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UNIVERSITY OF KERALA

POST GRADUATE PROGRAMMES IN CHEMISTRY


(Under Semester System wit effect from 2001 admission)

PREAMBLE

There are three independent PG programmes in Chemistry, namely M.Sc. Programme in Branch III – Chemistry,
M.Sc. Programme in Branch IV – Analytical Chemistry and M.Sc. Programme in Branch V – Applied
Chemistry. All these three M.Sc. Programmes are equivalent in all respect for employment and higher studies.
Each of these three PG programmes shall extend over a period of two academic years comprising of four Semesters,
each of 450 hours in 18 weeks duration. The syllabi and schemes of examinations of these three programmes are
detailed below. The theory courses of first three Semesters and the practical courses of the first two semesters of the
three programmes are common, since all these three programmes are equated. Therefore, the Examinations of these
three PG programmes are to be conducted by a common Board of Examiners, and questions for the first three
Semesters will be common for all the these M.Sc. Programmes. These syllabi are effective from 2001 admission in
affiliated colleges of the University.

M.Sc. PROGRAMME IN BRANCH III – CHEMISTRY


(Under Semester System with effect from 2001 admission)

SYLLABUS AND SCHEME OF EXAMINATION

Course No. & Title Hours per Duration of Marks for Marks for Total
week ESA in CA ESA Marks
hours
L P
SEMESTER I*
CH 211 Inorganic Chemistry-I 5 3 25 75 100
CH 212 Organic Chemistry-I 5 3 25 75 100
CH 213 Physical Chemistry-I 5 3 25 75 100
CH 214 Inorganic Practical-I 3
(To be continued in Semester II)
CH 215 Organic Practical-I 3 (To be continued in Semester II)
CH 216 Physical Practical-I 4 (To be continued in Semester II)

Total Marks for Semester I 300

*Distribution of teaching hours/week: - Theory – 15 hours, Practical – 10 hours (1 hour for Seminar)

SEMESTER II*

CH 221 Inorganic Chemistry-II 5 3 35 75 100


CH 222 Organic Chemistry-II 5 3 25 75 100
CH 223 Physical Chemistry-II 5 3 25 75 100
CH 214 Inorganic Practical-I 3 6 25 75 100
CH 215 Organic Practical-I 3 6 25 75 100
CH 216 Physical Practical-I 4 6 25 75 100

Total Marks for Semester II 600

*Distribution of teaching hours/week: - Theory – 15 hours, Practical – 10 hours (1 hour for Seminar)
SEMESTER III*
CH 231 Inorganic Chemistry-III 5 3 25 75 100
CH 232 Organic Chemistry-III 5 3 25 75 100
CH 233 Physical Chemistry-III 5 3 25 75 100
CH 234 Inorganic Practical-II 3
(To be continued in Semester IV)
CH 235 Organic Practical-II 3 (To be continued in Semester IV)
CH 236 Physical Practical-II 4 (To be continued in Semester IV)
Total Marks for Semester III 300

*Distribution of teaching hours/week: - Theory – 15 hours, Practical –10 hours (1 hour for Seminar)

SEMESTER IV*
CH 241(a) Advanced Inorganic **
Chemistry
CH 241(b) Advanced Organic 15 3 25 75 100
Chemistry
CH 241(c) Advanced Physical
Chemistry
CH 234 Inorganic Practical-II 3 6 25 75 100
CH 235 Organic Practical-II 3 6 25 75 100
CH 236 Physical Practical-II 4 6 -- 100 100
CH 242 Dissertation -- 100 100
Comprehensive Viva Voce
Total Marks for Semesters IV 600

Grand Total (for Semesters I – IV) 1800

*Distribution of teaching hours/week: - Theory – 15 hours ( 10 hours for Discussion on Project) Practical –20
hours (1 hour for Seminar)

**Each student has to choose either (a),(b) or (c) as elective in accordance with the Dissertation chosen.

SYLLABUS FOR M.Sc. PROGRAMME IN BRANCH III – CHEMISTRY


(Under Semester System w.e.f. 2001 Admission)

SEMESTER I

CH 211 INORGANIC CHEMISTRY – I


Total 90 h

Unit I Main Group and Transition Elements 18 h

Noble gas compounds: Preparation, properties, and structure and bonding. Halogens in positive oxidation
states. Interhalogen compounds: Preparation, Properties, structure and bonding, and uses. Pseudohalogens:
Preparation, properties, and structure and bonding. Polyhalide ions. Astatine: Synthesis, stability and properties.

Survey of the transition elements. General characteristics of transition elements. Electronic configurations
and oxidation states. Study of the following groups of elements and their compounds with peculiar structures, and
their recent chemistry.

Ti V Cr Mn
Zr Nb Mo Tc
Hf Ta W Re
Unit II Isopoly and Heteropoly Acids 18 h

Isopoly and heteropoly acids of Mo and W: Preparation, properties and structure. Classification,
preparation, properties and structures of borides, carbides, nitrides and silicides. Silicates: Classification and
structure, Silicones: Preparation, properties and applications.

Unit III Sulphur, Nitrogen, Phosphorus and Boron Compounds 18 h

Sulphur-Nitrogen compounds: Tetrasulphur tetranitride, disulphur dinitride and polythiazyl. SxNy


compounds. S-N cations and an ions. Other S-N compounds. Sulphur-phosphorus compounds: Molecular
sulphides such as P4S3, P4S7, P4S9 and P4S10. Phosphours-nitrogen compounds: Phosphazines. Cyclo and linear
phosphaziens. Other P-N compounds. Boron-nitrogen compounds: Borzine, substituted borazines and boron
nitride.

Boron hydrides: Reactions of diborane. Structure and bonding. Polyhedral boranes: Preparation,
properties, and structure and bonding. The topological approach to boron hydride structure. Styx numbers.
Importance of icosahedral framework of boron atoms in boron chemistry. Closo, nido and arachno structures.
Structural study by NMR. Wade’s rules. Carboranes. Metallocarboranes. Organoboron compounds and
hydroboration.

Unit IV Analytical Principles 18h

Evaluation of analytical data: Accuracy and precision. Standard deviaton, variance and coefficient of
variation. Student ‘t’ test. Confidence limits. Estimation of detection limits. Errors: Classification, distribution,
propagation, causes and minimization of errors. Significant figures and computation rules. Correlation analysis:
Scatter diagram. Correlation coefficient 'r'. Calculation of 'r' by the method of least squares.
Volumetric methods: Classification of reactions in volumetry. Theories of indicators: Acid-base, redox,
adsorption, metallochromic, fluorescent and chemiluminescent indicators. Complexation titration: Titration using
EDTA, NTA and Titriplex. Precipitation titrations. Redox titrations. Gravimetric methods: Mechanism of
precipitate formation. Aging of precipitates. Precipitation from homogeneous solutions. Coprecipitation and
postprecipitation. Contamination of precipitates. Washing, drying and ignition of precipitates. Orgnic reagents
used in gravimetry: Oxine,dimethylglyoxime and cupferron.

Thermal methods of analysis: Principles and instrumentation of TG and DTA. Complementary nature of
TG and DTA. Differential scanning calorimeter (DSC). Applications of thermal methods in analytical chemistry
and in the study of mineral and polymers.

Unit V Nuclear Chemistry 18 h

Nuclear structure, mass and charge. Nuclear moments. Binding energy. Semiemperical mass equation.
Stability ruels. Magic numbers. Nuclear models: Shell, Liquid drop, Fermi gas, Collective and Optical models.
Equation of radioactive decay and growth. Half life and average life. Radioactive equilibrium. Transient and
secular equilibria. Determination of half-lives. Nuclear reactions: Energetics of nuclear reactions. Types of
nuclear reactions. Spontaneous and reduced fission. Neutron capture cross section and critical size. Principles of
working of the reactors of nuclear power plants. Breeder reactor. Nuclear fusion reaction. Detection and
measurement of radiation. Principles of working of different counters: GM, Proportional, Ionization and
Scintillation counters. Applications of radioactivity.

References

1. M.C.Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press.


2. F.A.Cotton and G.Wilkinson, “Advanced Inorganic Chemistry”, John Wiley & Sons
3. J.E.Huheey, “Inorganic Chemistry-Principles of Structure and Reactivity”, Harper Collins College
Publishers.
4. C.J.Mooday and J.D.R.Tanas, “Noble Gases and Their Compounds”, Pergamon Press.
5. J.H.Hollaway, “Noble Gas Chemistry”, Methuen, New York.
6. H.R.Alcock, “Phosphorus-Nitrogen Compounds”, Academic Press
7. K.F.Purcell and J.C.Kotz, “Inorganic Chemistry”, Saunders.
8. A.I.Vogel,”A Text Book of Quantitative Inorganic Analysis”, Longman.
9. D.A.Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College
Publishing.
10. W.W.Wendlandt, ‘Thermal Methods of Analysis”, John Wiley & Sons.
11. G.Friedlander and J.W.Kennady, “Introduction to Radiochemistry”, John Wiley & Sons
12. G.Fiedlander, J.W.Kennady and J.M.Mites, “Nuclear and Radiochemistry”, John Wiely & Sons.
13. S.Glasston, “Source Book on Atomic Energy”, Associated East-West Press.
14. H.J.Arnikar, “Essentials of Nuclear Chemistry” IV Edition, New Age International, New Delhi.

