionic clouds with finite sized ions. The ion size parameter and
comparison of the finite-ion-size model with experiment.
Asymmetry and electriphoretic effects. Stoke’s law and Walden product. Debye-Huckel-Onsager
equation. Conductance ratio and the Onsager slope. Verification of Debye-Huckel-Onsager equation.
Conductivity of weak electrolytes and conductance in nonaqueous solvents. Modifications of DebyeHuckel-Onsager equation. Fuoss-Onsager and other equations. Wien and Debye-Fakenhagen effects.
Viscosity of electrolyte solutions-Jones-Dole equation and significance of A and B coefficients.
Ion association in an electrolyte solution. Formation of pairs, triplets etc. The probability of finding
oppositely charged ions near each other. Bjerrum theory of ion association.
SECOND PAPER
(Spectroscopy, Magnetochemistry and Macromoleculs)
Time : 3 Hrs.
Max. Marks : 75
MAGNETOCHEMISTRY
Magnetic susceptibility and its determination, Susceptibility equivalents.
Pascal’s law and its applications. Diamagnetism of elements, compounds and ions. Langevin’s theory of
paramagnetism. Curie’s law. Weiss molecular field theory of paramagnetism, Curie-Weiss law.
Determination of Curie point. Orbital and spin moments, electrons and multielectons systems. Magnetic
property of complex compounds in relation to their structure. Bohr magnetion. L-S and J-J couplings.
SPECTROSCOPY
Electronoic spectra of molecules, Born-Oppenheimer approximation. Franck-Condon principle. Rotational
fine structure of Electronic-Vibration transitions. Predissociation spectra. Molecular photoelectron
spectroscopy (PES). Quantum theorty of Raman Spectra. Stokes and Antistokes lines. Rotation and
vibration Raman spectra. Mutual exclusion principle. Laser Raman spectra. Theory of NMR relaxation
process and chemical shift. The coupling constant. Nuclear spin interaction. Principle of ESR. Magnetic
moment of electron and splitting factor. Hyper-fine splitting and double reasonance in ESR. Mossbauer
spectroscopy and its principle. Origin of line width. Isomer shift. Quadropole effects. Application of
Raman, ESR, NMR and Massbaur spectra. C13 NMR spectroscopy, p31 NMR spectroscopy STM
(Scanning Tunneling Microsocpy)-theory and application. AES (Auger Electron Spectroscopy), EELS
(Electron Energy Lom Spectroscopy).
MACROMOLECULES
Kinetic of initiation retardation, chain polymerization and ionic polymerization (anionic and cationic),
Copolymerisation (with special reference to monomer reactivites ratios). Coordination polymerization.
Degradation of polymers (oxidative, chemical and photolytic). An introduction to conducting polymers.
Polyelectolyes.
THIRD PAPER
(Intermoleuclar Forces, Chemical Kinetic, Non-Equilibrium Thermodynamics, Electrolysis and
Polarization)
Time : 3 Hrs.
Max Marks : 75
INTERMOLECULAR FORCES
Nature of intermolecular forces. Various contributions of intermeolecular forces. London theory of
dispersion forces. Intemrolecular potentials for polar and non-polar molecules. Potential parameters of L-J
potential and evaluation of second virial coefificients. Partition function of imperfect gas and Virial
equation of State. Critical constants and L-J parameter.
CHEMICAL KINETICS
Kinetics of fast reactions : Techniques of study of fast reactions with reference to stop flow, T-Jump, Flash
photolysis and relaxation phenomena.
Kinetics of oscillating reactions with special reference to Belousov-Zhabotinskii mechanism (B-Z
mechanism).
Study of Mechanism of Catalysis.—Kinetics and mechanism of reactions on surface. Mechanism of
surface reactions. Uni and bi-molecular surface reactions. Langmuir-Hinshelwood mechanism. LangmuirRideal mechanism. Inhibition of surface reactions. Absolute reaction rate theory of surface reactions.
Comparisoon of homogeneous and heterogenous reactions. Study of equilibrium constant and steady
state treatment for Arrhenius and Vant Hoff’s complexes.
Mechanistic Study of Ion-Dipolar Molecular Reactions :
(a) Oxidation of sugars by K3Fe (CN)6 and Cu+2 in alkaline medium.
(b) Oxidation of organic molecules by K3Fe (CN)6 and Ce (IV).
(c) Platinum group Os (VIII), Ru (III) etc. Catalysed oxidation of organic molecules by K3Fe (CN)6 Ce (IV)
etc. Influence of substitutents on reaction rates (inductive and electromeric effects). Linear free
energy relationships. Taft equation. Compensation effect. Hemmett acidity functions.
NON-EQUILIBRIUM THERMODYNAMICS
Thermodynamic functions for non-equilibrium states. Postulates and methodology. Linear laws. Gibbs
equation. Entropy production and entropy flow. Phenamenological equations. Microscopic reversibility
and Onsager’s reciprocity relations. Transformations of the generalized fluxes and forces. Electrokinetic
phenomena. Diffusion. Electric conduction. The stationary non-equilibrium states. States of minimum
entropy production.
ELECTROLYSIS AND POLARIZATION
Mechanism of electrode reactions. Overpotential. The current-potential relation. The Tafel equation.
Hydrogen overvoltage and decomposition potential. Butler-Volmer equation. H2-Evolution mechanism.
M.SC. (FINAL) PHYSICAL CHEMISTRY PRACTICAL
Time : 14 Hours (2 Days)
Max Marks : 150
1. Elementary programming in Basic with specific applications to computation in practical
exercises.
2. Viscosity of polymer solutions and calculation of radius of gyration, end to
distance and
stiff parameter.
