IIS University - International College for Girls - ICG Courses

M.Sc. (Chemistry)

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Duration: 2 Years

Eligibility: Graduation

Course Structure

Course Code	Course Title
Semester – I
CHY- 121	Bonding in Co-ordination Chemistry and Inorganic Reaction Mechanism
CHY- 122	Basics of Organic Chemistry
CHY- 123	Quantum Chemistry and Chemical Kinetics
CHY-124	Principles of Spectroscopy
CHY-125	(a) Mathematics for Chemists (For students without Maths in B.Sc.)
CHY-125	(b) Biology for Chemists (For students without Biology in B.Sc.)
CHY-126	Laboratory Course I
CHY-127	Communication Skill
Semester – II
CHY- 221	Advanced Inorganic Chemistry
CHY- 222	Mechanism of Organic Reactions
CHY- 223	Thermodynamics
CHY- 224	Spectroscopy of Organic Compounds
CHY- 225	Computer for Chemists
CHY-226	Laboratory Course II
CHY-227	Seminar
Semester – III
CHY- 321	Thermal and Photochemical Reactions
CHY- 322	Organotransition Metal Chemistry
CHY- 323	Electrochemistry and Surface Phenomena
CHY- 324	Analytical Methods
CHY-325	Projects and Work Visit
CHY-326	Laboratory Course III
CHY-327	Laboratory Course IV
CHY-328	Laboratory Course V
Semester – IV
CHY 421	Introduction to Green Chemistry
CHY 422	Research Project / Dissertation
Group - A Elective Paper I CHY-423-A Polymers Objective Elective Paper II CHY 424-A Environmental Chemistry Elective paper III CHY 425-A Biomolecules and Bio-organic Chemistry
Group - B Elective Paper I CHY 423-B Inorganic Materials Elective Paper II CHY-424-B Bioinorganic Chemistry Elective Paper III CHY 425-B Nuclear and Radiation Chemistry
Group -  C Elective Paper I CHY 423-C Heterocyclic Chemistry Elective Paper II CHY 424-C Organic Synthesis and Chemistry of Natural Products Elective paper III CHY 425-C Biomolecules and Bio-organic Chemistry Elective paper IV CHY 426-C Computational Chemistry
Group -  D Elective Paper I CHY 423-D Biophysical and Corrosion Chemistry Elective Paper II CHY 424-D Solid State and Supramolecular Chemistry Elective Paper III CHY 425-D Physical Organic Chemistry

 

Course Syllabus

Semester - I

CHY- 121 Bonding in Co-ordination Chemistry and Inorganic Reaction Mechanism

 Objective

To learn about kinetics and reaction mechanism of transition metal complexes and acquaint them with the nature of metal-ligand bonding in coordination compounds.

Unit  I Stability of Complex ions in Solutions

Stepwise and overall formation constants, effect of ligands and metals on stability constants of complexes, chelate effect; determination of the composition and formation constants of complexes – mole ratio method, solubility method, spectral methods (sloperatio and Job’s method) and Bjerrum’s method (pH-metry).

Self Study: Kinetic and thermodynamic stability of complex ions.

Unit  II Reaction Mechanism of Transition Metal Complexes-I

Ligand Substitution Reactions: patterns of reactivity, classification of mechanisms, energy profile of reaction transition states; inert and labile complexes; kinetics of substitution reactions in octahedral complexes, factors affecting SN1 and SN2 mechanism acid hydrolysis and factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidence in favour of conjugate mechanism; anation reactions; reactions without metal ligand bond cleavage.

Unit  III Reaction Mechanism of Transition Metal Complexes-II

Mechanism of substitution in square planar complexes, trans effect, theories of trans effect and its uses, factors affecting substitution reactions in square planar complexes, cis effect, cis-trans isomerization.

Redox Reactions: classification, mechanism of one electron transfer reaction – outer sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions.

Unit  IV Molecular Orbital Theory-I (bonding)

Pre requisite: Crystal field theory.

Ligand field theory; introduction to the molecular orbital diagrams of some simple polyatomic molecules like BeH2, H2O; complexes involving only _ bonding, LCAO’s approximation; _-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes.

Unit  V Molecular Orbital Theory-II (bonding)

_-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes; effect of pi-bonding (_- type ligands); experimental evidences for pi-bonding (crystallography, Infra red spectroscopy); angular overlap model – principles, angular overlap and geometry.