CH 212 ORGANIC CHEMISTRY-I


Total 90 h

Unit I Stereochemistry of Organic Compounds 18 h

Molecular chirality and stereochemical nomenclature. Molecules with chiral axes and planes. Molecular
shape, topology and optical activity. Atropisomerism and its designation. Racemisation, resolution,
prostereoisomerism, stereotopicity and enantiomeric excess. Non-carbon chiral centres. Introduction to chiroptical
properties. ORD, CD and their application in assigning configuration and conformation. Octant and axial
haloketone rules. Conformational analysis of cycloalkanes, decalins and their substituted derivatives.
Unit II Structure, Reactivity and Intermediates 18 h

Electronic and steric effects. Influence of structural features on acidity, basicty and reactivity of organic
compounds. Structure, formation and properties of carbenes, nitrenes and arynes. Singlet and triplet carbenes,
formation and reactions. Carbon free radicals: Structure, formation and stability. Radical reactions, autoxidation
and radical chain reactions. Structure, stability and formation of carbocations and carbanious. Arynes: Formation
and structure. Benzyne SNI and SNAr mechnaisms in aromatic nucleophilic substitution. Orientational effects of
substituents in aromatic electrophilic substitutions.

Unit III Substitution and Elimination Reactions 18 h

Nucleophilic substitution at sp3 carbon, its mechanisms and stereochemical aspects. Effect of solvent,
leaving group and substrate structure. Neighboring group participation. Non-classical carbocations. Elimination
reactions leading to C=C bond formation and their mechanisms. Stereospects of C=C bond formation. Effect of
leaving group and substrate structure. Hoffman and Saytzeff elimination.

Unit IV Reactivity of Unsaturated Systems 18 h

Stereoaspects of the addition of X2, HX, boranes and hydroxylation to C=C systems. Cis and trans
Hydroxylation of cycloalkenes. Nucleophilic addition to activated C=C systems. Michael addition. Mechanism,
with evidence, of Aldol (normal, crossed and directed), Perkin, Stobbe, Knovenagel, Darzen, Reformatsky and
Benzoin condensations. Grignard, Cannizzaro Witting and Wittig-Horner reactions. Mechanism and
stereochemistry pf addition to C=O systems. Cram’s rule. Mechanism of esterification and ester hydrolysis.

Unit V Separation Techniques 18 h

Chromatographic methods: Classification of chromatographic separations. Theory of chromatography.


Applications of chromatographic mehtods: Adsorption and partition chromatography. Paper, thinlayer and column
chromatographic methods. LC, HPLC and GC. Column matrices. Detectors. Affinity and chiral columns. Solvent
extraction. Liquid-liquid extraction. Distribution law. Successive extractions. Craig method. Uses of oxine,
dithizone, high molecular weight amines, dithiocarbamates and crown ethers in extraction. Normal and
ultracentrifugation.
Reference

1. D.Nasipuri, “Stereochemistry of Organic Compounds”, Wiley Eastern


2. I.L.Finar, “Organic Chemistry” Vol 2, Longman
3. P.Sykes, “A Guidebook to Mechnaisms in Organic Chemistry”, Longman
4. S.N.Issacs, “Physical Organic Chemistry”, Longman
5. J.March, “Advanced Organic Chemistry”, Wiley
6. C.J.Moody and W.H.Whitham, “Reactive Intermediates”, Oxford University Press
7. D.A. Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College
Publishing.
8. R.A.Day and A.L.Underwood, “Quantitative Analsis”, Prentice Hall.

CH 213 PHYSICAL CHEMISTRY-I


Total 90 h

Unit I Development of Quantum Mechanics 18 h

Introduction to Classical Mechanics: Newtonian Mechanics. Lagrange and Hamiltonian equation of


motion. Conservation of angular momentum. Hamiltonian function and energy. Classical wave equation.
Experimental foundation of quantum mechanics. The blackbody radiation, photoelectric effect, Compton effect and
atomic spectra. Failure of classical mechanics to explain these phenomena. Quantum mechanical explanations.

Formulation of quantum mechanics: The wave nature of sub-atomic particles – The de Broglie relation.
Experimental proof for the de Broglie relation. Group velocity and phase velocity. The uncertainty principle and its
consequences. The postulates of quantum mechanics. Setting up of the Schrodinger wave equation. Concept of
operators. Laplacian, Hamiltonian, linear and Hermitian operators. Angular momentum operators and their
properties. Commutator. Eigen function and eigen values. Physical interpretation of wave function. Orthogonality
theorem. Orthonormality. Boundary conditions and well-behaved solutions. Solutions of Schrodinger wave
equation for a free particle, particle on a ring, particle in one-dimensional box and particle in three-dimensional box.

Unit II Application of Quantum Mechanics-I 18 h

Application of Quantum Mechanics to simple systems: Linear harmonic oscillator. Derivation of expression for
frequency of oscillation. Classical treatment of simple linear harmonic oscillator and its limitation. Quantum
mechanical treatment. Complete solution for linear harmonic oscillator in one dimension. Hermite polynomial,
recurrence formula and orthogonality. Normalized solution and energy values.

Hydrogen-like atom: Schrodinger wave equation in polar coordinates. Separation of Variables and
complete solution of the Ø equation. Statement of the wave functions of the θ and radial parts (complete
mathematical steps not required). Atomic orbitals. Total wave function of hydrogen atom. Space quantisation.
Approximate methods: Perturbation theory. A set of successive corrections to an unperturbed problem. The
variation principle. Secular equations.

Many electron atoms: Slater’s treatment of complex atoms. Exchange of spectra. Degeneracies.
Solutions of secular equations. Self-consistent field method. Electron correlation in the helium atom. Angular
momenta. The spin of electrons. The exclusion principle. Vector atom model. Spin orbit coupling. Term symbols
and explanation of atomic spectra. Slater’s approximation. Slater’s rules and their application in empirical
calculation of ionization energy of multielectron atoms.

Unit III Applications of Quantum Mechanics-II 18 h

MO theory of hydrogen molecule ion. Secular equation and its solution. Electron density distribution and
stability of H2+ ion. MO and VB theories of H2. Resonance. MO theory of homonuclear diatomic molecules.
Bond order and stability. MO theory of simple heterogeneous diatomic molecules like HF, LiH, CO and NO.
Directed Valences: The hybridization. Expressions for hybrid orbitals in terms of wave functions of s and
p orbitals and explanation of directed valences of sp, sp2 and sp3 hybrid orbitals. The ‫ٱ‬-bonds and the treatment of
delocalised electrons. Qualitative picture of butadiene and benzene. Bonding and hybridization involving d-
orbitals.

Ionic Bonding: Ionic bonding and potential energy field. Lattice energy. Born theory and Born-Haber
cycle. Elctronegativity: Pauling, Mullikan and Allred-Rochow scales. Electronegativity and percentage of ionic
character. Secondary bond forces: The van der Waals' forces, ion-dipole, ion-induced dipole, dipole-dipole, dipole-
induced dipole and London dispersion forces. The hydrogen bond.

Unit IV Chemical Kinetics 18 h

Complex reactions: Reversible, consecutive, concurrent and branching reactions. Free radical and chain reactions.
Steady state treatment. Reactions like H2-Cl2, H2-Br2, and decompositions of ethane, acetaldehyde and N2O5. Rice-
Herzfeld mechanism. Unimolecular reaction. Lindemann treatment. Semenoff-Hinshelwood mechanism of chain
reaction and explosion. Kinetics of fast reactions: Relaxation method, relaxation spectrometry, flow method, shock
method, fast mixing method, field jump method and pulse method.

Theories of reaction rate: Influence of temperature on reaction rate. Arrhenius equation and its limitations,
activation energy. Collision theory and absolute reaction rate theory. Free energy of activation and volume of
activation. Thermodynamic formulation of reaction rate. Effects of pressure and voulume on the velocity of gas
reaction.

Reactions in soulution: comparison between reactions in gas phase and in solution. Factors determining
reaction rates in solution. Reaction between ions and influence of ionic strength. Primary and secondary kinetic salt
effects. Influence of solvent on reaction rate. Significance of volume of activation. Hammet and Tafel equation.

Photochemistry: Effect of radiation on the rate of reaction. Law of photochemistry. Quantum yield.
Radiative and non-radiative transitions. Fluorescence and quenching of fluorescence. Photosensitization. Flash
photolysis. Photochemical reactions of H2-Cl2 and H2-Br2. Photostationary state. Chemiluminescence.

Unit V Surface Chemistry, Colloids and Catalysis 18 h

Different types of surfaces. Examination of surfaces using ESCA, Auger, SEM and STM. Properties of
surface phase. Thermodynamics of surface. Surface tension of solutions. Gibbs’ adsorption equation and its
verification. Surfactants and miscelles. Surface films: Different types. Surface pressure and surface potential, and
their measurements and interpretation.

The gas-solid inter phase: Types of adsorption. Hear of adosrption. The Langmuir theory-kinetic and
statistical derivation. Multilayer adsorption- the BET theory and Harkins-Jura theory. Adsorption from solutions on
solids. Langmuir and classical isotherms. Chemisorption-differences with physical adsorption. Adsorption
isotherms. Adsorption with dissociation. Adsorption with interaction between adsorbate molecules. Measurement
of surface area of solids: Harkins-Jura absolute method, entropy method, and the point B method. Use of
Langmuir, BET and Harkins-Jura isotherms for surface area determination.

The colloidal state: Multimolecular, macromolecular and associated colloids. Stability of collids. The zeta
potential. Kinetic, optical and electrical properties of colloids. Electrokinetic phenomena: Electrophoresis,
electroosmosis, sedimentation potential and streaming potential. Donnan membrane equilibrium.

Catalysis: Mechanism and theories of homogeneous and heterogeneous catalysis. Acid-base and enzyme
catalysis. Bimolecular surface reactions. Langmuir-Hinshelwood mechanism.

At least 100 problems to be worked out from all units together.