3. Determination of viscosity of lubricating and full oils.
4. Determination of flash points of petroleum products.
5. Potentiometric titration of strong acid and strong base.
6. Potentiometric titration of weak acid and strong base.
7. Potentiometric titration of KCI, KBr and KI and mixtures against AgNO3.
8. Potentiometric estimation of Fe (SO4). (NH4)2 SO4 Soln and determination of redox potential.
9. Determination of freezing point depression constant.
10. To study the effect of dilution on freezing point depression.
11. Determination of activity coeff. Cryoscopically.
12. Establishing the formula of K2HgI4 and KMnO4 cryoscopically.
13. Determination of molecular weight of some electrolytes and non-electrolytes
cryoscopically and calculation of Vant Hoff’s factor and osmotic coefficient.
14. Conductometric titration of mixtures of acid and base.
15. Verification of Ostawald’s dilution law.
16. To test the validity of D-H-O equation.
17. Determination of bassicity of and acid.
18. Titration of acid versus base using pH meter and calculation of pKa value of an acid.
19. Determination of variation of referactive index with composition for mixture of
A
B.
20. Kinetics of reaction between K3Fe (CN)6 and sugars in alkaline medium.
21. Kinetics of reaction between copper sulphate and sugars in alkaline medium.
22. Kinetics of reaction between N-bromosuccinimide/or chloramines-T and aminoacids
uncatalysed and/or catalysed by Ru (III) chloride in acidic/or alkaline media.
23. Kinetics of reaction between K2S2O8 and KI.
24. Determination of magnetic susceptibility.
and
INORGANIC CHEMISTRY
FIRST PAPER
(Molecular Symmetry and Structural Methods in Inorganic Chemistry)
Time : 3 Hrs.
Max Marks : 75
1. Group Theory and Molecular Symmetry.—Definitions and theorems of group theory. Symmetry point
groups, multiplication tables of simple point groups. Systematic identification of point groups of inorganic
molecules, representation of groups, character tables and its applications. Symmetry consideration in
coordiantioan compounds. Symmetry aspects of molecular orbital theory and ligand filed theory.
2. Quantum Mechanical Treatment of Odd Electron Systems.—Hydrogen molecule ion. Method of
Directed Valence Bond-Hybridized bond eigen functions-sp, sp2 and sp3, molecular orbital equivalent of
hybridization, delocalization, resonance, molecular orbital equivalent of resonance.
3. Magnetochemistry.—Types of magnetic behaviour. Van Vleck equation and its application. Temperature
dependence of magnetic susceptibility, Temperature independent paramagnetism (T.I.P.). Antisotropy in
magnetic susceptibility. Pascal constants, diamagnetic correction and calculation of effective magnetic
moment. Orbital contribution to the magnetic moment, spin-orbit coupling. Methods for magnetic
susceptibility measurement. Magnetic properties of : mononuclear weak filed 3d metal complexes with A,
E and T crystal field terms and spin-paired complexes of cubic filed summetry, complexes of heavier
metal ions, binuclear metal complexes involving antiferromagnetic exchange interaction. High spin-low
spin cross-over. Temperature dependence of magnetic moment.
4. N.M.R. Spectroscopy.—Basic principles of nuclear magnetic resonance. Bloch equations. Linewidth and
relaxation processes. Chemical shift. Nuclear spin-spin splitting. Factros affecting chemical shift and spinspin coupling constant, and its applications in structural determination of inorganic molecules. Contact
shift, pseudo contact shift and their applicantions in structural studies of paramagnetic complexes. Shift
reagents. NMR studies of fluxional molecules. FT NMR Spectroscopy.
5. E.S.R. Spectroscopy.—Basic principles of electron spin resonance. Line width and relaxation
mechanisms. Electron spin-nuclear spin hyperfine splitting. Isotropy and anisotrpy in g and A values.
Covalent bonding and ligand nuclear superhyperfine splitting. Zero filed splitting and Kramer’s
adegeneracy. ESR applications to electronic and structural studies of simple inorganic species and
transition metal comaplexes (3d1 and 3d9 systems) including single crystals and excited triplet states.
6. Mossbauer Spectrosocpya.—The Mossbauer effect. Isomer shifts, quadrupole and magnetic
interactions. Applications of Mossbauer spectroscopy to 57Fe and 119Sn compounds.
7. Vibration and Rotation Spectrosocpy.—Principles and appalications of I.R. and Raman spectroscopy
in structural elucidation of simple inorganic and coordination compounds. Comparison of Raman and I.R.
spectroscopy. FT-IR spectroscopy. Laser-Raman spectroscopy. Microwave spectroscopy. Determination
of bond lengths. Dipole moment-its theory and application to molecular structure.
8. Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Photoelectron Spectroscopy
(XPS).—Basic principles of EXAFS and XPS, spectral features and their applications to simple inorganic
molecules and transition metal complexes.
9. Thermal Analysis.—Fundamentals of thermogravimetry (TGA). Differential thermal analysis (DTA) and
their applications. Derivatography.
SECOND PAPER
(Inorganic Reaction Mechanism, Organometallic Chemistry, Inorganic Polymers and Metal
Alkoxides)
Time : 3 Hrs.
Max Marks : 75
1. Mechanism of Inorganic Reactions.—Inert and labile complexes. Possible mechanism of ligand
replacement reactions SN1, SN2 and SN1 CB mechanisms. Ligand displacement reactions in octahedral
complexes-Acid and base hydrolysis. Mechanism of ligand displacement reactions in squre planar
comaplexes Trans effect. Mechanism of isomerization and recemization reactions.
2. Electron Transfer and Metal ION Catalysis.—Mechanism of electroan transfer reactins (outer sphere
and inner sphere mechanisms). Two electron transfers. Electron exchange reaqctions. Metal ion
catalysis. Palladium catalyzed reqactions. Phtochemical reactions. Solar energy conversion and storage
through coordination compounds.
3. Organometallic Compounds.—Major types of transition metal-to-carbon bonds excluding complexes.
Classification of organometallic compounds based on hapticity and polarity of M-C bond, nomenclature
and genral characteristics. General methods of preparation and important reactions of transition metal
complexes of unsaturated hydrocarbons such as alkenes, alkynes, allyl, cyclopentatdiene and arene.
Structure and bonding in Zeise’s salt, ferrocene and dibenzene chromium Fluxional molecules.