 

CHY- 122 Basics of Organic Chemistry

Objective

To learn the basics of organic chemistry and the three dimensional concepts of molecules, elements of symmetry and stereochemistry.

Unit  I Nature of Bonding in Organic Molecules

Pre requisite: Delocalized chemical bond – conjugation, cross conjugation, resonance and field effects. hyperconjugation, tautomerism. Aromaticity in benzenoid and non-benzenoid compounds, alternant and non-alternant hydrocarbons, Huckel’s rule and Möbius system, energy level of _ molecular orbitals in simple systems (ethylene, 1, 3 butadiene, benzene and allylic system), Huckel’s theory of conjugated systems, bond order and charge density calculations, applications to ethylene, and butadiene. Annulenes, fullerenes, antiaromaticity, homoaromaticity, PMO approach, steric inhibition to resonance.

Bonds weaker than covalent – addition compounds, phase transfer catalysis and crown ether complexes, cryptands, inclusion compounds, cyclodextrins, catenanes, rotaxanes and Kekulene.

Unit  II Reaction Mechanism: Structure and Reactivity

Structure and Reactivity: Concept of linear free energy relationship-Hammett and Taft equations, application in the determination of organic reaction mechanisms. Hammond’s postulates, Nucleophilicity, Curtin- Hammett principle

Pre requisite: Types of reactions, types of mechanisms, general principles for the determination of reaction mechanism. Organic Reaction Dynamics and Reactive Intermediates: general methods for the  determination of reaction mechanism – product analysis, determination of presence of  intermediates, study of catalysis, isotopic labelling, stereochemical evidences, kinetic evidences and isotope effects. Methods of generation, structure and reactivity of carbocations, carbanions, radical-anions and radical-cations, arynes, carbenes and nitrenes.

Unit  III Molecular Rearrangements

General mechanistic consideration –

A detailed study of the following rearrangements: Pinacol-pinacolone rearrangement, Wagner-Meerwein rearrangement, Damjanov rearrangement, Benzil-benzilic acid rearrangement, Favorskii rearrangement, Arndt-Eistert  rearrangement, Neber rearrangement, Beckmann rearrangement, Hofmann rearrangement, Curtius rearrangement, Lossen rearrangement, Schmidt rearrangement, Wolff rearrangement, Baeyer-Villiger oxidation, Shapiro reaction, Dienone- phenol rearrangement, Wittig rearrangement.

Unit  IV Stereochemistry – I

Pre requisite: Conformation, configuration, erythro and threo isomers, E,Z and D,L nomenclature. Optical isomerism, elements of symmetry chirality, enantiomers, diastereomers, R,S nomenclature, absolute configuration, optical purity resolution, prochirality; enantiotopic and diastereotopic atoms, groups and faces.

Pseudoasymmetry: optical activity in the absence of chiral carbons (biphenyls, allenes, spiranes, ansa compounds and cyclophanes), chirality due to helical shape; chirality in the compounds containing N, S and P.

Unit  V Stereochemistry - II

Geometrical isomerism in cyclic and condensed systems (decalins, decalols and decalones), conformational analysis of cycloalkanes (5, 6, 7 membered rings) and decalins, effect of conformation on reactivity, conformations of sugars (glucose,maltose and sucrose), steric strain due to unavoidable crowding. Asymmetric synthesis, Cram’s rule, Prelog’s rule, CD, ORD, octant rule, Cotton effect and their application in determination of absolute and relative configuration and conformation.

Self Study - Geometrical isomerism in acyclic systems.

 

CHY- 123 Quantum Chemistry and Chemical Kinetics

Objective

To learn chemical bonding and quantum mechanical concepts.To learn rate laws from a proposed mechanisum and analyze kinetics in gases and solutions.

Unit  I Introduction to Quantum Mechanical Results

Schrodinger equation, postulates of quantum mechanics, operators and commutation relations, discussions of solutions of the Schrodinger equation to some model systems – particle in a box, harmonic oscillator, rigid rotor, hydrogen atom.

Unit  II Approximate Methods and Angular Momentum

The variation theorem, linear variation principle, perturbation theory (first order and non – degenerate), application of variation method and perturbation theory to helium atom, ordinary and generalized angular momentum, eigen functions and eigen values for angular momentum, operator using ladder operators, addition of angular momenta, spin, antisymmetry and Pauli’s exclusion principle.