30% of the questions for Examination shall contain problems.
References

1. M.W.Hanna: “Quantum Mechanics in Chemistry”, Benjamin


2. M.C.Day and J.Selbin: “Theoretical Inorganic Chemistry”, Affiliated East West Press
3. I.N.Levine: “Quantum Chemistry”, Prentice Hall
4. Manas Chanda: “Atomic Structure and Chemical Bond including Molecular Spectroscopy”, Tate McGraw-
Hill
5. Donald A McQuarrie: “Physical Chemistry-A Molecular Approach”, Viva Low Priced Edition
6. C.A.Coulson: “Valence”, Oxford University Press
7. G.W.Castellan: “Physical Chemistry”, Narosa Publishing House
8. S.Glasstone and H.S.Taylor: “Treatise on Physical Chemistry”, D.Van Nostrand
9. A.A.Frost and Pearson: “Kinetics and Mechanism”, John Wiley and sons
10. K.J.Laidler: “Chemical Kinetics”, McGraw-Hill
11. S.Glasstone, K.J.Laidler and H.Eyring: “ The theory of Rate Process”, McGraw Hill
12. P.H.Emmet, “Catalysis – Vol I – Fundamental Principles”, John Wiley Sons
13. A.E.Alexander and P.Johnson: “Colloid Science”, Oxford University Press
14. J.N.Gurtu and H.Sneji: “Advanced Physical Chemsitry”, Pragati Prakash
15. A.W.Adamson: “The Physics and Chemistry of Surfaces”, Interscience
16. S.J.Gregg: “The Surface Chemistry of Solids”, Chapman and Hall
17. N.K.Adam: “The Physics and Chemistry of Surfaces”, Oxford University Press
18. F.Daniels and R.A.Alberty: “Physical Chemistry”, Wiley Eastern.

CH 214 INORGANIC PRACTICLS-I


Total 125 h

1. Sepration and identification of rare/less familiar metal ions such as Ti,W,Sc,Mo,Ce,Th,Zr,V,U,Li.


2. Volumetric estimations using EDTA, ammonium vanadate, ceric sulphate, chloramine-T and potassium
iodate.
3. Colorimetric determinations of Cr,Fe,Mn,Ni,Ti,W and Cu.
4. Preparations of atleast 8 metal complexes.

References

1. A.I.Vogel, “A Text Book of Quantitative Inorganic Analysis”, Longman.


2. A.I.Vogel, “A Text Book of Qualitative Inorganic Analysis”, Longman.
3. D.A.Skoog and D.M.West, “Analytical Chemistry: An Introduction”, Saunders College Publishing
4. W.G.Palmer, “Experimental Inorganic Chemistry”, Cambridge University Press.

CH 215 ORGANIC PRACTICAL-I


Total 125 h

1. General methods of separation and purification of organic compounds with special reference to:
(a) Solvent extraction.
(b) Fractional crystallization
(c) Steam distillation and distillation under reduced pressure.
(d) Column, paper and thin layer chromatography.

2. Analysis of organic binary mixtures: Separation and identification of organic binary mixtures containing
atleast one component with two substituents. (A student is expected to analyze atleast 10 different binary
mixtures).
3. Preparation of organic compounds: Single stage preparations by reactions involving nitration,
halogenation, oxidation, reduction, alkylation, acylation, condensation and rearrangement. (A student is
expected to prepare atleast 10 different organic compounds by making use of the reactions given above).
References

1. A.I.Vogel, “A Text Book of Practical Organic Chemistry”, Longman.


2. A.I.Vogel, “Elementary Practical Organic Chemistry”, Longman.
3. F.G.Manu and B.C.Saunders, “Practical Organic Chemistry” Longman.

CH 216 PHYSICAL PRACTICAL-I


Total 125 h

A student has to carry out atleast 35 experiments without omitting any of he topics given below:

1. Phase rule

(a) Distribution Law: Partition of iodine between water and carbon tetrachloride. Equilibrium
constant of I- + I2 □ I3-. Concentration of unknown potassium iodide. Partition of ammonia
between water and chloroform. Equilibrium constant of Cu 2+ + 4NH3 □ Cu(NH3) 42+. Partition of
aniline between benzene and water. Hydrolysis constant of aniline hydrochloride. Association of
benzoic acid in benzene.

(b) Solid-Liquid Equlibria: Construction of phase diagrams of simple eutectics, systems with
congruent melting points and solid solutions. Determination of composition of unknown
mixtures. Analytical and synthetic methods for the determination of solubilities and heat of
solution.

(c) Partially Miscible Liquids: Critical solution temperature, influence of impurities on the miscibility
temperature (KCl, NaCl and/or succinic acid). Determination of compositions of unknown
mixtures.

(d) Completely Miscible Liquid Systems: Construction of phase diagrams of two-component liquid
system. Zeotropic and Azeotropic.

(e) Three Component Systems: With one pair of partilally miscible liquids. Construction of phase
diagrams and tie lines. Compositions of homogeneous mixtures.

2. Dilute Solutions

(a) Depression in Freezing Point: Determination of molar depression constant, molecular mass, mass
of solvent and composition of solution using solid solvents. Study of dissociation and association
of solutes. Atomicity of sulphur. Measurement of activity coefficient and partial molar properties.

(b) Transition Temperature: Determination of molar transition point depression, molecular mass,
mass of solvent and composition of solution.

3. Thermochemistry

Determination of water equivalent, heat of neutralization, heat of ionization, integral heat of solution, heat
of displacement and thermometric titrations.

4.Chemical Kinetics

Acid hydrolysis and alkali hydrolysis of esters. Arrhenius parameters. Persulphate-iodide reaction. Effect
of ionic strength and solvent on reaction rate.
5. Adsorption

Verification of Langmuir and classical isotherms for adsorption of solutes on solids. Estimation of surface
excess and molecular area. Preparation of simple colloids and determination flocculation value.

References

1. A.Finlay and J.Akitchener, “Practical Physical Chemistry”, Longman


2. F.Daniels and J.H.Mathews, “Experimental Physical Chemistry”, Longman.
3. A.M.James, “Practical Physical Chemistry”, J.A.Churchil.
4. H.H.Willard, L.L.Merritt and J.A.Dean, “Instrumental Methods of Analysis”, Affiliated East-West Press.
5. D.P.Shoemaker and C.W.Garland, “Experimental Physical Chemistry”, McGraw-Hill.

SEMESTER II

CH 221 INORGANIC CHEMISTRY-II


Total 90 h

Unit I Theories of Metal Complexes 18 h

Valence bond theory and its limitations. Ligand field theory: Splitting of d orbitals in different ligand
fields such as octahedral, tetragonal, square planar, tetrahedral trigonal bipyramidal and square pyramidal fields.
Jahn-Teller effect. Ligand field stabilization energy (LFSE) and its calculations. Thermodynamic effect of LFSE.
Factors affecting the splitting parameter Spectrochemical series. Molecular orbital theory based on group theoretical
approach and bonding in metal complexes Σ and π bondings in complexes. MO diagrams of complexes with and
without π bonds. Effect of π bond on the stability of Σ bond. Nephelauxetic series. Critical comparison of the three
theories as applied to metal complexes.

Unit II Spectral and Magnetic Properties of Metal Complexes 18 h

Spectral properties of complexes: Term symbols for d-ions. Characteristics of d-d transitions. Selection
rules for d-d transitions. Orgel diagrams. Tanabe-Sugano diagrams. Effects of Jahn-Teller distortion and spin-orbit
coupling on spectra. Charge transfer spectra.

Magnetic properties of metal complexes: Types of magnetism shown by complexes. Magnetic


susceptibility measurements. Gouy method. Spin-only value. Orbital contribution to magnetic moment.
Ferromagnetism and antiferromagnetism in complexes. Application of magnetic measurements to structure
determination of transition metal complexes.

Unit III Reactions of Metal Complexes 18 h

Isomerism: Geometrical, optical and other types. Stepwise and overall formation (stability) constants.
Chelate effect. Irwing-William order of stability. Factors affecting stability of complexes. Kinetics and mechanism
of reactions involving complexes in solution. Inert and labile complexes. Ligand displacement (substitution)
reactions in octahedral and square planar complexes. The trans effect. Ligand field effects on reaction rate.
Influence of acid and base on reaction rate. Redox reactions in complexes: Electron transfer and electron exchange
reactions. Outersphere and innersphere mechanisms of redox reactions.

Unit IV Organometallic Compounds 18 h

Metal carbonyls, nitrosyls and cyanides. Synthesis, structure and bonding in polynuclear carbonyls with
and without bridging. Complexes with liner π -donor ligands: Olefins, acetylenes, dienes and allyl complexes.
Hapto nomenclature. Complexes with cyclic π -donors: Cyclopentadiene, benzene, cycloheptatriene and
cyclooctatetraene complexes, structure and bonding. Fluxional molecules. Catalysis by organometallic compounds:
Hydrogenation, hydroformylation and polymerization reactions.

Unit V Bioinorganic Chemistry 18 h

Metalloporphyrins: Porphyrin ring system. Chlorophyll – synthetic model for photosynthesis.


Cytochromes: Biological importance of iron. Availability and transport of iron. Haemoglobin and myoglobin.
Synthetic oxygen carrier. Iron in enzymes. Catalytic functions of metalloenzymes in biological processes.
Cobaltamine in amin oacid catabolism. Synthetic model of enzyme action. Inhibition and poisoning by metal ions.
Copper in cytochrome oxidase and in respiratory chain. Na and K in blood, in Urine, transport in kidney and in
intracellular fluid. Zn in aldolase activity. Nitrogen fixation and nitrogenases. Dinitrogen complexes.
References

1. M.C.Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press.


2. F.A.Cotton and G.Wilkinson, “Advanced Inorganic Chemistry”, John Wiley & Sons
3. J.E.Huheey, “Inorganic Chemistry-Principles of Structure and Reactivity”, Harper & Collins College
Publication.
4. S.F.A.Kettle, “Coordination Chemistry”, Longman
5. J.C.Bailar, “Chemistry of Coordination Compounds”, Reinhold
6. F.Baselo and R.Johnson, “Coordination Chemistry”, Bejamin Inc.
7. H.J.Emeleus and A.G.Sharp, “Modern Aspects of Inorganic Chemistry”, Van Nostrand.