4. Organometallics and Transition Metal Complexes as Catalyst in the synthesis of Organic
Compounds.—General idea of important catalytic steps Coordinative unsaturation. Reactiosn of
coordinated ligands and coordinated molecular oxygen, template synthesis. Oxidative addition, reductiveelimination and migration (insertion) reactions. Hydrogenation of alkenes using Wilkinson’s catalysts,
carbonylation of methanol to acetic acid (Monsanto process), palladium catalyzed oxidation of ethylene
(Wacker process). Polymerization of alkenes (Ziegler-Natta synthesis).
5. Inorganic Free Radicals.—Free radicals and intermediate species in inorganic reactions. Detection of
free radicals. Free radicals induced reactions. General chemistry of OH0, OH02, Br+ and I+.
6. Reactions in Nonaqueous Solvents.—Classification of solvents. Characteristic properties of an ionising
solvent. Reactions in liquid ammonia, liquid sulphurdioxide, liquid hydrogen fluoride, dimethyl formamide
(DMF), dimethyl sulphoxide (DMSO) and dioxane. Chemistry of fused salt systems.
7. Inorganic Polymes.—Classification, general properties. Inorganic polymers, based oan Boron, Silicon,
Phophorus and Sulfur. Coordination polymers.
8. Metal Clusters, Polyanions and Metal Alkoxides.—(a) Metal-metal multiple bonds in binuclear
compounds. Trinuclear, tetranuclear and octahedral clusters. Synthesis and bonding in metal clusters, (b)
Polymolybdates and polytungstates, (c) Metal alkoxides Preparation. Properties structural characteristics
and industrial applications.
THIRD PAPER
(Coordination Chemistry and Bio-inorganic Chemistry)
Time : 3 Hrs.
Max Marks : 75
1. Typical Complexes.—Acquaintance with different types of ligands and their complexes containing
N,P,As,O,S, and halogens as donors. Polydentate lignads, macrocylic ligands. Ambidentate ligands, tipod
ligands. Dioxygen superoxo, peroxo and dinitrogen as ligands. Cyanide, isocyanide, bipyridine and ophenanthroline and polyamines. Inophores and their ion-complexes-Valinomycin and Nigercin groups.
Crown ethers and cryptates.
2. Metal Complexes in Solution.—Determination of stability constant by (a) potentiomety-pH titration
technique (Bjerrum’s and Irving-Rossotti’s methods) and ion selective electrode methods. (b)
spectrophotmetry, (c) polarography, (d) solvent extraction, and (c) ion-exchange methods. Mixed-ligand,
mixed-metal and polynuclear complexes.
3. Electrochemical Studies of Metal Complexes.—Principles of differential pulse polarography, cyclic
voltammetry, anodic and cathodic strippings and their applications in the study of metal complexes.
4. Ligand Field and Molecular Orbital Theories.—M.O. energy level diagrams of octahedral tetrahedral
and square plannar coamplexes. Effect of pi bonding on the energy of t2g orbitals and on Dq.
Experimental evidences for metal-ligand orbital overlap.
5. Electronic Spectra of Coordination Compounds.—Orgel diagrams for high spin d2 d3, d7 and d8
configurations and assignments of electronic transitions. Tanabe-Sugano diagrams. Effect of sistortions
(Jahn-Teller effect and spin-orbit coupling) upon d-d transitions. Recah parameters (B and C and CordonShortley parameters (F0F2 and F4) and Calculatioan of 10 Dq.
and 0 (for high-spin octahedral Cr (III)
and (Ni) (II) and tetrahedral V (III) and Co (II) complexes). Nephelauxetic effect and Nephelauxetic series.
Charge transfer spectra.
6. Complexes of Biological Signivicance.—Metal complexes of amino acids and peptides. Metal
complexes of nucleic acid bases, nucleosides and nucleotides. Metal complexesof porphyrins and
phthalocyanins. Synthetic model oxygen carrier complexes and model dinitrogen complexes. Phophates
and bioenergetics. Phosphorylation and phosphorolysis. Adenine nucleotides in metabolic energy
transfer. Oxidation of glucose and the role of phosphate.
7. Role of Metal IONS in Biological Systems.—Essential and trace metal ions. Metal ions storage and
transport (Na, K, Ca, Mg, Fe, Cu and Zn)-Ferritin and Transferrin. Metal ion toxicity and its cure by
chelating agents. Pharamacological activity and metal chelates. Carcinogenic metals, carcinogenic and
carcinostatic ligands.
8. Metallo Proteins and Metallo Enzymes.—Function, Electronic Structure, bonding and Sterochemistry of
the Active Site. (1) Natural Oxygen Carrying Proteins-Haemoglobin, Myoglobin, Hemerythrins and
Hemocyanin, (2) Electron Transport Proteins (a) Iron-Sulfur Proteins-Rubredoxin and Ferrodoxins, (b)
Cytochromes (types a b and c).
Redox Enzymes.—(a) Mo-Containing Enzymes-Nitrogenase, Xanthine Oxidase, Sulphite oxidase and
Nitrate reductase, (b) Iron-Containing Enzymes-Cytochrome-c oxidase, Catalases, Peroxidases, (c)
Copper-Containing Enzymes-Super oxide dismutase (SOD) Bovine Superoxide dismutase (BOD),
ascorbic acid oxidase, and (d) Zinc-Containing Enzymes-Carboxy-peptidase A and B, Carbonic anydrase
and Urease. Vitamines B12 and B6- Chlorophills.