Unit  III Theories of Reaction Rate

Pre requisite: Factors affecting rate of chemical reactions, comparison between order and molecularity, units of rate constants for different orders of reactions Scope, laws of chemical kinetics, order of reaction and determination of order of reaction, methods of determining rate laws, differential and integrated form of rate expression (1st, 2nd …….nth order), rate expression for opposing, parallel and consecutive reactions; collision theory of reaction rates, steric factor, activated complex theory, comparison between collision theory and activated-complex theory.

Unit  IV Elementary Reactions in Gas Phase and in Solution

Unimolecular gas reactions, dynamics of unimolecular reactions (Lindemann, Hinshelwood and Rice-Ramsperger – Kassel-Marcus RRKM theories); primary and secondary salt effects-influence of ionic strength and dielectric constant on reactions involving (i) ions (ii) dipoles (iii) ion and dipole.

Unit  V Complex Reactions

Steady state approximation in reaction mechanisms; kinetic and thermodynamic control of  the reactions; chain reactions – thermal and photochemical reactions, dynamic chain (mechanism of hydrogen-bromine and hydrogen-chlorine reactions), decomposition of ethane, pyrolysis of acetaldehyde; oscillatory reactions – Belousov-Zhabotinsky reaction; enzyme catalysis – Michaelis-Menten kinetics.

Self Study: Factors affecting enzyme catalyzed reactions, effect of pH on enzymes

 

CHY-124 Principles of Spectroscopy

Objective

To learn the basic principles of spectroscopy beneficial in their further endeavours in research.

Unit  I Basic Elements of Spectroscopy

Pre requisite: Interaction of electromagnetic radiation with matter. Characterization of electromagnetic radiation, quantisation of energy,  Regions of the spectrum, representation of spectra, basic elements of practical spectroscopy, signal-to-noise ratio – resolving power, line width – natural line broadening, Doppler broadening, Heisenberg uncertainity principle; intensity of spectral lines – transition probability, population of states, path length of sample; Born-Oppenheimer approximation; rotational, vibrational and electronic energy levels in molecules; transition moment, selection rules, Fourier Transform methods (IR and NMR)

Unit  II Rotational Spectroscopy: Microwave Spectroscopy

Diatomic molecules as rigid rotors: rotational energy levels, intensity of spectral lines, selection rules, effect of isotopic substitutions, calculation of bond length for linear, di- and tri-atomic molecules. Diatomic molecules as non rigid rotors: rotational transition, centrifugal distortion constant, rotational spectra of linear and symmetric top poly-atomic molecules; Stark effect, nuclear and electron spin interaction and effect of external fields; applications.

Unit  III Vibrational Spectroscopy

IR spectroscopy: vibrating diatomic molecule- energy of diatomic molecules as simple harmonic oscillator, zero point energy, force constant, bond strengths, vibrational transitions and selection rules, anharmonicity, Morse potential energy diagram, vibrational transitions and selection rules; vibrational-rotational spectroscopy - breakdown of Born – Oppenheimer approximation rules, selection rules, P, Q, R branches; vibration of poly atomic molecules- symmetry and fundamental vibrations, normal mode of vibrations, skeletal vibrations, group frequencies, overtones, hot bands, fermi resonance bands; influence of rotation on the spectra of polyatomic molecules – parallel and perpendicular vibrations in linear and symmetric top molecules. Raman spectroscopy: classical and quantum theories of Raman effect, Rayleigh and Raman scattering, stokes and antistokes radiation, molecular polarizability, selection rules; rotational Raman spectra – linear molecules, symmetric top and spherical top molecules;  vibrational Raman spectra- symmetry and Raman active vibrations, rules of mutual exclusion; rotation- vibration Raman spectra of diatomic molecules, polarized and depolarized Raman spectra.

Self Study: Resonance Raman spectroscopy, coherent antistokes Raman spectroscopy CARS (brief idea)

Unit  IV Electronic Spectroscopy

Atomic spectroscopy: energy of atomic orbital, vector representation of momenta and vector coupling, spectra of hydrogen atom and alkali metal atoms.

