M.Sc.

Chemistry

Paper I Inorganic chemistry

SYLLABUS

First Year

Paper –I Inorganic Chemistry Unit-1:Covalent and Ionic Bondings

V.B. approach to covalent bonding -Heitler -London, Pauling- Slater refinements,

Hybridization and structure of molecule. VSEPR theory -shapes of molecules. M.O. approach
to covalent bonding -symmetry and overlap of atomic orbitals -symmetry of molecular
orbitals -sigma- pi-and delta -bondings -energy levels in homo -and hetero nuclear diatomic
molecules -bond length, bond order and bond energy -ionic character in a covalent bond. The
concept of multi centre bonding. Structure and bonding in fluorine and oxygen compounds of
xenon and krypton. Bonding in simple tri atomic molecules/ions.

Lattice energy and its calculations by Born-lande and born-Meyer equations -Determinations
by Born –Haber cycle- Kapustinski equation, Energetics of dissolution of ionic compounds in
polar solvents. Properties of ionic compounds- Hardness and electrical conductivity.

Unit II: Chemistry of Lanthanides and Actinides and Studies on Magnetism

Lanthanides- occurrence, extraction and separation techniques (fractional crystalization,

precipitation, ion-exchange, solvent-extraction and thermal decomposition,
selective reduction and oxidation) -position in the periodic table. - electronic configuation -
oxidation states -size relationships -lanthanide contraction -spectral and magnetic properties -
condition compounds of lanthanides -uses of lanthanides and their compounds.

Actinides : Synthesis of elements -position in the periodic table, electronic configuration and
oxidation states- spectral and magnetic properties -comparative account of lanthanides and
actinides.

Magnetism: Types of magnetic behaviour -determination of magnetic susceptibilities by

Gcuy Method and Faraday method -calculation of magnetic moment from experimental data -
magnetic properties of free ions -Effects of ligand field and orbital contribution -magnetic
behaviour of complexes with A, E and T ground terms -Temperature independent
paramagnetism- evaluation of spin orbit coupling constant from spectral and magnetic
moment data -the orbital, contribution reduction factor k-magnetic properties of 3d, 4d, 5d, 4f
and 5f ions anti-ferromagnetic interactions in simple molecules and in lattice structures.

Unit III. Chemistry of Non-aqueous Solvents

Classification of solvents -properties of ionising solvents -a general study of the typical

reactions in liquid ammonia, sulphur dioxide, dinitrogen tetroxide, anhydrous hydrogen
fluoride, sulphuric acid and acetic acid -solution in fused salts non-acqueous titration's.

HSAB concept of acids and bases -acid, base strength and hardness and softness -symbiosis -
theories of hardness and softness -electronegativity and hardness and softness.
Unit IV: Nuclear Chemistry

Properties of nucleus -different types of nuclear forces -liquid drop model, shell model of
nucleus -nuclear reactions induced by charged particles -nuclear reaction cross -section,
significance and determination -theory of nuclear fission -conditions for controlled fission
chain reaction -Nuclear reactor and its components -Production of feed materials for nuclear
reactors -disposal of radioactive wastes- nuclear fusion, steller energy, Application of
radioisotopes in agriculture, industry and medicine -neutron activation analysis -hot atom
chemistry.

Unit V: Chemistry of Solid State

Close packing of atoms and ions FCC,HCP and BCC types of packing tetrahedral and
octahedral void redius ratio -derivation -its influence on structures -representative structures
of AB and AB., types of compounds- rock salt, calcium chloride,wurtzite, sine blende,rutile,
fluorite,antifluorite,cadmimum iodide and nickel arsenide. .Structure of graphite and diamond
-spinels normal and inverse types and perovskite structure.

Diffraction Studies

Crystallographic point groups -space groups -screw, axes and glide planes -Herman -Maugini
notatons seven crystal systems and Bravais lattice Interplanar distance in orthogonal crystal
systems -X-ray diffraction studies -Laue,powder and rotating crystal methods -systematic
absences of refelections and determination oflattice types-data analysis for cubic system.

Electron diffraction by gases: Principle and measurement: determination of structures -

comparison between electron, neutron and X-ray diffractions.

Theories of Metallic bonding Drude-Lorenz theorem and Sommerfield modifications -

MO,VB theories- conductors, insulators and semiconductors -Defects in solid state Schotky
and Frenkel defects-nonstochiometric defects and their consequences.
Paper II : Organic Chemistry - I

Unit I : Electron Displacement, Introduction to Reaction Mechanism and Aromaticity

Electron Displacement : Inductive and field effects - Bond distances - Bond energies-
Delocalised bonds - Cross conjugation - Rules of resonance - The resonance effect - Steric
inhibition of resonance - Hyperconjugation - Hydrogen bonding - Effect of structure on the
dissociation consants of acids and bases.