CH 222 ORGANIC CHEMISTRY-II


Total 90 h

Unit I Molecular Rearrangements 18 h

Mechanism, with evidence, of Wagner – Meerwein, Pinacol, Demjanov, Hafmann, Curtius, Schmidt,
Lossen, Beckmann, Wolff, Fries, Arylazo, Fischer – Hepp, Hofmann-Martius, von Richter, Orton, Bamberger,
Smiles, Dienone-Phenol, Benzilic acid, Benzidine, Favorskii, Stevens, Witting, Sommelet-Hauser, Baeyer-Villiger,
Hydroperoxide and borane rearrangements. Dakin reaction.

Unit II Aromaticity and Symmetry Controlled Reactions 18 h

Symmetry properties of Mos. LCAO-MO theory of simple conjugated polyenes and cyclic polyenes.
Aromaticity and antiaromaticity. Homo, hetero and nonbenzenoid aromatic systems. Aromaticity of annulenes.
mesoionic compounds, metallocenes, cyclic carbocations and carbanions. Classification of pericyclic reactions.
Mechanism and stereo course of electrocyclic, cycloaddition and sigmatropic reactions. Woodward-Hoffmann rules.
FO, CD and Huckel-Mobius analysis of electrocyclic and cycloaddition reactions. FO analysis of [l,j] and [3,3]
migration. Claisen rearrangement. Steroaspects of Diels-Alder reaction and Cope rearrangement. Fluxional
molecules. Retro Diels-Alder, Ene, cheletropic and cis elimination reactions. Synthetic applications.

Unit III Organic Photochemistry 18 h

Photochemical processes. Energy transfer, sensitization and quenching. Singlet and triplet states and their
reactivity. Photoreactions of carbonyl compounds, enes, dienes, and arenes. Norrish reactions of acyclic ketones.
Patterno-Buchi, Barton, photo-Fries and Di-π methane rearrangement reactions. Photoreactions of Vitamin D.
Photochemistry of vision and photosynthesis. Singlet oxygen generation and reactions. Applications of
photoreactions in laboratory and industrial synthesis.

Unit IV Chemistry of natural products 18 h

Structure and synthesis of alpha-Pinene, Camphor, Cadenine and Caryophyllene. Hofmann, Emde and von
Braun degradations in alkaloid chemisty. Structure elucidation of Papaverine, Quinine and Morphine. Synthesis of
Quinine and Papaverine. Structure and synthesis of beta-Carotene, Flavone, Isoflavone, Cyanin and Quercetin.
Biosynthesis of terpenes and alkoloids. Classification and structure of lipids and their biofunctions. Nomenclature,
structure (not elucidation) and biosynthesis of Prostaglandins PGE 2 and PGF 1V

Unit V Chemistry of Biomolecules 18 h

Nomenclature, reactivity and stereochemistry of steroidal system. Stereochemistry and structure


elucidation of cholesterol (no synthesis). Synthesis of Testosterone, Andestrone, Estrone and Progesterone. Steroid
biosynthesis. Structure and synthesis of Vitamins A, C, B1 and Biotin. Structure of penicillins. Synthesis of
paracetamol, phenobarbital, diazepam, sulfamethoxazole, benzyl penicillin and chloramphenicol.
Reference

1. L.M.Harwood, “Polar Rearrangements”, Oxford University


2. J.March, “Advanced Organic Chemistry”, Wiley
3. S.N.Issacs, “Physical Organic Chemistry”, Longman
4. P.Y.Bruice, “Organic Chemistry”, Prentice Hall
5. H.Arora, “Organic Photochemistry and Pericyclic reactions”
6. C.H.Dupuoy, and O.L.Chapman, “Molecular Reactions and Photochemistry”, Prentice Hall
7. J.M.Coxon and B.Holton, “Organic Photochemistry”, Cambridge University Press
8. S.H.Pine, “Organic chemistry”, McGraw-Hill
9. I.L.Finar, “Organic Chemistry”,Vol2, Longman ersity Press.
10. J.Kagan, “Organic Photochemistry”, Academic Press.
11. R.J.Simmonds, “Chemistry of Biomolecules”, Royal Society of Chemistry.
12. J.Mann and others, “Natural Products – Their Chemistry and biological significance”, Longman
13. I.L.Finar, “ Orgnic Chemistry” Vol 2, Longman
14. W.Kar, “Medicinal Chemistry”, Wiley Eastern

CH 223 PHYSICAL CHEMISTRY-II


Total 90 h

Unit I Molecular Symmetry and Basics of Spectroscopy 18 h

Symmetry and Character Tables: Symmetry elements and symmetry operations. Point groups.
Multiplication of operations. Conditions for a set of elements to form a group. Group multiplication table.
Similarity transformation and classification of symmetry operations. Matrix representation of point group.
Reducible and irreducible representations. Character of a matrix. Orthogonality theorem. Rules derived from
orthogonality theorem (proof not required). Setting up of the character tables of simple groups such as C 2v and C 3v
on the basis of the rules. The four areas of the character table.

Basics of molecular spectroscopy: origin of spectra. Energy levels in molecules. Origin of rotational,
vibrational, electronic and Raman spectra and the regions of electromagnetic spectrum where they appear. Intensity
of absorption: Beer-Lambert’s law, selection rule of rotational, vibrational, electronic and Raman spectra. Basic
elements of practical spectroscopy-signal to noise ratio, width and intensity of spectral transitions. Born-
Oppenheimer approximation.

Unit II Spectroscopy-I 18 h

Microwave spectroscopy: Rotation of diatomic molecules. Rotational spectrum: Intensity of spectral


lines. Calculation of internuclear distance. Non-rigid rotors and centrifugal distortion. Rotational spectra of
polyatomic molecules- linear and symmetric top molecules. Introduction to instrumentation. Infrared spectroscopy:
Vibrational spectra of harmonic and anharmonic diatomic molecules. Morse function. Fundamentals and overtones.
Determination of force constants. Interaction of rotation and vibration. Different branches of spectrum.
Asymmetry of vibrational-rotational spectrum. Vibrational spectra of polyatomic molecules. Vibrations of
polyatomic molecules, normal modes, classifications of vibrations: Stretching, bending, symmetric, asymmetric,
parallel and perpendicular vibrations. Overtones, combinations and Fermi resonance. Finger print and group
frequencies. Introduction to instrumentation and FT-IR.
Raman spectra: Scattering of light. Raman scattering. Polarisability and classical theory of Raman
spectrum. Rotational and vibrational Raman spectrum. Raman spectra of polyatomic molecules. Complimentarity
of Raman and IR spectra. Mutual exclusion principle. Introduction to instrumentation. Laser Raman spectrum.
Electronic spectra: Term symbols of molecules. Electronic spectra of diatomic molecules. Vibrational coarse
structure and rotational fine structure of electronic spectrum. Franck-Condon principle. Types of electronic
transitions. Fortrat diagram. Predissociation. Calculation of heat of dissociation. Electronic spectra of polyatomic
molecules: Electronic transitions among molecular orbitals and absorption frequencies. Effect of conjugation on
absorption frequencies. Introduction to instrumentation

Unit III Spectroscopy-II 18 h

Resonance spectroscopy: NMR spectrum. Nuclear spin. Interaction between nuclear spin and applied
magnetic field. Proton nmr spectrum. Population of energy levels. Nuclear resonance Chemical shift. Relaxation
methods. Spin-spin coupling. Fine structure. Elementary idea of 2D and 3D nmr. Mention of nmr spectra of other
nuclei. Introduction to instrumentation. ESR spectrum: Electron spin of molecules. Interaction with magnetic
field. The g factor. Determination of g values. Fine structure and hyperfine structure. Elementary idea of ENDOR
and ELDOR. Mossbauer spectroscopy: principle, Doppler effect, recording of the spectrum, chemical shift, and
quadrupole effect.

Photoelectron spectroscopy: Introduction to UV photoelectron and X-ray photoelectron spectroscopy.


Electron diffraction of gases. Incoherent scattering, Vierl’s equation, correlation and radial distribution.
Polarisation and dipole moment: Debye and Calusius- Mossotti equation. Determination of dipole moments.
Structural information from dipole moments.

Spectral methods: UV-Visible spectrophotometry: fundamental laws of photometry. Basic


instrumentation. Simultaneous determination of two components. Flame emission and atomic absorption
spectroscopy. Instrumentation for AAS. The flame spectra and flame characteristics. Atomiser used in
spectroscopy. Hollow cathode lamp. Interference in AAS. Application of AAS. Mossbauer spectroscopy:
principle and application.

Unit IV Basics of Chemical Thermodynamics 18 h

Thermodynamic properties: State and path properties. Intensive and extensive properties. Exact
differentials. Intrinsic energy, enthalpy, entropy, free energy and their relations and significances. Eulers relation.
Jacobians. Maxwll relations. Thermodynamic equations of state. Joule-Thomson effect. Joule-Thomson
coefficient for van der Waals’ gas. The third law of thermodynamics. Need for the third law. Nernst heat theorem.
Apparent exceptions to third law. Application of third law.

Properties of solutions: Thermodynamics of ideal solutions. Partial molar quantities. Chemical potentials.
Duhem-Margules equation. Nonideal solutions. Excess thermodynamic functions. Determination of partial molar
properties. Fugacity and activity: Fugacity of gases. Determination. Variation of fugacity with temperature and
pressure. Fugacity of liquids and solids. Fugacity of mixtures of gases. Lewis-Randall rule. Fugacity in liquid
mixtures. Activity and activity coefficients. Standard states. Determination of activity and activity coefficients of
electrolytes and nonelectrolytes.