Molecular spectroscopy: energy levels, molecular orbitals, vibronic transitions, vibrational progression; geometry of excited states, Franck-Condon principle, emission spectra, radiation and non-radiation decay, internal conversion.

Photoelectron spectroscopy: basic principle, ionization process, Koopmen’s theorem, photoelectron spectra of simple molecules, ESCA, chemical information from ESCA, Auger electron spectroscopy (basic idea).

Self Study: Spectra of transition metal complexes, charge transfer spectra.

Unit  V ESR and Mossbauer Spectroscopy

Electron spin resonance spectroscopy: basic principles, zero field splitting and Kramer’s degeneracy, factors affecting ‘g’ value, hyperfine coupling, isotropic and anisotropic hyperfine coupling constant, spin Hamiltonian, spin densities and McConnell relationship, measurement techniques, spin polarization for atoms and transition metal ions, application to transition metal complexes (having one unpaired electron) including biological systems and to inorganic free radicals such as PH4, F2 - and [BH3]-. Mossbauer spectroscopy: basic principles, spectral parameters and spectrum display, application of technique to studies of bonding and structure determination of compounds.

 

CHY-125 (a) Mathematics for Chemists (For students without Maths in B.Sc.)

Objective

To improve the analytical skills. To understand the subject as tool applicable in chemical science.

Unit  I Matrix Algebra

Matrix addition and multiplication, adjoint, transpose and inverse of matrices, special matrices (symmetric, skew-symmetric, unit, diagonal); determinants (examples from Huckel theory)

Unit  II Differential Calculus

Rules for differentiation, applications of differential calculus including maxima and minima (examples related to maximally populated rotational energy levels, Bohr’s radius and most probable velocity from Maxwell’s distribution etc.); partial differentiation, coordinate transformations.

Unit  III Integral calculus

Integral calculus: basic rules for integration, integration by substitution, integration by parts and through partial fraction.

Unit  IV Permutation, Probability ,Vector Algebra and Calculus

Permutation and Probability: permutations and combinations, probability and probability theorems, curve-fitting (including least squares fit etc.) with a general polynomial fit. Scalars and vectors, additional and subtraction of vectors, multiplication of vectors – scalar and vector product, vector operators – gradient, divergence and curl. (Expressions only).

Unit  V Elementary Differential Equations

Order and degree of differential equation solution of first order and first degree linear differential equation by variable-separable; homogenous and linear equations; applications to chemical kinetics, secular equilibria, quantum chemistry etc.

 

CHY-125 (b) Biology for Chemists   (For students without Biology in B.Sc.)

Objective

To learn the basic life processes which link the biological systems with the chemical systems.

Unit  I The Matrix of Life

Origin of life and living system, prebiotic evolution of macromolecules; elementary idea of prokaryotic and eukaryotic cells, cell organelles and their functions, difference between plant and animal cells.

Biomolecules: chemical composition and bonding; three dimensional configuration and confirmation, chemical reactivity; macromolecules and their monomeric units.

Unit  II Energetics of Life

Energetics of metabolic processes; energy rich phosphate compounds; glycolysis; TCA cycle, ETC, oxidative phosphorylation, HMP; fatty acid synthesis, _ and _ oxidation.

Unit  III Amino acids and Proteins

Structure of Zwitter ion; types of amino acids – essential and non essential; degradation and biosynthesis of amino acids, amino acid sequencing.

Proteins: covalent structure and three dimensional structure; _ helix and _ sheets; secondary, tertiary and quaternary structure; protein function – complementary and reversible interactions between proteins and ligands (immunoglobulins and O2 binding proteins).

Unit  V Carbohydrates

Monosaccharides, disaccharides and polysaccharides; structure, function and derivatives, structural and storage polysaccharides.

Glucocojugates: proteoglycans, glycoproteins and glycolipids. Lipids: fatty acids, essential fatty acids; triglycerols, steroids, cholesterol, sphingolipids and prostaglandins; structural lipids in membranes.

Unit  V Nucleic Acids

Purines and pyrimidines; linkages; structure of RNA and DNA, double helical structure, DNA replication, transcription and translation – the chemical basis for heredity.

 

CHY-126 Laboratory Course I

Organic Chemistry

Basic techniques involved in synthetic organic chemistry

• Different types of glass wares
• Filtration
• Distillation (distillation at atmospheric pressure, steam distillation, fractional distillation and distillation at reduced pressure).
• Recrystallization and melting point correction.
• Use of decolourising carbon.
• Thin layer chromatography.