Introduction to Reaction Mechanisms : Reactive Intermediates - Carbocations, cabanions,

free radicals, carbenes and nitrenes - formation and stability of reactive intermetiates -
Methods of determination of reaction mechanisms - Kinetic and non - kinetic methods -
Kinetic and thermodynamic control of chemical reaction - Priciple of microscopic
reversibility - Hammond postulate - Quantitative treatement of the effect of structure and
reactivity - substituent constants - Limitations and deviations - Taft equation.

Aromaticity : Concept of aromaticiy - Huckels and Criag' rules - Concept of homo - and anti
- aromaticity - cyclopentadienyl anion, fulvene, ferrocene azulene, tropolones, sydnone and
annulenes - Alternant and nonalternant hydrocarbons. NMR and aromaticity.

Unit: II Reaction Mechanisms I - Substitution Reactions

Aliphatic Nucleophilic Substituion : SN1 and SN2 mechanisms - Effect of substrate

structure, attacking nucleophile, leaving group and reaction medium -Ambient nucleophiles
and substrates - Neighbouring group participation -SNi mechanism - Nucleophilic substitution
at allytic, vinylic and aliphatic trigonal carbons-Mechanism of esterification and hydrolysis.

Aliphatic Electrophilic Substitution : Electrophilic substitution at aliphatic saturated carbon

- SE1 SE2 and SEi mechanisms

Aromatic Electrophilic Substitution : Orientation - Reactivity - Mechanisms of Friedel -

Craft reaction, Sulphonation and Gattermann - Koch formylation.

Aromatic Nucleophilic Substitution : SNAr, SN1 mechanisms - Benzyne

mechanism

Unit: III Reaction Mechanism II - Elimation and Addition Reactions

Elimination Reactions : Alpha and beta eliminations - El, E2 and El CB mechanisms -

Sterochemistry of elimination - Orientation of the double bond - Effects of the changes in the
substrate, base, leaving group and reaction medium on El, E2 and E1CB reactions -
Elimination versus substitution - Pyrolytic cis eliminaitons and their stereochemistry Bredt's
rule.

Addition to carbon - carbon multiple bonds : Electrophilic, nucleophilic and free radical
additions - Additions to conjugated systems- Orientation of the addendum -Stereochemical
factors in reactions of addition of hydrogen, HX and HOX -Regioselectivity and
chemoselectivity in additions - Addition of carbenes and carbenoids to double and triple
bonds. Addition to alpha, beta unsaturated carbonyl groups - Michael addition - of Grignard
reagents and lithium dimethyl cuprate - Diels Alder addition.

Addition to carbonyl groups : Mechanisms of Aldol, Benzoin, Claisen and Dieckmann

condensations - Perkin, Knoevenagel, Mannich, Cannizaro, Reformatsky and Darzen's
reactions - Wittig reaction and its modifications.

Unit: IV Stereochemistry and Free Radical Reactions :

Optical Isomerism : Elements of symmetry - Newmann, Sawhorse and Fischer projection

formulae - Concept of Chirality - Cahn Prelog - Ingold system of nomenclature -
Enantiotopic and diastereotopic atoms, groups and faces - Molecules with more than one
chiral center - Molecular dissymmetry due to chiral axes, planes and helicity - Optical
activity of biphenyl, allenes and spiranes, cyclooctene and hexahelicene - Optical activity of
nitrogen and sulphur compounds - Stereospecific and Stereoselective synthesis - Resolution,
recemisation and asymmetric synthesis - Crams' and prelog's rules.

Geometrical Isomerism : E, Z nomenclature - Determination of configuration of geometrical

isomers - stereomutation - Stereoisomerism in monocyclic compounds (upto six - membered
rings)

Free Radical Reactions : Formation, detection and stability of free radicals - Free radical
reactions - Halogenation, addition, oxidation, reduction and rearrangement reactions - Barton,
Sandmeyer, Gomberg - Bachmann, Ullmann, Pschorr and Hunsdiecker reactions.

Unit: V Heterocyclic compounds

Structure, synthesis and reactions of indole, carbozole, oxazole, imidazole and thiazole

Pyrimidines - Generai chemistry and detailed study of uracil, thymine and cytosine.

Purines - General chemistry and detailed study of uric acid and caffeine.