M.SC. (FINAL) INORGANIC CHEMISTRY PRACTICAL
Time : 14 Hours (2 days)
1. Preparations (Complex compounds) :
(a) Ferric alum (ferric ammonium sulphate)
(b) Tetraammine copper (II) sulphate
(c) Potassium trioxalatochromate (III)/aluminate (III)/ferrate (III)
(d) Silver/copper tetraiodomercurate (II)
(e) Sodium hexanitritocobaltate (III)
(f) Prussian blue
(g) Ammonium diamminetetrathiocyanato-chromate (III)
(h) Pentammine chloro-nitritocobalt (III) chloride
(i) Hexaureachromium (III) chloride trihydrate
Max Marks : 150
30
2. Instrumentation :
40
(a)
(b)
(c)
(d)
(e)
Colorimetry and spectrophotometry
Potentiometry
Conductometric titrations
Flame photometry
Ring oven technique
3. Chromatography :
(a)
(b)
(c)
(d)
(e)
(f)
40
Paper chromatography
Adsorption chromatography
Thin layer chromatography
Paper electrophoresis
Solvent extraction
Ion exchange
4.
Exercise involving principles and procedures of qualitative and quantitative analysis.
5. Application of statistical treatments and approaches in inorganic analysis.
6. Records and viva-voce
(25+15) = 40
Students are required to carry out three experiments. One preparatiaon of an inorganic complex
compoiund one exercise based on an instrument, and a nona-instrumental (chromatographic) exercise.
ANALYTICAL CHEMISTRY
FIRST PAPER
(Theoretical Aspects and General Procedure)
Time : 3 Hrs.
Max. Marks : 75
1. Statistical methods in aquantitative analysis; Evaluation and interpretation of analytical data. Normal law
of error and its application of finite sample, confidence level and confidence interval.
2. Tests of significance, the “t” test’ the “F” test, the x2 (chi-squares) (chisquasres) test, distribution normalcy
test.
3. Regression analysis; methods of least squares the correlation coefficient, Rejection of observations; the
“Q” test.
4. Graphic presentation of equilibrium data; acid base and complexes formation.
5. Activity and activity coefficients. Equilibriuam constants in analysis. Numerical problems based on
equilibrium constant, acid base equilibrium, solubility equilibrium, complexation equilibria.
6. Applications of reaction rate and mechanisms with special reference to catalytic reactions, non enzymatic,
enzymatic and reactions involving complexes.
Section B
7. Sampling principle and methods.
8. Safety in the laboratory; General Safety Rules, Waste Disposal, Incompatible Chemicals, Precautions
with potentially dangerous chemicals.
9. Determination of moisture by Karl Fischer’s method and active hydrogen by Zerwindtinoff’s method.
10. Micro and semi-macro determination of oxygen, phosphorous, arsenic and halogens (including fluorine) in
organic compounds.
11. Micro and semi-macro determination of functional groups like amino, nitro, azo, carbonyl, unsaturation,
acetylenic hydrogen, sulphonic acid sulphide sulphamide and peroxides.
12. Acquaintance with commercial analysis of food materials like milk, butter, tea, sugar and vitamins.
SECOND PAPER
(Electroanalytical, Separation, Radiochemical and other methods)
Time : 3 Hrs.
Max. Marks : 75
Section A
1. Potentiometry; Electrode potential Indicator electrodes, Electrodes of first and secnd kind; galvanic cell,
formal potential, over voltage, half reaction and their combination reversible and irreversible reactiosn
membrane potential and glass electrode.
2. Chemical sensors; Ion-Selective electrodes gas sensing electrodes and enzymes electrodes.
3. Conductometry; Conductometric and high frequency titration.
4. Voltametry : The voltametric cell, the current-voltage curve, the supporting electrolyte; polarography-the
dropping mercuery electrode, residual current, maxima; The Ilkovic Equation, Inorganic and Organic
polarography.
5. Anodic stripping voltametry, cyclic voltametry, amperometry.
6. Coulometry : Coulometric titrations, controlled potential electrtolysis-applications and Electrogravimetry.
Section B
7. Principles and applications of extraction techniques : Quantitative treatments of extraction equilibria,
solvent extraction of metals, analytical separations, multiple batch extraction, counter current distribution.
Synergistic extraction.
8. Size exclusion chromatography and electrophoriesis.
9. Gas chromatography and High performance Liquid Chromatography.
10. Ion-exchange chromatography
chromatography.
:
Ion-exchange
equilibria,
Properties
on
ion-exchangers.
Ion
11. Analytical applications of magnetic succeptibility, Polarimetry and Polarising microscope.
12. Radiochemical methods; Proportional Geiger and Scintillation counters, counting errors and corrections,
Activation analysis, Applications of radioactive tracers in analysis; Isotopic dilution method; Radiometric
titrations.
THIRD PAPER
(Spectroscopic Technique)
Time : 3 Hrs.
Max. Marks : 75
Section A
1. Principles of electromagnetic radiation, atomic spectra, molecular spectra, dissipation of absorbed
radiation.
2. Methodology and instrumentartion of spectrophotometry in visible, ultraviolet and infra red regions,
spectrometric error, deviation froam Beer’s law, analysis of mixtures.
3. Spectrophotmetric methods for investigations of composition and stability of metal complexes in
solutions.
4. Fluorimetry : Principles of fluorescence, practical considerations, relationship between concentration and
fluorescence intensity, fluorescence instrumentation-fluorometers and spectrofluorometers.
5. Principles and applications of Infrared spectrophotometry and Raman spectrosocopy.
6. Turbimetry and nephelometry and their appalications.
Section B
7. Atomic spectrometric methods : Emission spectroscopy; Plains Emission Spectrometry
Plasma Emission Spectrometry and their applications.
and
8. Atomic Absorption Spectrophotometry : Principles, sources, burners, flames, interferences,
sample preparation-internal standards and Standard Addition Calibrations. Appalications.
9. X-ray methods : Diffraction, absorption and fluorescence.
10. NMR and ESR Spectrosocpy : Principles, Instrumentation and Applications.
11. Mass spectrometry-Principles, Basic idea of techniques and applications.
12. Basic ideas of computer based analytical chemistry.
M.SC. FINAL ANALYTICAL CHEMISTRY PRACTICAL
Time : 14 Hrs.
1.
2.
3.
4.
5.
6.
Max. Marks : 150
(Which include 20 marks for project work)
Separation techniques : Ion-exchange and solvent extraction.