Unit V Application of Thermodynamics 18 h

Chemical equilibrium: Equilibrium constant in real systems. Equilibrium in homogeneous and


heterogeneous system. Reaction quotient. Reaction isotherm and spontaneity of reaction. Variation of eqilibrium
constant with temperature and pressure. Variation of standard free energy with temperature. Simultaneous
equilibria and addition of free energies. Standard free energy of formation and its determination. Free energy
functions.

Phase equilibria: Criteria of eqilibrium. Derivation of phase rule. Discussion of two component systems
forming solid solutions with and without maximum or minimum in freezing point curve. Systems with partially
miscible solid phases. Three component systems: Graphical representation. Three component liquid systems with
one pair of partially miscible liquids. Influence of temperature. Systems with two pairs and three pairs of partially
miscible liquids. Two salts and water systems. Isothermal evaporation. Transition point and double salt formation.

Thermodynamics of irreversible processes: Simple examples of irreversible processes. General theory of


near equilibrium processes. Entropy production from heat flow. Matter flow and current flow. Generalized
equation for entropy production. The phenomenological relations. Onsager reciprocal relation. Application of
irreversible thermodynamics to diffusion. Thermal diffusion. Thermoosmosis and thermomolecular pressure
difference. The Glansdorf-Prigogine theorem. Quantitative introduction to treatment of far from equlibrium states.

At least 100 problems to be worked out from all the units put together
30% of the questions for examination shall contain numerical problems.

References

1. F.A.Cotton, “Chemical Applications of Group Theory”, John Wiley & Sons.


2. V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry” Vishal Publications.
3. H.H.Jaffe and M.Orchin, “Symmetry in Chemistry” John Wiley and Sons
4. P.J.Wheately, “The Determination of Molecular Structure”, Oxford University Press
5. R.L.Carter, “Molecular Symmetry and Group theory”, John Wiley & Sons
6. C.N.Banwell, “Fundamentals of Molecular Spectroscopy”, McGraw Hill
7. Manas Chanda, “Atomic Structure and Chemicl Bonding including Molecular Spectroscopy”, Tate
McGraw Hill
8. G.Herzherg, “Molecular Spectra and Molecular Structure”, D.van Nostrand.
9. S.Glasston, “Theoretical Chemistry”, D van Nostrand.
10. D.C.Gilbert: “Investigation of Molecular Structure”, ELBS
11. R.A.Roberty and R.J.Silbey, “Physical Chemisty”, John Wiley & Sons
12. P.W.Atkins, “Physical Chemistry”, Oxford University Press.
13. D.A.Skoog,D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College
Publishing.
14. R.A.day and A.L.Underwood, “Quantitative Analysis”, Prentice Hall
15. A.I.Vogel, “Textbook of Quantitative Inorganic Analysis”, Longman.
16. S.Glasstone: “Thermodynamics for Chemists”, Affiliated East West Publishers.
17. S.Flasstone and H.S.Taylor, “Ttreatise of Physical Chemistry”, D van Nostrand
18. I.Pregogine, “Introduction to Thermodynamics of Irreversible Processes”, Inter science.

SEMESTER III

CH 231 INORGANIC CHEMISTRY –III


Total 90 h

Unit I Crystalline State 18 h

Crystal systems and lattice types. Bravais lattices. Crystal symmetry. Point groups and space groups (No
detailed study). Miller indices. Reciprocal lattice concept. Close packed structures: BCC, FCC and HCP. Voids.
Coordination number. Crystal binding: Molecular, covalent, metallic and hydrogen-bonded crystals. X-Ray
diffraction by crystals: Functions of crystals. Transmission grating and reflection grating. Braggs equation.
Diffraction methods. Powder, rotating crystal, oscillation and Weisenbeerg methods. Indexing and determination of
lattice type and unit cell dimensions of cubic crystals. Structure factor. Fourier synthesis.

Unit II Solid State Chemistry 18 h

S Electronic structure of solids. Band theory. Refinements to simple band theory; k space and Brillouin
zones. Conductors, insulators and semiconductors. Band structure and applications. Colour in inorganic solids.
Crystal defect: Perfect and imperfect crystals. Point, line and plane defects. Thermodynamics of
Schottkyand Frenkel defects. Colour centers in alkali halide crystals. Defect clusters. Extended defects:
Crystallographic shear structure and stacking faults. Dislocations and crystal structure.

Unit III Electrical and Magnetic Properties of Solids 18 h

Electrical properties of solids: Conductivity of pure metals. Superconductivity. Photoconductivity.


Photovoltaic effect. Dielectric properties. Dielectric materials.

Ferroelectricity, pyroelectricity and piezoelectricity. Applications of ferro, piezo and pyroelectrics.

Magnetic properties of solids: Behaviour of substances in a magnetic field. Diamagnetism,


paramagnetism, ferromagnetism, antiferromagnetism and ferrimagnetism. Effect of temperature. Curie and Curie-
Weiss laws. Calculation of magnetic moments. Magnetism of ferro and antiferromagnetic ordering. Super
exchange. Lasers and their applications.

Unit IV Lanthanides and Actinides 18 h

Lanthanides: Characteristic properties. Electronic configurations and tern symbols Occurrence and
extraction. Separation techniques. Oxidation states. Spectral and magnetic properties. Shapes of f orbitals and
their splitting in cubic ligand field. Actinides: Occurrence and general properties. Electronic configuration and tern
symbol. Oxidation states. Spectral and magnetic properties. Comparative properties of lanthanides and actinides.
Trans-uranium elements and their stabilities. Applications of lanthanide and actinide compounds. Comprehensive
study of the chemistry of beach sands of Kerala and their important components such as monazite, illmenite zircon
and siliminite.

Unit V Nonaqueous Solvents 18 h

Nonaqueous solvents: General properties and classification of solvents. Self-ionization and leveling effect.
Reactions in nonaqueous solvents: Solute-solvent interaction. Reactions in liquid NH3. Solutions of metals in
liquid ammonia. Reactions in anhydrous sulphuric acid, liquid SO2, liquid HF, liquid halogens and interhalogens,
and liquid dinitrogen tetroxide. Titrations in nonaqueous solvents: Acid-base and redox titrations.

References

1. L.V.Azaroff, “Introduction to Solids”, McGraw-Hill.


2. N.B.Hannay, “Solid State Chemistry”, Prentice Hall.
3. F.C.Phillips, “An Introduction to Crystallography” Longman.
4. C.Kittel, “Introduction to Solid State Physics”, John Wiley & Sons.
5. T.Moeller, “The Chemistry of the Lanthanides”, Reinhold.
6. G.T.Seaborg, J.J.Katz and W.M.Manning, “The Transuranium Elements”, McGraw-Hill
7. G.T.Seaborg, “Manmade Transruanium Elements”, Prentice Hall
8. F.A.Cotton (Ed.), “Progress in Inorganic Chemistry”, Interscience.
9. Simon Cotton, “Lanthanides and Actinides”, Macmillan
10. H.Sisler, “Chemistry of Nonaqueous Solvent.
11. Day and J.Selbin, Theoretical Inorganic Chemistry”, East-West Press
12. J.Kucharsky and L.Safarik, Titrations in Nonaqueous Solvents”, Elsevier.

CH 232 ORGANIC CHEMISTRY –III


Total 90 h

Unit I UV-VIS, IR and Mass Spectroscopy 18 h

Electronic transitions in enes, enones and arenes. Woodward-Fieser rules. Effect of solvent polarity on UV
absorption. Principle of characteristic group frequency in IR. Identification of functional groups and other
structural features by IR. Hydrogen bonding and IR bands. Sampling techniques. FTIR and its instrumentation.
Organic mass spectroscopy. Ion production methods: EI, CI,FAB, Electrospray and MALDI, Magnetic, TOF,
Quadrupole and Ion cyclotron mass analyzers. MS n technique. Characteristic EIMS fragmentation modes and MS
rearrangements.

Unit II NMR Spectroscopy and Structure Elucidation 18 h

Chemical shifts, anisotropic effects and coupling constants in organic compounds. Spin-spin interactions in
typical systems. Analysis of 1st order spectra. Simplification methods ofr complex spectra: use of high field NMR,
shift reagents, chemical exchange and double resonance. Introduction to FT (pulse) NMR; NOE; DEPT and
2DNMR. 13C NMR and 13C chemical shifts. Spectral interpretation and structure identification. Spectral
interpretation using actural spectra taken from standard texts. Solving of structural problems on the basis of
numerical and spectrum-based data.

Unit III Organic Synthesis 18 h

C-C and C=C bond forming reactions – Mannich, Reimer-Tiemann, Simon-Smith, Vilsmeier-Haack,
reformatsky and Ullmann reations. Stork enamine reaction. Shapiro, Witting – Horner, Peterson, Heck, Stille and
McMurray reactions. Ring formation by Dieckmann, Thorope and Acyloin condensations. Robinson ring
annulation. Synthesis of small rings. Simon-Smith reaction. Reduction and oxidation in synthesis. Catalytic
hydrogenation. Alkali metal reduction. Birch eduction. Wolff-Kishner reduction. Huang-Milon modification.
Clemmenson reduction. Boranes. LAH, Sodium borohydride as reductants. Dehydrogenations. Oppenauer
oxidation. HIO4, OsO4 and m-ClC6H4COOOH and their applications.

Unit IV Chemistry of Biopolymers 18 h

Peptides and their synthesis. Protecting groups and peptide bond formation in SPPS. Helical and sheet
conformations of polypeptides. Structure organization of proteins. Chemistry of nucleic acid bases A.G.C.T and U
and their synthesis. Synthesis of adenosine and ATP. Structure of DNA. Automated oligonucleotide synthesis by
Phosphoramidite method – Reagents and protecting groups. Sequencing of polynucleotided and polypetides.
Structure of Starch, Cellulose, Glycogen and Chitin.