Flavones - General chemistry and detailed study of quercetin. Isoflavones - General

chemistry and detailed study of genistein. Anthocyanins - General chemistry and detailed
study of cyanidin chloride

Coumarins - General chemistry and detailed study of umbelliferone.

PAPER–III

PHYSICAL CHEMISTRY -1

Unit I : Thermodynamics

Second law of thermodynamics – Entropy – Entropy changes of an ideal gas – Entropy in

changes of state – Entropy of mixing – Free energy and its temperature dependence –
Equilibrium constant Gibbs free energy – Maxwell relations and thermodynamics equations
of state. Third law of thermodynamics – Third law entropies – Partial molar quantities –
Partial molar volume – chemical potential – Gibbs – Duhem equation – Fugacity and activity
– Elements of non-equilibrium thermodynamics.

Unit II : Electrochemistry

Ion activity and activity coefficient – Ionic strength – Debye – Huckel theory – Limiting Law
– Ionic association – Molar conductivity – Debye – Huckel – Onsager equation –
Applications of conductivity measurement – Electrode potential. Standard electrode
(reduction) potentials – Nernst equation. Potential diagrams – free energy contribution to
electrode potentials. Types of electrodes and electrochemical cells – Applications of cell
EMF values G, S and H calculations. Calculation of equilibrium constants and solubility
products – Over voltage – Butler – Volmer equation, Tafel equation – Fuel cells – Corrosion.

Unit III : Chemical Kinetics and Catalysis

Theory of reaction rates – Collision theory – Absolute reaction rate theory –Theory of
unimolecular reactions – Chain reactions – Explosive reactions – Kinetic salt effect – Kinetic
isotope effect – Fast reactions – Chemical relaxation – Reactions in flow sysems – Chemical
Kinetics in crossed molecular beam – molecular dynamics – Temperature dependence of
reaction rates – Homogeneous catalysis – acid – base catalysis – acidity functions – Enzyme
catalysis.

Unit IV : Quantum Theory–I

Black body radiation – Photoelectric effect – de Broglie relation and Heisenberg's uncertainty
principle – Postulates of quantum theory – Operator algebra – Schrodinger equation. Eigen
functions and eigen values for particle in a ID and a 3D box, rigid rotor and simple harmonic
oscillator – tunnel effect.

Unit V : Quantum Theory–II

Angular momentum – Hydrogen atom problem – radial distribution functions. Need for
approximation methods. Variation and perturbation methods – Applications to hydrogen and
helium atoms – SCF method – HMO calculations for allyl system butadiene, and benzene.
SYALLABUS

Paper-IV

Analytical Chemistry

Unit- I: Applications of UV, IR and NMR Spectrosopic Techniques

UV- Visible spectroscopy: Basic principle - Process of electronic excitation n-π and π-π
transitions - Transition probability - Solvent effect -Factors affecting position and intensity
ofabsorption bands -Spectra of dienes, polyenes and unsaturated ketones -Woodward -Fiesher
rules.

I R Spectroscopy: Stretching vibrations -Hooke's Law -Stretching and ending vibrations -

force constants -Fundamentals, overtone and combination bands -Fermi resonance -
Applications of 1R spectroscopy -Identity of samples -Characteristic group frequency -
Effects of substitution, conjugation, bond angle distortion of geometry and hydrogen bonding
on vibrational frequencies-detecting inter-and intra-molecular hydrogen bondings.
Frequencies of absorption for sulphate, nitrate, chlorate ions and ammonia and water
molecule-shift in frequencies upon coordination.

Infrared instrumentation and techniques. Source of ir-radiations, monochromatization,

cell and prim materials, measuring intensities of ir radiations. Sample handling techniques
NMR
spectroscopy: HNMR -Introduction, to principles -instrumentation -Chemical shift,
spin-spin coupling - peak area -homotopic, enantiotopic and diastcreotopic relationships -first
order and non first order spectra factors - aftecting spin-spin splitting-width of lines-
Dueterium substitution and shift reagents- double reasonance technique. Basic concepts of FT
-MMR13 CNMR. Comparison of Hand and CNMR -Fourier transformation -Chemical shift
and its dependence -C-C & C-H couplings -Off resonance and broad band decouplings -
Application in structural elucidation, application ofl9F 31T,10,11 B resonance studies to
inorganic systems and organometailics- fluctional behaviour.

Unit II :Mass Spectrometry, ORD and CD and Chromatographic Methods

Mass spectometry: Principle- Parent ion, metastable ion& isotopic ions -Base peak -Genera!
rules of fragmentation -MacLafferty rearrangement -Retro Diels-Alder reaction.