Chromatography : Paper, TLC, Electrophoriesis.
Sepectrophotometry.
Electrometric techniques : pH, Conductometry and Ion-Selective Electrodes, Polarography.
Flamephotometry and Atomic Absorption Sepectrometry
FTIR
ORGANIC CHEMISTRY
FIRST PAPER
(Reaction Mechanism and Reagents)
Time : 3 Hrs.
Max. Marksa : 75
I. Molecular Rearrangements
1. Migration to electron deficient carbon atom.— Pinacole-Pinacolone rearrangement, WagnerMeerweian rearrangement, Tiffenev-Demjanov ring expansion, Dienone-Phenol rearrangement, Benzil
Benzilic acid rearrangement, Favorski rearrangement.
2. Migration to electron deficient nitrogen atom.—Wolf, Hofmann, Curtius, Losen, Schmidt, Beckmann
rearrangement.
3. Migration to electron deficient oxygen atom.—Baeyer-Villiger rearrangement.
4. Stevens, Witting, Neber rearrangements and rearrangement of amino ketones.
II. Sigmatropic rearrangement
6 Hrs.
Suprafacial and antarafacial shift of H, sigmatropic shifts involving carbon moieties, retention and
inversion of configuration, (3, 3) and (5, 5) sigmatropic rearrangements, detailed treatment of Claisen
and Cope-rearrangements. Fluxional tautomerism, Aza-Cope rearrangements. Introduction to Enereactins. Simple problems on pericyclic reactions.
III. Organic Photcohemistry
7 Hrs.
1. Photochemistry of Carbonyl Compounds :
Photochemistry of enones, hydrogen abstraction, rearrangements of
cyclohexadienones, photochemistry of p-benzoquniones.
,
unsaturated ketones and
2. Photochemistry of unsaturated system :
9 Hrs.
Olefins, cis-trans isomerisation, dimerisation, hydrogen abstraction and additions.
Acetylenes-dimerisation, Dienes-photochemsitry of 1, 3-butadiene (2+2) additions leading to cage
structures, photochemistry of cyclohexadienes. Photochemistry of aromatic compounds-exited state of
benzene and its 1, 2 and 1, 3-shifts, Photo-Fries rearrangement, Photo-Fries reaction of anilides,
photosubstitution reaction of benzene derivatives. Photolysis of nitride esters and Barton reaction.
IV. Oxidation
7 Hrs.
Introduction—Different oxidative processes.
Hydrocarbons-alkenes, aromatic, rigns, saturated, C-H groups (activated and unactivated). Alcohols,
diols, aldehydes, ketones and carboxylic acids. Amines, hydrazines, and sulphides.
Oxidations with ruthenium tetraoxide, iodobenzene diacetate and thallium (III) nitrate.
V. Reduction
7 Hrs.
Introduction. Different reductive process.
Hydrocarbons : alkanes, alkenes, alkynes and aromatic rings.
Carbonyl compounds : aldehydes, ketones, acids and their derivatives.a
Epoxides : Hydrogenolysis.
VI. Metallocenes, Non-benzenoid Aromatics and Polycyclic Aromatic Compounds 9 Hrs.
General considerations, synthesis and reactins of some representative compounds.
VII. Organometallic Reagents
20 Hrs.
Principle, preparations, properties and appalications of the following, in organic synthesis with
mechanistic details :
Group I and II metal organic compounds.
Li, Mg, Hg, Cd, Zn, and Ce compounds.
Transition metals : General reactisn given by transition metals with ligands.
Cu, Pd, Ni, Fe, Co, Rh, Cr and Ti compounds.
SECOND PAPER
(Spectroscopy and Natural Products)
Time : 3 Hrs.
Max. Marks : 75
1. Nuclear Magnetic Resonance Spectroscopy
10 Hrs.
PMR Spectroscopy chemical exchange, effect of deuteration, complex spin-spin interaction between two,
three four and five nuaclei (first order spectra), virtual coupling. Stereochemistry, hindered rotation,
Karplus curve-variation of coupling constant with dihedral angle. Simplication of complex spectra-nuclear
magnetic double resonance, contact shift reagents, solvent effects. Fourier transform technique, Nuclear
Overhauser Effect (NOE). Resonance of other nuclei : F and P.
II. Carbon-13 NMR Spectroscopy
3 Hrs.
General considerations, chemical shift (aliphatic, olefinic, alkyne, aromatic, heteroaromatic and carbonyl
carbon), coupling constants.
Two dimension NMR spectroscopy : COSY, NOESY, DEPT, INEPT, APT and INADEQUATE techniques.
III. Mass Spectrometry
8 Hrs.
Introduction ion production-EI, CI, FD and FAB, factors, affecting fragmentation, ion analysis, ion
abusndance. Mass spectral fragmentation of organic compounds, common functional groups, molecular
ion peak, metastable peak, Mc-Lafferty rearrangement. Nitrogen rule. High resolution mass
spectrometery. Examples of mass spectral fragementation of organic compounds with respect of their
structuere determination.
Solution of Structural problems by joint application of UV, IR, NMR 1H &
(7Hrs.)
13
C) and mass spectroscopy
IV. Optical Rotary Dispersion (ORD) and Circular Dichroism (CD)
Definition, deduction of absolute configurastion, octant rule for ketones.
(a)
(b)
(c)
(d)
3Hrs.
V. Bio-synathesis of Natural Products
8 Hrs.
The acetate hypothesis, poly B-Ketoacids, their aldol type cyclisastion, meta-orientation of hydroxy
group in naturally occurring phenols. Biogensis of fatty acids.
Isoprene rule, mevalonic acid from acetyl Co-enzyme A. Biogenesis of mono sesqui, di and triterpenes.
Shikimic acid pathway for biogenesis of aromatic ring.
General biogenesis of alkaloids.