Unit V Chemistry of Polymers 18 h

Types and mechanism of polymerization reactions. Step-growth, free radical, addition, ionic, ring opening
and gorup transfer polymerizations. Copolymers. Characterization of polymers. Methods of mesurement of
molecular mass and size. Sterochemistry of polymers. Steroregularity and its control. Ziegler-Natta catalysts.
Gelation and network formation. Polymer architecture, configuration and conformation. Frictional properties and
mechanical properties. Glassy and rubbery states, visco-elasticity, crystallization and melting of polymers. Relation
between structure, property and performance. Manufacture and applications of polyolefins, thermoplastics,
polyamides, polyesters, polyurethanes, epoxies and industrial polymers.

References

1. D.H.Williams and I.Fleming, “Spectroscopic Methods in Organic Chemistry”, Wiley.


2. W.Kemp, “Organic Spectroscopy”, Longman
3. J.March, “Advanced Organic Chemistry”, Wiley
4. R.O.C.Norman and A.Coxon, “Modern Synthetic Reactions”, Chapman and Hall
5. M.B.Smith, “Organic Systhesis”, McGraw-Hill
6. R.K.Bansal, “Synthetic Applications in Organic Chemistry”, Narosa
7. R.J.Simmonds, “Chemistry of Biomelecules”, Royal Society of Chemistry
8. I.L.Finar, “Organic Chemistry” Vol 2, Longman
9. R.J.Young, “Introduction to Polymer Science”, John Wiley & Sons
10. F.wW.Billmayer, Text Book of Polymer Science”, John Wiley & Sons
11. G.Odian, “Principles of Polymerization”, John Wiley & Sons
12. J.M.G.Cowie, “Polymers: Chemistry and Physics of Modern Material”, Blackie
13. K.J.Saunders, “Organic Polymer Chemistry”, Chapman and Hall
CH 233 PHYSICAL CHEMISTRY –III
Total 90 h

Unit I Gases Liquids and Liquid Crystals 18 h

Random movement of molecules. Brownian movement and determination of Avogadro number. The
distribution of molecular velocities. Deviation and discussion of Maxwells equation Gamma function. Deviation of
average and most probable velocities from Maxwells equation. Influence of temperature on molecular velocities.
Molecular collisions and mean free path. Homogeneous and heterogeneous collisions. Collision of molecules with
a surface and effusion. Effect of molecular interaction on collision. Transport properties: Viscosity, thermal
conductivity and diffusion. Determination of viscosity of gases. Influence of temperature and pressure on transport
properties.

Liquid state: X-ray diffraction study of simple liquids and their structure. Theories of liquid state.
Oscillator, free space and van der Waals therories. Lennard-Jones theory of melting. Specific heat of liquids.

Liquid crystals: Mesomorphic state, types, examples and application of liquid crystals. Theories of liquid
crystals. Chiral thermotropic liquid crystal polymers. Nematic liquid crystals formed from flexible molecules.
Molecular field theory. Order and odd-even effects in thermotropic nematic polyesters. Photoconducting liquid
crystals. Electro-optic effects in smectogenic polysiloxane side chain liquid crystal polymer.

Unit II Statistical Thermodynamics 18 h

Statistical thermodynamics: Mechanical description of molecular systems. Thermodynamic property and


entropy. Microstates. Canonical and grand canonical ensembles. Equation of state for ideal quantum gases.
Maxwell-Boltzman distribution. The partition functions. Partition function for free linear motion, for free motion in
a shared space, for linear harmonic vibration. Complex partition functions and partition functions for particles in
different force fields. Langevins partition function and its use for the determination of dipole moments.
Electrostatic energies. Molecular partition functions. Trnslational, rotational, vibrational and electronic partition
functions. Total partition functions. Partition functions ant thermodynamic properties.

Unit III-Quantum Statistics and Heat Capacity 18 h

Quantum Statistics-Bose-Einsein statistics. Bose-Einstein distribution, Thermodynamic probability, Bose


Einstein Distribution Function, Example of particles. Theory of paramagnetism. Bose-Einstein condensation.
Kiquid helium. Supercooled liquid. Fermi-Dirac statistics. Fermi-Dirac Distribution, Examples of particles.
Fermi-Dirac Distribution Function, Thermionic emission. Relations between Maxwell-Boltzman, Bose-Einstein and
Fermi-Dirac statistics.

Heat capacity of gases. Equipartition principle and quantum theory of heat capacity. Calculation of Heat
Capacity of gases-Limitation of the Method. Heat capacity of solids. Dulong and Petit’s Law, Kopp’s Law,
Classical theory and its limitation, The vibrational properties of solids. Einstein theory of heat capacity. The
spectrum of normal modes. Limitation of Einstein theory, The Debye theory. The electronic specific heat.

Unit IV Electrochemistry 18 h

Ionics: Ions in solution. Deviation from ideal behaviour. Ionic activity. Ion-solvent interaction. Born
equation. Ion-ion interaction. Activity coefficient and its determination. Debye-Huckel limiting law. Equation for
appreciable concentration. Osmotic coefficient. Activities in concentrated solutions. Robinson-Stoke theory. Ion
association. Strong electrolytes. Ion transport.

Debye-Huckel treatment. Onsager equation. Limitation of the model. Conductance of high frequencies and high
potentials.
Electrodics: Different types of electrodes. Electrochemical cells. Concentration cell and activty
coefficient determination. Origin of electrode potential. Liquid junction potential. Evaluation of thermodynamic
properties. The electrode double layer: Electrode-electrolyte interface. Theory of multiple layer capacity.
Electrocapillary. Loppmann potential. Membrane potential. Elecrokinetic phenomena. Mechanism of charge
transfer at electrode-electrolyte interface. Electrolysis. Current-potential curves. Dissolution, deposition and
decomposition potentials. Energy barriers at metal-electrolyte interface. Different types of over potentials. Butter-
Volmer equation. Tafel and Nemst equations. Rate determining step in electrode kinetics. The hydrogen over
voltage. The oxygen over voltage. Theories of over voltage.

Unit V Electroanalytical Methods 18 h

Potentiometric methods: Reference electrodes and indicator electrodes. The hydrogen calomel, Ag-AgCl
electrodes. The glass electrode – its structure, perofrmance and limitations. Measurement of pH. Petentiometric
titrations. Redox and precipitation titrations. Electrogravimetry: Principle and method. Determination of Cu.
Separation of metals. Conductometry: Principle and method. Conductance measurements. Conductometric
titrations. Coulometry: Principle and method. Coulometric titrations.

At least 150 problems to be worked out from all the units put together.
30% of the questions for Examination shall contain numerical problems.

References

1. G.W.Castellan, “Physical Chemistry”, Addison-Lesley Publishing Co.


2. E.A.Moelwyn Hughes, “Physical Chemistry”, Pergamon Press
3. L.C.Chapoy, “Recent Advances in Liquid Crystalline Polymers”, Elsevier.
4. Denbigh, “Chemical equilibria”, D Van Nostrand.
5. F.W.Sears and Salinger, “An introduction to Thermodynamics, Kinetic Theory of Gases and Statistical
Mechanics”, Addison Wesely.
6. M.C.Gupta, “Elements of Statistical Thermodynamics”, New Age International (P) Ltd.
7. L.K.Nash, “Elements of Statistical Thermodynamics”, Addison Wesley Publishing Co.
8. Kestin and Dofman, “Statistical thermodynamics”,
9. J.Rose, “Dynamic Physical Chemistry”, Sir Issac Pitman & Sons
10. A.W.Adamson, “The Physics and Chemistry of Surfaces”, Interscience
11. D.R.Crow, “The Principles of Electrochemistry”, Chapman and Hall
12. J.O.M.Bokris and A.K.N.Reddy, “Modern Electrochemistry”, Plenum Rosatta.
13. D.A.MacInnes, “ The Principles of Electrochemistry”, Dover Publishers
14. D.A.Skoog, D.M.West and F.J.Holler, “Fundamentals of Analytical Chemistry”, Saunders College
Publishing
15. C.L.Wilson and D.W.Wilson, “Comprehensive Analytical Chemistry”, D van Nostrand.
16. J.G.Dick, “Analytical chemistry”, McGraw Hill

CH 234 INORGANIC PRACTICAL-II


Total 125 h

1. Estimation of simple mixture of metal ions in solution (involving quantitative separation) by volumetric
and Gravimetric and methods.

2. Analysis of some typical ores and alloys: Carbonate ore, sulphide ore, ilmemte, monazite, brass bronze and
type metal.

3. Ion-exchange separation of binary mixtures such as those of zinc and magnesium and cobalt and nickel.
References

1. A.I.Vogel, “A Textbook of Quantitative Inorganic Analysis”, Longman.


2. A.I.Weining and W.P.Schoder, “Technical Methods of Ore Analysis”.
3. W.R.Schoder and A.R.Powell, “Analysis of Minerals and Ores of Rare Elements”.

CH 235 ORGANIC PRACTICAL-II


125 Hrs

(1) Quantitative analysis: Determination of (a) carboxylic acid ester in a mixture, (b) equivalent
weight of a carboxylic acid, (c) reducing sugars using Fehling’s solution, (d) phenol, salicylic
acid aspirin and aniline using bromate-bromidemixture, (e) ketomethyl group in water soluble
ketone such as MEK and Acetone, (f) iodine and saponification values of vegetable oils, and (g)
nitrogen by semimicro Kjeldahl method and sulphur gravimetrically.

(2) Preparation of the following organic compounds by the indicated routes:

(a) p-Nitroaniline: Acetanilide --> p-nitroacetanilide --> p-nitroaniline.