Synthesis

• One step synthesis (any two)
  • Cis-trans isomerization (maleic acid to fumaric acid)
  • Aldol condensation (dibenzal acetone from benzaldehyde)
  • Acetylation (synthesis of acetanilide from aniline)
• Two step synthesis (any six)
  • Benzoin _ benzil _ benzilic acid
  • Benzoin _ benzil _ dibenzyl
  • Benzophenone _ benzopinacol _ benzapinacolone
  • Hydroquinone _ hydroquinone diacetate _ 2,5 dihydroxyacetophenone
  • Acetanilide _ p-nitroacetanilide _ p-nitroaniline
  • o-hydroxyacetophenone _ o-benzyloxyacetophenone _ o-hydroxy dibenzylmethane
  • Acetanilide _ p-bromoacetanilide _ p-bromoaniline
  • Benzophenone _ benzophenone oxime _ benzanilide
  • Resorcinol _ flouroscein _ Eosin
• Three step synthesis (any two)
  • Phthalic anhydride _ phthalimide _ anthranilic acid _ methyl red
  • Phthalic anhydride _ phthalimide _ anthranilic acid _ o-chloro benzoic acid
  • Aniline _ benzanilide _ p-bromobenzanilide _ p-bromoaniline

Extraction of organic compounds from natural resources (any three)

• Isolation of caffeine from tea leaves
• Isolation of casein from milk
• Isolation of lactose from milk
• Isolation of nicotine dipicrate from tobacco

Physical Chemistry

A list of experiments under different heading is given below. Students are required to perform 8-10 experiments.

Adsorption

• To study the absorption of acetic acid or oxalic acid from aqueous solution by activated charcoal or animal charcoal and examine the validity of Freundlich and Langmuirs adsorption isotherms.
• To compare cleansing power of samples of two detergents.
• Study the variation of surface tension of solution of n-propyl alcohol with concentration and hence determine the limiting cross section area of alcohol molecule.

Thermochemistry

• Determine the solubility of benzoic acid at two temperature and calculate the enthalpy change of the dissolution process.
• Determine the solubility of benzoic acid in water-DMSO mixture (4:1) and calculate the enthalpy change of the dissolution process.
• Determine the lattice energy of calcium chloride from its heat of solution using Born-Haber cycle. You are provided the Enthalpy changes for Ca+2 (g) _ Ca(g) 2Cl- (g) _ 2Cl (g), Ca (g) _ Ca (s), 2Cl (g) _ Cl2 (g) and Ca (s) + Cl (g) _ CaCl2 (s) as -451.1, 174.3, -38.8, - 58.0 and -190.0 Kcal/mole respectively.

Chemical Kinetics (any three)

• Determine the relative strength of two acids (hydrochloric acid and sulphuric acid) by studying the hydrolysis of an ester (methyl acetate or ethyl acetate) at the room temperature).
• Determine the rate constant of the hydrolysis of an ester such as methyl acetate catalyzed by an acid (0.5N HCl or 0.5N H2SO4) and determine the energy of activation.
• Study the kinetics of the reaction between K2S2O8 (potassium persulphate) and KI (potassium iodide) and determine the rate constant and the energy of activation of the reaction.
• Study the kinetics of saponification of ethyl acetate by sodium hydroxide and determine the rate constant.

Polarimeter

• Determine the rate constant of the inversion of cane sugar in presence of hydrochloric acid and sulphuric acid by using polarimeter and evaluate the relative strength of the two acids.

pH Metry

• Titrate the given mixture of CO3-2 and HCO3- ions against a strong acid, 0.1N HCl solution and determine their strength.
• Titrate a tribasic acid (H3PO4) against a strong base (NaOH).
• Determine the dissociation constant of a weak acid.

Electrochemistry

• Estimate the amount of halide ions present in a given solution by titration with silver nitrate conductometrically.
• Determine the solubility and solubility product of a sparingly soluble salt like BaSO4, or PbSO4 or AgCl in water conductometrically.