VI. Terpenoids and Carotenoids
9 Hrs.
Classification, general methods of structure determination, isoprene rule. Structure determination,
stereochemistry, synthesis of the following representative molecules : citral,
terpenol, farnesol,
santonin, abietic acid, -carotene, sqauralenes, -amyrin and menthol. For structure elucidation emphasis
is to be placed on the use of spectral data wherever possible.
VII. Alkaloids
10 Hrs.
Definition and physiological action, general methods of structure elucidation, degradation, classification
based on nitrogen heterocyclic ring, role of alkalodis in plants. Structure, stereochemistry and synthesis of
the following : Ephedrine, (+) nicotine, atropine, quinine and morphine. For structure elucidatioan
emphasis is to be placed on the use of spectral data wherever possible.
VIII. Steroids
10 Hrs.
Basic skeleton Diel’s hyadrocarbon and stereochemistry, structure determination and synthesis of
cholesterol, bile acids and rosterone, testosterone, estrone, progesterone, aldosterone. Obsynthesis of
steroids. For structure elucidation emphasis is to be placed on the use of spectral data wherever possible.
IX. Prostaglandins
Occurrence, nomenclature, classification and physioligcal effects. Synthesis of PGE2 and PGF2a
3 Hrs.
X. Plant Pigments
6 Hrs.
General methods of structure determination, synthesis of Apigenin, Quercetin Cyanidin Hirsutitin.
Quercetin-3 glucoside, Diazein cyanidine-7 arabinoside and Emodine. For structure elucidation emphasis
is to be placed on the use of spectral data wherever possible.
THIRD PAPER
(Medicinal Chemistry & Biomolecules)
Time : 3Hrs.
Max. Marks : 75
I. Enzymes
8 Hrs.
Introduction and historical perspective, chemical and biological catalysis, remarkable properties of
enzymes like catalytic power, specificity and regulation. Nomenclature and classification, extraction and
purification. Fisher’s lock and key and Koshland’s induced fit hypothesis, concept and identification of
active site by the use of inhibitors, affinity labeling and enzyme modification by site-directed mutagenesis.
Enzyme kinetics, Michaelis-Menten and Lineweaver-Burk plots, reversible and irreversible inhibition.
II. Mechanism of Enzyme Action
6 Hrs.
Transition-State theory, orientation and steric effect, acid-base catalysis, covalent catalysis, strain or
distortion. Examples of some typical enzyme mechanisms for chymotrypsin, ribonuclease, lysozyme and
carboxypeptidase A.
III. Biotechnological Applications of Enzymes
8 Hrs.
Large-scale production and purification of enzymes, techniques and methods of immobilization of
enzymes, effect of immobilization on enzyme activity, application of immobilized enzymes, use of
enzymes in food and drink industry-brewing and cheese-making, syrups of com starch, enzymes as
targets for drug design. Clinical uses of enzymes, enzymes therapy, enzymes and recombinant DNA
technology.
IV. Drugs
2 Hrs.
Relationship of chemical structure and biological activities and theories of drug action.
(i) Antineoplastic Agents
4 Hrs.
Introduction, cancer chemotherapy, role of alkylating agents and antimetabolites in treatement of cancer.
Mention of carcinolytic antibiotics and mitoptic inhibitors. Synthesis of mechlorethamine,
cyclophosphamide, melphalan, uracil, amustards, and 6-merrcaptopurine products.
(ii) Cardiovascular Drugs
6 Hrs.
Cardiovascular diseases, drug inhibitionof peripheral sympathetic function. Direct acting arteriolar dilators.
Synthesis of amyl nitrate, hydrolaxine verapamil, methyldopa and diazoxide propanol.
(iii) Local Anti-infective Drugs
7 Hrs.
Antiubercular drugs and Antimalerial drugs : Introduction and general mode of action. Synthesis of
sulphonamides, ciprofloxaction norflocation , dapsone amino salicylic acid, ethionamide, ethambutal,
griseofulvin, chloroquin and primaquin.
(iv) Psychoactive Drugs
6 Hrs.
CNS depressants general anaesthetics, hypnotics, sedatives, anti-anxiety drugs, benzodiazipies mental
diseases. Antipsychotic drugs. Synthesis of diazepam, alprazilam trimethadione barbiturates and
glutethimide.
(v) Antihistaminic Agents
2 Hrs.
Anatazotine diphenhydramins
(vi) Antibiotics :
10 Hrs.
Synthesis of penicillin G, chloramphenicol, cephalosporin, tetracycline and streptomycin.
V. Vitamins :
8 Hrs.
Detailed study of chemistry of Vit. B1, Vit. C1 Pantothenic acid Biotin (Vitamin H) and a-tocopherol
(Vitamin E). Biolaogical action of vitamins.
VI. Harmones
5 Hrs.
Insect harmones : Pheromones and Juvenile harmones Plant harmones : Gibbrellins
VII. Pyrethroids and Rotenones
3 Hrs.
Synthesis and reactions of Pyrethroids and Rotenones.
(For structure elucidation, emphasis is to be placed on the use of parameters wherever possible).
M.SC. (FINAL)-ORGANIC CHEMISTRY PRACTICAL
1. Qualitative Analysis
Separation purification and identification of the components of a mixture of three organic compounds
(three solids or two liquids and one solid, two solids and one liquid). Using TLC for checking the purity of
the separated compound, chemical analysis, IR, PMR and mass spectra.
2. Multi-step synthesis of Organic Compounds
The exercises should illustrate the use of organic reagents and may invlve purificatioan of the products by
chromatographic techniques.
Photochemical reaction: Benzophenon Benzpinacol Benzpinacolone.
Beckmann Rarrangement : Benzanilide from benzene Benzene
oxime benzarrlide
Benzophenone
Benzophenone
Benzilic acid rearrangement : Benzilic acid from benzoin
Benzoin Benzil Benzilic acid
Synthesis of heterocyclic compounds.
Skraup synthesis : Preparation of quinoline from aniline.
Fischer-Indole synthesis : Preparation of 2 phenylindole from phenylhydrazine
Enzymatic synthesis :
Enzymatic reduction : Reduction of ethylacetoacetate using Baker’s yeast to yield enantiomeric excess of
S (+)ethytl-3-hydryybutanoate and determine its optical purity.