(b) 1,3,5-Tribromobenzene: Aniline --> 2,4,6-tribromoaniline --> 1,3,5-tribromobenzene
(c) Methyl organe: Aniline --> sulphanilic acid --> methyl orange.
(d) p-Aminoazobenzene: Aniline --> diazoaminobenzene --> P-aminoazobenzene
(e) N-Acetyl anthranilic acid: o-Toluidine --> o-methylacetanilide --> N-acetyl anthranilic
acid
(f) P-Chlorobenzoic acid: p-Toluidine --> p-chlorotoluens --> P-chlorobenzoic acid
(g) m-Nitroaniline: Nitrobenzene --> m-dinitrobenzene --> m-nitroaniline
(h) Benzilic acid: Benzoin --> benzil --> benzilic acid
(i) m-Nitrobenzoic acid: Methyl benzoate --> m-nitromethyl benzoate --> m-
nitrobenzoic acid
(j) Benzanilide: Benzophenone --> oxime --> benzanilide

References

1. A.I.Vogel, “A Textbook of Practical Organic Chemistry”, Longman


2. A.I.Vogel, “Elementary Practical Organic Chemistry – Part 3: Quantitative Organic Analysis”, Longman
3. F.G.Mann and B.C.Saunders, “Practical Organic Chemistry”, Longman

CH 236 PHYSICAL PRACTICAL-II


Total 125 h

A student has to carry out at least 35 experiments without omitting any of the topics given below:

1. Physical properties of liquids

(a) Viscosity: Viscosity of liquids and mixtures of liquids. Verification of Kendall’s equation.
Composition of unknown mixtures. Determination of molecular masses polymers by viscosity
measurements.

(b) Surface tension: Surface tension and parachor of liquids by stalagmomenter and differential
capillary methods. Calculation of atomic parachor. Variation of surface tension with

concentration. Unknown concentration of a mixture. Interfacial tension. Determination of surface excess


and area per molecule.
2.Beckmann method

Determination of molar depession constants of benzene and water using Beckmann thermomenter.
Determination of molecular mass. Study of he complex, K2HgI4.

3.Optical methods

(a) Polarimetry: Measurement of specific rotation. Concentrations of glucose and sucrose in a mixture.
Tate of inversion of sucrose.

(b) Spectrophotometry: Absorption spectra of coloured compounds. Verification of Beer’s law.


Determination of equlibrium constants of acid-base indicators. Determination of rate constant.
Simultaneous determination of Mn and Cr in a solution of KmnO 4 and K 2Cr2O7.

4.Refractometry

Refractive index and molar refraction of liquids. Atomic refractions. Composition of mixtures. Molar
refraction of solid solutes. Study of the complex, K2HgI4. Molecular and ionic radii from molar refractions.

5.Electrochemistry

(a) Conductance: Equivalence conductance of solutions of strong electrolytes and ewak electrolytes.
Application of Kohlrausch’s law. Onsager constant. Solubility of sparingly soluble substances.
Ostwald’s dilution law. Hydrolysis of salts. Ionic products of solvents. Basicity of acids.
Dissociation constants of acids and bases. Conductometric titrations involving acid-base and
precipitation. Solubility of calcium sulphate in water-alcohol mixture.

(b) Electromotive force: Cell potentials. Electrode potentials. Concentration cells. Redox potentials.
Determination of activity coefficeint. Degree of hydrolysis. Determination of pH using quinhydrone,
antimony and glass electrodes. Potentiometric titrations involving acid-base, redox and precipitation.
Application of Henderson’s equation.

(c) Polarography: Determination of half-wave potentials of single ions and mixture of ions.
Determination of formulae and stability constants of complexes. Polarographic titrations.

References

1. A.Finlay and J.A.Kitchener, “Practical Physical Chemistry”, Longman


2. F.Daniels and J.H.Mathews, “Experimental Physcial Chemistry”, Longman
3. A.M.James, “Practical Physical Chemistry”, J.A.Churchil
4. H.H.Willard, L.L.Merritt and J.A.Dean, “Instrumental Methods of Analysis”, Affiliated East-West Press
5. D.P.Shoemaker and C.W.Garland, “Experimental Physical Chemistry”, McGraw-Hill

SEMESTER IV

CH 241(a) – ADVANCED INORGANIC CHEMISTRY


Total 90 h

Unit I Group Theory 18 h

Properties of a group. Point groups. Abelian groups. Cyclic group. Subgroup. Similarity transformation.
Classes of symmetry operation. Matrix representation of symmetry operation. Representation of groups. Trace of a
matrix. Reducible and irreducible representations of groups. Orthogonality theorem. Rules of irreducible
representation and their properties. Construction of character tables for C2v and C3v systems.
Unit II Applications of Group Theory 18 h

Hybrid orbitals and molecular orbitals for simple molecules. Transformation properties of atomic orbitals.
Hybridization schemes for σ and π bonding with examples. MO theory for ABn type molecules. Molecular orbitals
for regular octabedral, tetrahedral and metal sandwich compounds.

Ligand field theory: Splitting of d orbitals in different environments using gorup theoritical considerations.
Construction of energy level diagrams. Correlation diagram. Method of descending symmetry. Tanabe-Sugano
diagrams. Molecular orbitals in octahedral complexes. Formation of symmetry adapted group orbitals of ligands.
MO diagram.

Symmetry and selection rules: Symmetry properties of common orbitals. Application of character tables to
infrared and Raman spectroscopes.

Unit III Bonding, Symmetry and Structure of Solids 18 h

Types of solids: Ionic, covalent, molecular, metallic and hydrogen bonded solids. Cohesive forces in
crystals. Lattice energy. Madelung constant. Determination of lattice energy. Zone theory. Superconductivity.
High temperature superconductivity Packing of atoms and ions in solids. Voids. Coordination of voids.

Crystal systems. Bravais lattices. Crystal symmetry. Point groups. Representation as stereogarms.
Examples from orthorhombic, cubic and hexagonal systems. Space groups. Representation as parallelograms.
Some important structural types: Rutile, pervoskits, rock salt, zinc blende, antifluorite, wurtzite and nickel, arsenide.
Spinels and inverse spinels.

Unit IV Properties of Solids 18 h

Diffusion in solids: Types of diffusion. Mechanisms of diffusion. Theories of diffusion. Diffusion and
defects. Diffusion controlled reactions. Order-disorder transformations. Super strictires. Crystal growth.
Electrical properties: Electrical conductors. Dielectric properties. Piezoelectricity, ferroelectricity and ionic
conductivity. Optical properties: Photoconductivity, luminescence, colour centers, lasers, refractions and
bifringence. Magnetic properties: Diamagnetism, paramagnetism,ferromagnetism, antiferromagnetism and
ferrimagnetism. Thermal properties: Thermal conductivity. Specific heat. Thermal decomposition of solids.
Photographic process. Self-heating and explosion.

Unit V Solid State Reaction Kinetics 18 h

Isothermal and nonisothermal decompositions. Types of solid-state reactions. Analysis of decomposition


data using different methods: Approximation, differential and integral methods
Choosing Horrowitx-Metzger, Coasts-Redfern and Freeman-Carroll methods as examples. Evaluation of kinetic
parameters such as order parameter, pre-exponential factor, energy of activation and entropy of activation from these
methods. Critical comparison between the three different methods. Factors influencing the rate of solid-state
reactions. Elucidation of mechanisms of decomposition reactions of solids.

References

1. F.A.Cotton, “Chemical Applications of Group Theory”, Interscience.


2. M.C. Day and J.Selbin, “Theoretical Inorganic Chemistry”, Affiliated East-West Press.
3. P.K.Bhattacharya, “Group Theory and its Chemical Application”, Himalayan Publishing House
4. V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry”, Vishal Publications
5. L.V.Azaroff, “Introduction to Solids”, McGraw-Hill
6. Antony R.West, “Solid State Chemistry and its Applications”, Wiley Eastern
7. N.B.Hannay, “ Solid State Chemistry”, Prentice Hall
8. D.A.Young, “Decomposition of Solids”, Pergammon Press
9. R.M.Rose and J.Wulf, “The Structure and Properties of Materials” ,Vol I & II, Wiley Eastern
10. William W.Portfield, “Inorganic Chemistry – A Unified Approach”, II Edition, Academic Press
11. W.W.Wendlandt, “Termal Methods of Analysis”, John Wiley & Sons
12. T.Hatakeyama and F.X.Quinn, “Thermal Analysis”, John Wiley & Sons

CH 241 (b) – ADVANCED ORGANIC CHEMISTRY


Total 90 h

Unit I Physical Organic Chemistry 18 h

Reactivity in relation to molecular structure and conformation. Steric effect. F strain. Ortho effect. Bond
angle strain. Conformational effects on the reactivity of substituted cyclohexanes. The Hammett equation and its
applications. Taft equation. Linear free energy relationships. Solvent polarity and parameters. Y,Z and E
parameters and their applications. Primary and secondary kinetic isotope effects. Salt effects and special salt effects
in SN reactions. Kinetic and thermodynamic control of reactions. The Hammond postulate. Principle of
microscopic reversibility. Marcus theory. Methods of determining reaction mechanisms. Phase transfer catalysis
and its applications.

Unit II Methods in Organic Synthesis 18 h

Retrosynthetic analysis and disconnection approach. Synthetic strategy and synthons. Regioselectivity in
enol and enamine alkylations Steroselective and stereospecific synthesis. Mitsonobu reaction. 1,3-dipolar
cycloaddition in the construction of rings. Story synthesis. Olefin synthesis by extrusion reactions. Olefin
metathesis. FMOC, BOC, Z, trityl, phthalimide, benzyl, tetrahydropyranyl, silyl, t-butyl, trichloroethyl, acetal and
thioacetal as amino, hydroxy, thiol, caroxyl and carbonyl protecting groups in synthesis. Umpolung.
Electrochemical reduction and oxidation reactions. Cathodic reduction of organic halogen, nitro and carbonyl
compounds. Reductive coupling reactions. Conversions of C=O to C=CH2; epoxide to alkene and alkene to cis and
trans diols. Prevost and woodward procedures.