ORD & CD : Principle- Circular birefringence and circular dichroism -Cotton effect -Types
of ORD curves-Applications of plain dispersion curves -Application of Cotton effect curves -
Alpha halo ketone and Octant rules-Applications for determination of conformation and
configuration.

Chromatographic methods: Definition and classification of chromatographic techniques -

Elementary treatment of the principle & practice of adsorption, partition, paper, thin-layer,
HPLC and gas chromatographic techniques.
Unit III : Electrochemical analysis

Reference electrodes -indicator electrodes - ion-exchange membrance and solid state

electrodes -their construction and working Direct potentiometry -potentiometric titration's-
acid-base, redox, precipitation and complexometric titrations by potentiometry. Theory of
electrolysis-concentration and kinetic over potentials -estimate of applied voltage for
electrolysis -depolarisers -electrogravimetry -constant potential and constant current
electrolysis. Coulometry and coulometric titrations polarography- dropping mercury and
rotating mercury electrodes -polarograms half-wave potential- diffusion current and Ilkovic
equation -amperometry -cyclic voltammetry.

Unit - IV: Error Analysis and Computer Programming

Significant figures and their importance in calculations -precision and accuracy -determinate
and indeterminate errors-measures of precision -statistical concepts -standard or normal error
curve and its features -reliability of mean values -confidence limits -distribution and
confidence levels -Regression -distribution of data of a liner curve-method of propagation of
errors -Rejection of observation 2. 5a, 4a and Q tests.

Basic Programming: Constants, variables- expressions -hierarchy of operations -arithmetic

statements -I/O state-Statements -Branching -conditional branching - loops -library functions.
.

Subscripted variables and subroutines-DIM statements - Array - one-dimensional and two-

dimensional-matrix manipulations -DEF function -GOSUB and Return statements -Graphics
LINE, CIRCLE, PSET statements-Simple programs for Chemistry.

MS EXCELL PACKAGE: (Version Excel 2000) components of spread sheets -Books-sheets-

pages- naming files -formatting cell and rows. Editing data in a cell-copying- pasting -
constructing cell and rows. Editing data in a cell-copying- pasting -constructing formula in
cells -absolute and - relative referencing of cell and inter transfer of data inserting Charts -
constructing spread sheets for calculation in chemistry by invoking functions in cells -least
square, Curve fitting -polynomials and evaluating coefficients invoking Excel Solver -
statistical calculations -developing spread sheets for potentiometric titration -data processing
-pKa values of weak acids from pH volume data employing Henderson equation. (Text book:
Ira N Levine, 'Physical Chemistry', Tata Mcgraw Hill, New Delhi, Edn. V, 2002 and Rick
Winter & Patry N. Winter, "Using Microsoft Office & Professional (que series), special
edition, Printice Hall of India Pvt.Ltd., New Delhi, 5th Edn., 1998 or later Version ).

UNIT V : Thermal and spectrophotometric methods of analysis and environmental

chemistry.

Principles of TGA, DTA and DSC -application to simple salts -oxy salts, carbonates and
complex salts. Thermometric titrations.
Laws of absorption and quantitative law of luminescence -principles and applications of
photometry, fluorimetry, turbidimetry and nepheometry -photometric titrations -
multicomponent analysis -tlame spectrophotometry -absorption and emission photometry.

Environmental Chemistry :

Water pollution -dissolved oxygen -BOD, COD -heavy metals as pollutants -thermal
pollution -chemical pollution -role of fertilizers and detergent builders and pesticides -
industrial wastes and purification of water by classical and modern methods. Air pollution -
sources -pollutions SO2, NO, CO, hydrocarbons and industrial and photochemical smog.
Pollution of upper atmosphere -greenhouse effect. Chemical at toxicology -biochemical
effect of heavy metals -PAN and cyanide. Use of IR in environmental pollution studies.

PRACTICALS

Practical Paper -1

Organic Chemistry Practicals

1. Analysis of two-component mixtures

Seperation and Characterization of components.

2. About a dozen single stage preparations of organic components

preparations illustrating - o - acylation, N - acylation, bromination, nitration, Benzolation

diazotisation, rearrangements, hydrolysis, oxidation etc.

Practical Paper - II

Analytical Chemistry Practicals

1. Quantitative Estimations

Quantitative estimation of aniline,phenol,ethyl mthyleketone and glucose (by both Betrane's

and Lane and Bynon methods).

2. Semi-micro Qualitative Analysis

Analysis of mixtures containing two familar and two less familiar cations from among the
following:

Ti, W, Se, Te, Mo, Ce,Th,Ti,Zr,V,Be,U and Li.