Biosynthesis of ethanol from sucrose.
Synthesis using microwaves : Alkylation of diethyl malonate with benzyl chloride.
Synthesis using phase transfer catalyst : Alkylation of diethyl malonate or ethyl acetoacctate with an alkyl
halide.
3. Extraction of Organic Compounds from Natural Sources
1. Isolation of caffeine from tea leaves.
2. Isolation of nicotine dipcirate from tobacco.
3. Isolation of lycopene from tomatoes.
4. Isolation of b-carotene from carrots.
5. Isolation of eugenol from cloves.
6. Islation of (+) limonine from citrus rinds.
4. Paper Chromatography
Separation and identification of the components present in the given organic mixture by chromatographic
methods.
5. Spectroscopy
Identification of organic compound by the analysis of their spectral data (UV, IR, PMR, CMR and MS).
6. Spectrophotometric (UV/VIS) Estimations
1. Amino acids
Cholesterol
7. Caffeine.
2. Proteins
5. Ascorbic acid
3. Carbohydrates
6. Aspirin
4.
FOURTH PAPER
ELECTIVE A
(Nuclear Chemistry)
(Theoretical Aspects and General Procedure)
Time : 3 Hrs.
Max. Marks : 75
1. Interaction of Radiation with matter-Effect of radiation on matter-energy transfer and radiation dose,
measurement of radiation dose including chemical dosimetry. Radiation effects on metals, inorganic nonmetallic compounds and covalent compounds. Radiolysis of water and aueous solutins. Effect of
radioactive pollutants. Radiation hazards-protection and waste management.
2. Counting Technique-Geiger-Muller, ionization, proportional and scintillatioan counters.
3. Nuclear Reactions :
(i) Energetics-mechanics of induced nuclear reaction mass energy, dissecting and nuclear
reaction, columb barrier, inelastic and elastic scatterings.
(ii) Mechanics and models-reaction cross-section, resonance and tunneling, neutron capture and
scattering neutron-diffraction, models for nuclear reactins, nuclear fission, neuclar fusion and photonlear
reactions.
(iii) Production and applications of radioisotopes.
4. Nuclear Energy.
(i) Energy release in fission, chain reactions, controlled release of fission energy, use of
moderators. Nuclear reactors including breeder reactors.
(ii) Energy release in fusion reactions. Principle of atom and hydrogen bombs.
5. Accelerators :
(i) Principles of van de graph generator, Linear accelerators, Cyclotron and synchrotron.
(ii) Nuclear chemistry with accelerators inclidng synthesis of superheavy elements.
6. Chemistry of Nuclear Fuels :
(i) Uranium and thorium-distribution in nature production as nuclear fuels, Enrichment of uranium.
Fuel cycles. Fuel reprocessing.
(ii) Peaceful use of nuclear programme of India-Nuclear Reactors in India.
7. Radiochemical analysis :
(i) Activiation analysis
(ii) Radiometric and radio-release methods.
8. Environmental radioactivity and safety : Fall out from nauclear weapons testing and nuclear power
production, other sources of radioactive contamination, protective actions.
Elective B
(Synthetic Organic Chemistry & Organic Solids)
Time : 3 Hrs.
Max Marks : 75
1. Organic Synthesis
(i) Disconnection Approach
10 Hrs.
General introduction to synthons and Synthetic equivalents, Disconnections, (C-C, C-S, C-O, bonds),
Functional group interconversion, chemoselectivity, cyclisation reaction choosing, synthetic route for small
and large scale synthesis.
(ii) Synthetic Strategies
5 Hrs.
(i) For formation of carbon-carbon bond.
(ii) For formation of carbon-nitrogen bond.
(iii) Formation of carbon-halogen bond.
(iv) Ring Synthesis.
(v) Multistep Synthesis.
(III) Protecting Groups
5 Hrs.
Principle of protection of alcoholic, amino, carbonyl and carboxylic groups.
(iv) Stereochemistry in Organic Synthesis
10 Hrs.
Stereoselectivity and stereospecificity. Regioselectivity and regiospecificity : Assymmetric synthesisSharpless asymmetric epoxidation.
An introduction to computer aided designing of organic synthesis.
II. Reagents in Organic Synthesis
20 Hrs.
Use of following reagents in organic shythesis and function group transformation (including
stereochemistry where possible)
(i) Complex metal hydrides.
(ii) Gilman’s reagent.
(iii) Lithium disopropyl amide (LDA).
(iv) Dicyclohexylcarbodimide (DCC).
(v) 1,3-Dithiane (Reactivity Umpolung).
(vi) Trimethylsily iodide.
(vii) Tri n-butyltin hydride.
(viii) Crown ethers.
(ix) Merrifield resin.
(x) Wilkinson’s Reagent.
(xi) Peterson’s Synthesis
(xii) Organic per acids.
(xiii) Baker’s yeast
III. Selective Organic name reaction and their
Synthetic Application
10 Hrs.
(i) Stork Enamine reaction.
(ii) Favorskii reaction.
(iii) Ene Reaction.
(iv) Barton Reaction.
(v) Hofmann-Loffler-Freytag Reaction.
(vi) Shapiro Reaction.
(vii) Chichibabin Reaction.
(viii) Robinson annulation.
IV. Nitrogen, Sulphur and Phosphorus Ylides
5 Hrs.
Preparation and their synthetic applications.
V. Green Chemistry
5 Hrs.
Introduction of green chemistry basic principles of green chemistry, principles of microwave induced
organic synthesis and combinational chemistry.
VI. Organic Solids
5 Hrs.
Electrically conducting solids, organic charge transfer complex organic super-cunductors-Fullerenes and
doped fullerenes as superconductor.
Elective C
(Statistical Mechanics Thermodynamics of Non-Electrolyte Solutions, Quantum Mechanics &
Thermodynamics of Biochemical Systems)
Time : 3 Hrs.