Unit III Reagents in Organic Synthesis 18 h

Applications of hydrogenation catalysts, hindered boranes, bulky metal hydrides, NaCNBH3. DIBAL, Li
trialkyl borohydrides, tri-n-butyl tin hydride, diimide, Kindlar catalysts and Rosenmund reduction. McFadeyan-
Stevens reactions. Oxidation using SeO2, lead tetraacetate, ozone, peracids,

DDQ and Cr(VI) reagents. Swern oxidation, Moffatt oxidation, allylic and benzylic oxidation Sommelet reaction.
Elbs reactions. Oxidative coupling of phenols. Sharpless assymetric epoxidation Chemo and regioselectivity in
reductions and oxidation. Use of XeF2, SbF5,VF5,MoF6,CF3OF,SF4, HF and F2 as fluorinating agents

Unit IV Organometallic Chemistry 18 h

Preparation of organo Mg, Li, Cu, Zn and Re compounds. Reactions of Grignard reagents in organic
synthesis – Alkylation, oxirane addition, carbon dioxide addition, carbonly addition enone addition (1,2- and 1,4-
additions), reduction and enolisation reaction. Reactions of organolithium reagents – Li exchange reaction and its
use in the preparation of Rli compounds, addition to C=O COOH and CONR2, Li dialkylcuprates (Gilman reagent) –
preparation reaction with alkyl halides with acyl halides and with enones. Alkynyl Cu(I) reagents. Glaser coupling.
Dialkyl Cd compounds preparation and reaction with acyl halides. Benzenetricarbonyl Chromium – preparation and
reaction with carbanions. Tebbe reagent

Unit V Molecular Tecognition and Supramolecular Chemistry 18 h

The concepts of molecular recognition, host, guest and receptor systems. Forces involved in molecular
recognition. Hydrogen bonding, ionic bonding, π – stacking, van der Walls and hydrophobio interactions.
Introduction to molecular receptors: Tweezers, Cryptands and Carcerands, Cyclophanes Cyclodextrins and
Calixarenes-Typical examples. Non-covalent interactions in biopolymer strructure organization. Importance of
molecular recognition in DNA and protein structure, their function and Protein biosynthesis.

References

1. N.S.Issacs, “Physical Organic Chemistry”, Longman


2. R.A.Y.Jpmes, “Physical and Mechnaistic Organic chemistry”, Cambridge Univ. Press
3. J.Hine “Physical Organic Chemistry”, Academic
4. M.B.Smith, “Organic Synthesis”, McGraw Hill
5. H.O.House, “Modern Synthetic Reactions” Benjamin Cummins
6. R.K.Mackie, D.M.Smith, and R.A.Aitken, “Guide Book to Organic Synthesis Longman, 2Edn
7. W.Carruthers, “Some Modern Methods of Organic Synthesis”, Cambridge Univ. Press
8. M.Bochmann, “Organomettalics Vols. I and II” Oxford Chem. Primer No. 12 ann 13, OUP
9. R.M.Merhora and Singh, “Organometallic Chemistry”
10. H.Vogtle, Supramolecular Chemistry”, Wiley
11. J.M.Lehn, “Supramolecular Chemistry”, VCH
12. D.Nasipuri, “Stereochemistry of Organic Compounds”, Wiley.
13. J.Mann and others, “Natural Products – Their Chemistry and Biological Significance Longman
14. D.Voet and J.G.Voet, “Biochemistry”, Wiley
15. H.Dugas, “Bioorganic Chemistry” 3Edn, Springer

CH 241(C) – ADVANCED PHYSICAL CHEMISTRY


Total 90 h

Unit I Molecular Symmetry and Character Table 18 h

Molecular symmetry: Symmetry elements and symmetry operations. Point groups Properties of a group.
Abelian, cyclic and subgroups. Classification of elements. Groups representation and character table. Derivation of
character tables of point groups such as C2h C 4v and D3h. Mullikans symbols. Transformation properties of dipole
moment components. Rotational motion of molecules. Polarisability tensors. Construction of representation using
different base vectors such as Cartesian coordinates, mathematical functions and atomic orbitals.

Reduction formula: Reduction of reducible representations to irreducible representations. Transformation


properties of atomic orbitals in various point groups. Construction of hybrid orbitals. Identification of atomic
orbitals participating in the hybridization of triangular planar-AB3, tetrahedral-AB4, square planar-AB4, square
pyramidal-AB4, triangular bipyrmaidal-AB5, square pyramidal-AB5 and octahedral-AB6 molecules.

Unit II Application of Character Table 18 h

Spectroscopic Applications: Transition moment integral and transition moment operator. Vasishing matrix
element- symmetry and selection rules for IR, Raman and electronic spectra. Dipole and polarisability transition
moment operators. Identification of IR and Raman active normal modes in molecules coming under different point
groups such as C2v, C3v, C4v, D3h, Td and Oh. Verification of mutual exclusion and complimentarity principles of IR
and Raman spectra and their use in identification of molecular structure. Probability of overtones and combination
bands. Identification of allowed and forbidden electronic transitions in carbonly group. Vibronic transitions.

Application to MO theory: Symmetry adapted LCAO-MO theory of π -bonded bydrocarbons. Projection


operator and its use in the construction of wave functions of π molecular orbitals, secular equations and use of
symmetry for simplifying the calculations of energy and wave function. HMO calculation of energy and wave
functions of ethylene, butadiene and carbocyclic systems such as benzene and naphthalene.

Unit III Exactly Solvable systems 18 h

Recapitulation of simple harmonic oscillator: Wave equation, soulution and Hermite polynomial. The
three dimensional harmonic oscillator. Potential energy in three dimension and Schrodinger wave equation in
Cartesian coordinate. Separation of variables and solution of he equations for energy and wave function.
Degeneracy.

Rigid Rotor: Schrodinger in polar coordinates. Angular momentum operator for rigid ortor, separation of
variables and complete solution of the Ø and θ equations. Legendre polynomials and associated Legendre funcions.
Normalisation of associated Legendre fuction and evolution of the values of orbital angular momentum quantum
number. Recurrence relation. Rigid rotor wave function and energy. The spherical harmonics.

The Hidrogen atom: Schrodinger wave equation in polar coordinates. Separation of variables and
complete solution of the radial part. The associated Laguarre polynomial. Normalisation. The evolution of the
values of the principal quantum number. The spherical harmonic and radial part of the wave functions. The total
wave function of H-atom. The wave functions of H-atomic orbitals and explanation of the shapes of various
orbitals.

Unit IV Approximate Systems I 18 h

Schrodinger wave equations for belium atom and anharmonic oscillator and difficulty to get the exact
solution of these equations. The variation method: Variation theorem and its proof. The variation integral and its
properties. Variational parameters. Trial wave functions. Illustration of use of trial wave function for calculation of
energy taking H atom as example. Setting up of secular determinants.

Trial functions as linear combination of orthonormal functions. Linear combination of functions containing
variational parameters as trial function. Variation methods of normal state of helium atom- use of atomic units, the
more generalized variation method. The self-consistent field method, SCF and variation method. Strength and
limitations of the method.

The WKG approximation: Schrodinger wave equation in powers of h/2... and solution to obtain the general
form of the wave function. Validity of the approximation.

Unit V Approximate Systems II 18 h

The perturbation theory: The generalized perturbation theory and the idea of successive correction to
uperturbed problem. First order perturbation. Correction of wave function and energy. Theory of non-degenerate
level perturbation. The mormal helium atom. The first order perturbation of the degenerate level. The hydrogen
atom. Second order perturbation theory. Correction for wave function and energy, Stark effect.

Time dependent perturbation theory: Variation in the state of a system with time. Emission and absorption
of radiation. The Eistein transition probabilities and their calculations. Selection rule and intensity of spectrum for
harmonic oscillator, rigid rotor and hydrogen atom.

Slater’s treatment of complex molecules: Wave function for the system of three hydrogen atoms.
Generalized valence bond method. The generalized Hellmann-Feynmann theorem and its significance.

At least 100 problems to be worked out from all the units together
20% of the questions for examination shall contain problems.

References

1. F.A.Cotton, “Chemical Applications of Group Theory”, John Wiley & son


2. V.Ramakrishnan and M.S.Gopinathan, “Group Theory in Chemistry”, Vishal Publications
3. J.D.Donaldson and F.D.Ross, “Symmetry and Stereochemistry”, Inter text
4. R.L.Cater,” Molecular Symmetry and Group Theory”, John Wiley & Son
5. J.M.Anderson, “Mathematics for Quantum Chemistry”, W.A.Benjamin
6. D.A.McQuarrie, “Physical Chemistry- A Molecular approach”, Viva Low-priced Student Edition
7. S.Glasstone, “Theoretical Chemistry”, D van Nostrand
8. L.Pauling and E.B.Wilson, “Introduction to Quantum Mechanics”, McGraw Hill
9. G.W.Castellan, “Physical Chemistry”, Narosa Publishing House.

CH 242 DISSERTATION
Total 180 h

Each of the students has to carry out original research in a topic in accordance with the Elective paper
chosen for Semester IV under the guidance and supervision of a teacher in the concerned Department of the College.

Instructions to Question Paper Setters

The syllabus of each theory paper has five Units. While setting the question papers, equal weight is to be
given to each of the Units for choosing questions. Each question paper is of 3 hours duration and has three Sections,
namely Section A, Section B and Section C constituting a total of 75 marks as detailed:

Section A – Five questions, one from each Units containing three short answer questions marked (a), (b), and (c),
each of which has 2 arks. One has to answer any two of (a), (b), or (c) from each of the five questions. (2 x 10 = 20
marks)

Section B – Five questions, one from each Unit containing two short essay questions marked (a) and (b), each of
which has 5 marks. One has to answer either (a) or (b) from each of the five questions. (5 x 5 = 25 marks)

Section C – Five essay questions, one from each Unit having 10 marks. One has to answer any three questions from
the five questions asked. (10 x 3 = 30 marks)