 

 

CHY-127 Communication Skill

Needs of the Learners:

• Presentations (Writing and Speaking)
• Participation in Seminars/Conferences
• Participation in Group Discussions
• Writing Scientific Reports
• Teaching – Readout to students, floor management, use of white board/black board/LCD

Language-skills required:

• Reading
• Writing
• Speaking
• Listening

As regards listening skill it is recommended that a language laboratory be developed and a few sessions be given to the students in the lab.

Unit  I Grammar

• Conditionals/Tenses
• Relative Clauses
• Subject – Verb Agreement
• Passive Voice

Unit  II Written Communication

Discuss a topic of general interest, but related to science in about 300 words. (Analyse, Comment, Argue, Reflect, Persuade, etc.)(can also be used for oral presentations by the students, followed by discussion)

Unit  III Scientific Writing

Writing a Scientific Report on a project undertaken or an experiment conducted (Theory +Practice)

Unit  IV Oral Communication I

• Consulting a dictionary for correct pronunciation (familiarity with Phonetics Symbols and Stress-marks only)
• Dialogue

Unit  V Soft Skills

• Gestures/ postures – Body language, gesture, posture.
• Group discussion – Giving up of PREP, REP Technique, how body language during group discussion.
• Presentation Skills
  • How to make power point presentation
  • Body language during presentation
• Resume writing
  • Cover letter, career objective
  • Resume writing (tailor made)
• Mock Interview
  • Each student to face an interview and to demonstrate the above taught skills.
• Positive Attitude
  • Positive skills enhancement with power point presentation.
  • fields of chemistry.

 

 

Semester - II

CHY- 221 Advanced Inorganic Chemistry

Objective

To learn the importance of metal ions in living systems and to know the unique bonding system in inorganic chains, clusters and cages.

Unit  I Symmetry and Group Theory

Symmetry elements and symmetry operations, definitions of group and subgroup,  relation between orders of a finite group and its subgroup, conjugacy relation and classes, point group symmetry, schonfiles symbols, representations of group by reducible and irreducible presentations and relation between them (representation for the Cn, Cnv, Dnh etc. groups to be worked out explicitly), character of a representation, the great orthogonality theorem (without proof) and its importance, character tables and their use.

Unit  II Electronic Spectra of Transition Metal Complexes

Pre requisite: Determination of ground state – Hund’s Rule, spin orbit coupling. Selection rules for electronic transitions, spectroscopic ground states, splitting of dn terms in octahedral and tetrahedral field; correlation diagrams, Orgel and Tanabe-Sugano diagrams (d1-d9 states); spin cross-over; field strength, spectrochemical series, nephelauxetic series; calculations of Racah parameters; applications of Tanabe-Sugano diagrams in determining Do from spectra; charge transfer spectra and its application in inorganic & coordination compounds.

Unit  III Metal _-complexes

Pre requisite: Mononuclear carbonyls. Metal carbonyls: preparation, properties, structure and bonding with special reference to dinuclear and polynuclear carbonyls; vibrational spectra of metal carbonyls for bonding and structural elucidation,differentition of bridging and terminal carbonyls; dinitrogen and dioxygen complexes; metal carbonyl clusters,

Unit  IV Boron Cage Compounds and Metal Clusters

Higher boranes, carboranes, metalloboranes and metallocarboranes; compounds with metal-metal multiple bonds.

Unit  V Role of Metal ions in Biosystems

Transport and storage of dioxygen: haeme proteins and oxygen uptake; models of oxygen binding; structure and functions of haemoglobin, myoglobin, haemocyanin and haemerythrin. Structure and function of metalloproteins in electron transport processes – cytochromes with special reference to cytochrome C; iron sulphur proteins – ferredoxins; biological nitrogen fixation and its mechanism, nitrogenenases, dinitrogen complexes as models for nitrogen fixation.

 

CHY- 222 Mechanism of Organic Reactions

Objective

To learn the concept of substitution, addition and elimination reactions and their reaction mechanism.

Unit  I Substitution v/s Elimination

Pre requisite: SN1 and SN2 mechanism of alkyl halides Aliphatic Nucleophilic Substitution: SN1, SN2, mixed SN1 and SN2, ion pair and SN1 mechanism, SNi mechanism, SET mechanism; neighbouring group participation and anchimeric assistance; substitution at allylic and vinylic carbon atoms; ambident nucleophiles; effects of substrate structure, attacking nucleophile, leaving group and reaction medium on reactivity; regioselectivity.