Max Marks : 75
Statistical Mechanics & Thermodynamics
Indistinguishasbility of gas molecules. Maxwell-Boltzmann law for gaseous system. Thermodynamic
functions for gaseous systems. Molar heat capacity of gases. Heat capacity of hydrogen at low
temperatures. Heat capacities of monatomic crystals. The Einstein model. Debye’s theory of solid Heat
capaciyties of crystals at very low temperatures. Calorimetric entropy. Spectroscopic entropy,
Comaprison of calorimetric and spectroscopic entropies. Third Law of thermodynamics (i) Nernst heat
theorem, (ii) Entropy of chemical reactions (iii) statements of third law of thermodynamics and (iv)
Conventional entropies. Expression for equilibrium constant in terms of partition functions. Equilibrium
constants of simple system—(i) Ionization of metal atoms, (ii) Dissociation of diatomic molecules and (iii)
Isotopic exchange equilibria. Calculatin of thermodynamic properties from spectroscopic data. BoseEinstein stastics, Fermi-Dirac Statistics, Comparison of M-B, B-E and F-D statistics. Fermi-Dirac gas
(electron gas in metals)-Bose-Einsatein gas (liquid Helium).
Thermodymics of Non-Electrolyte Solutions
Ideal and non-ideal solutions. Inter-connection between Raoult’s law and Henry’s Law. Determination of
Partial Molar Properties. Thermodynamic functions of mixing of non-ideal solutions. Excess
thermodynamic functions. Gibbs-Duhem-Margules equation and its applications. Activity and activity
coefficients. Activity coefficients from excess thermodynamic functions.
The theory of Van Laar. Scatchard Hildebrand theory. Wilson model and Flory-Huggins theory.
QUANTUM MECHANICS AND CHEMICAL BONDING
Concept of operators in quantum mechanics—operators for velocity, kinetic energy, momentum and
angular momentum. Detivation of Heisenberg’s uncertainty principle. Solution for Hydrogen atoma. BornOppenheimer approximation. Valence bond theory and its application to homonuclear (Hydrogen) and
heteronuclear (HCI) diatomics. LCAO-MO treatment of hydrogen molecule ion. Comparative study of MO
and VB theory. Huckel molecular orbital theory and its application to hybridization systems (ethylene,
butadiene, allyls and benzene). Calculation of delocalization energy. Physical significance of charge
density and bond order. Calculation of bond length. Pauling and Wheland’s modification in HMO theory
and it application to heteromolecules (pyrimidine). Perturbation methods in LCAO-MO theory. Extende
Huckel molecular orbital theory and SCF-MO method.
THERMODYNAMICS OF BIOCHEMICAL SYSTEM
Different types of chemical process accounting in living systems Relation between microscopic and
macroscopic dissociation constants (acid dissociations of amino acids). Calculation of binding curves
binding of protons by phosphate). Relationship between number of ligands bond per molecule of base
and the partition function. Themodynamics of hydrolysis of adenosine triphosphare (ATP). Standard
Gibbs free energies of a number of phosphate esters. Binding of oxygen by Myoglobin and hemoglobin.
Elective - D
(Environmenal Chemistry And Monitoring)
Time : 3 Hrs.
Max. Marks 75
1. Atmosphere Structure, Particles, the ions and Readicals in the atmosphere, chemical process for
the formation of inorganic and organic particulate matters and their effects, Chemical and
photochemical reactions in the Atmosphere, Oxygen, Ozone chemistry, Ozone hole, Greenhouse
gases and their effects.
2. Air Pollution : primary air-pollutants, hydrocarbons and photochemical smog, Radioactivity.
3. Air quality standards, air quality monitoring and measurements, air pollution control and
equipments.
4. Hydrosphere : Chemistry of Sea water, complex ion in natural and waste water.
5. Water pollution: Classification of water pollutants and impact of each type of water pollutants,
pathways of various pollutants in water.
6. Water quality standards : Sampling and measurements of various parameters; DO, BOD, COD,
TOC, pH, total suspended solids, total dissolved solids, hardness, amount of organic matters and
inorganic ions.
7. Sewage and Fertilizers: Sewage treatment, sewage farms, microbiology and biochemistry of
sewage Fertilizers-nitrogen, ammonification, nitrification, denitrification, biochemistry and ecology
of nitrogen fixation, Entrophication, hdrocarbons and surfactants.
8. Pollution of metals and metalloids : Lead, Mercury, Zinc, Cadmium, Nickel, Chromium, and
Arsenic.
9. Instrumental methods in environmental chemical analysis: Neutron activation analysis Anodic
stripping Valtammetry Atamic absorption, spectrometry, X-ray fluorescence, Faurier Transform
Infrared Spectroscopy, Gas chromatography, Ion Selective Electrodes.
Elective – E
(Biotechnology)
Time : 3Hrs.
(i)
(ii)
(iii)
(i)
(ii)
(iii)
Max. Marks :75
Section – A
Chemistry of biomolecules, proteins, nucleic acids, carbohydrates, lipids and enzymes.
Cell chemistry, structure of cell and its organelles, their functions, constituents of nucleus and
cytoplasm, structure of chromosomes. mitosis and meiosis, cell membrane, its constituents
and functions.
Basic concepts of bacteria and viruses.
Section – B
Biophysical techniques, HPLC, electrophoresis (paper & gel) ion exchange chromatography
and autoradiography.
Genetic Engineering (Recombinant DNA technology), sequencing of biopolymers,
(oligonucleotides & peptides) site directed mutagenesis and southern transfer.
Biosensors and bio-electromics (concept only)
(i)
(ii)
(iii)
(iv)
Section – C
Application of genetic engineering for producing chemicals and pharmaceuticals, food
industry, beverages and dairy products, environmental pollution, bioenergy and fuels,
agriculture and veterinary science.
Immunology (antibodies, defensive proteins), theories of drug action and quantitative
structure activity relationship (QSAR)
Application of thermodynamic principles to simple bio-systems.
Application of enzymes and other biocatalysts.