Pre requisite: E1, E2 mechanism of alkyl halides, Hoffmann and Saytzeff rules.  Elimination Reaction: E2, E1, E1CB and E2C (syn elimination) mechanisms; E1 – E2 –E1CB spectrum; orientation of the double bond; effect of substrate structure, attacking base, leaving group and reaction medium on reactivity; mechanism and orientation in pyrolytic elimination.

Self Study: hydrolysis of esters (acid and base catalyzed mechanism).

Unit  II Aromatic Nucleophilic Substitution

SNAr, SN1, benzyne and SRN1 mechanism; effect of substrate structure, leaving group and attacking nucleophiles on reactivity; typical reactions – Bucherer reaction, Rosenmund Von-Braun reaction, von-Richter, Sommelet-Houser and Smiles rearrangement.

Unit  III Electrophilic Substitution Reaction

Aliphatic Electrophilic Substitution: bimolecular mechanism – SE2 and SEi; the SE1 mechanism, substitution by double bond shift; addition-elimination mechanism and cyclic mechanism; effect of substrates, leaving group and solvent polarity on the reactivity, nitrogen electrophiles- aliphatic diazonium coupling, direct formation of diazo compounds, direct amination, metalation with organometallic compounds, trans metalation with metal and metal halides.

Aromatic Electrophilic Substitution: Arenium ion mechanism, orientation and reactivity; energy profile diagrams; directive influence and its explanation in different substitutions. o/p ratio; ipso attack, substitution reactions involving diazonium ions; Vilsmeir-Haack reaction., Friedel-Craft reaction- alkylation, arylation ( scholl reaction), acylation (ring closer, Haworth reaction, Hoesch reaction).

Unit  IV Free radical Substitution Reactions

Long lived and short lived radicals, detection and characteristics of free radicals; neighbouring group participation and free radical rearrangements; mechanism at an aromatic substrate, reactivity for aliphatic, aromatic substrate at bridge head carbon atom, reactivity of the attacking radical, effect of solvent. Important reactions involving free radicals – Wohl-Ziegler bromination, autooxidation, Sandmeyer and Gattermann reaction, Hunsdiecker reaction, Gomberg-Bachmann reaction,oxidation of aldehydes to carboxylic acid, coupling of alkynes .

Unit  V Addition to C-C and C-Hetero Multiple Bonds

Addition to C-C multiple bond: mechanistic and stereochemical aspects of addition reaction involving electrophiles, nucleophiles and free radical, regio and chemo selectivity, orientation and reactivity, addition to cyclopropane ring, hydrogenation of double and triple bonds, hydrogenation of aromatic rings, hydroboration, Michael reaction, Sharpless asymmetric epoxidation.  Addition to C-Hetero Multiple Bonds: mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles; Tollens reaction; addition of grignard reagents, organozinc and organolithium reagents to unsaturated carbonyl system Mechanism of condensation reactions involving enolates – Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions.

 

CHY- 223 Thermodynamics

Objective

To learn the fundamentals of thermodynamics and to describe thermodynamics at a molecular level and apply the concepts for the study of equilibrium reactions and reaction  rates.

Unit  I Classical Thermodynamics

Pre requisite: Laws of thermodynamics, free energy, chemical potential and entropies.Therodynamics of open system: Partial molar properties, chemical potential , Gibbs- Duhem equation , variation of chemical potential with temperature and pressure , chemical potential in a system of ideal gases, Clasius-Clapeyron equation and its application, fugacity and activity, determination of fugacity , the concept of activity and activity coefficient.

Unit  II Introduction to Statistical Thermodynamics

Introduction, quantum mechanical aspects, common terms- canonical ensemble, occupation number, statistical weight factor, configuration, phase space, macroscopic state, microscopic; state, system, assembly and ensemble; statistical equlibrim,Boltzmann distribution law, type of statistics, Bose-Einstein statistics, Fermi-Dirac statistics.

Unit  III Partition Function Molecular partition function for an ideal gas, translational partition function, rotational partition function, vibrational partition function, electronic partition function, nuclear partition function, translational energy of the gas, translational entropy of a monoatomic gas, translational enthalpy, translational heat capacity, translational helmholtz function.

Unit  IV Statistical Approach to Thermodynamics Properties

Internal energy, enthalpy, entropy, helmholtz function, pressure, Gibbs functions, residual entropy, equilibrium constant, equipartition principle, chemical potential, heat capacity of mono and diatomic gases, o and p- hydrogen and mixture of the two ring o-hydrogen and p-hydrogen heat capacity of solids.

Unit  V Statistical Treatment of Entropy Entropy, probability, Boltzmannn-planck equation, significance of thermodynamics probability, entropy of expansion of ideal gas, molecular basis of residual entropy,  statistical calculation of entropy, entropy of monoatomic molecules – the Sackur-Tetrde equation vibrational entropy, nuclear spin entropy, virtual entropy, rotational entropy, comparison of third law and statistical entropies, random orientation in the solids, entropy of hydrogen and deuterium

CHY- 224 Spectroscopy of Organic Compounds

Objective

To learn the concepts of spectroscopy for the study and structural elucidation of molecules.

Unit  I Mass Spectrometry

Introduction, ion-production—EI, CI, FD and FAB, detection of molecular formula – molecular ion, molecular ion peak, nitrogen rule, isotope peak, metastable ions; fragmentation – basic fragmentation types and rules, factors influencing fragmentation, McLafferty rearrangement, fragmentation pattern of hydrocarbons, alcohols, ethers, ketones, aldehydes, carboxylic acids, amines, nitro compounds, alicyclic and heterocyclic compounds. High resolution mass spectrometry.

Self Study: Problems of mass spectral fragmentation of organic compounds for structure determination.

Unit  II UV and Visible Spectroscopy

Electronic transitions (185-800nm), Beer- Lambert law, bathochromic and hypsochromic shifts, characterization of organic compounds – application of Woodward-Fieser rule to conjugated dienes, _,_-unsaturated carbonyl compounds, benzene and its substituted derivatives, polycyclic aromatic hydrocarbons, polyenes and polyenynes; steric effects in biphenyls.

Unit  III IR Spectroscopy

Quantitative studies: calculation of force constants, factors effecting the shift in group frequencies – isotope effect, hydrogen bonding, solvent effect, electronic effects (indu ctive and mesomeric) and steric effect; different absorption regions in IR spectra. Characteristics functional group absorptions in organic compounds: carbon skeletal vibrations (alkanes, alkenes, alkynes, aromatic compounds), alcohols, phenols, ethers, ketones, aldehydes, carboxylic acids, amides, acid anhydrides, conjugated carbonyl compounds, esters, lactones, amines, amino acids; interpretation of IR spectra of typical organic compounds.

Self Study: Overtones, combination bands and fermi-resonance.

Unit  IV Proton magnetic resonance spectroscopy

Introduction, chemical shift and factors affecting chemical shift, spin-spin interaction, factors affecting coupling constant, shielding mechanism, chemical shift values and correlation for protons bonded to carbon (aliphatic, olefinic, aldehydic and aromatic) and  other nuclei (alcohols, phenols, enols, carboxylic acids, amines, amides and mercaptides),chemical exchange, effect of deuteration, complex spin-spin interaction between two, three, four, and five nuclei (first order spec tra), hindered rotation, Karplus curve variation of coupling constant with dihedral angle, simplification of complex spectra – nuclear magnetic double resonance, contact shift reagents, dynamic NMR spectroscopy. Solvent effects, Fourier transform technique and its advantages, nuclear overhauser effect (NOE).

Unit  V 13C NMR Spectroscopy and Combined Applications

13C NMR spectroscopy: general considerations, chemical shift, (aliphatic, olefinic, alkyne, aromatic, heteroaromatic & carbonyl carbon), proton (1H) coupled 13C NMR spectrum, offresonance and noise decoupled 13C NMR spectrum. Structure elucidation of simple organic compounds by joint application of IR, UV, NMR and mass spectroscopy.

 

CHY- 225 Computer for Chemists

Objective

This course will help the students to learn the basics of computer in order to deal with chemical equations.

Unit  I Introduction to Computers and Computing

Basic structure and functioning of computers PC as an illustrative example; memory – RAM, ROM, IROM, EPROM, EEPROM, I/O devices – keyboard, mouse, printer, scanner,  joystick, lightpen, digitizer, secondary storage-floppy disk, compact disk, DVD, computer languages (generation of languages) differences between different types OS, internet surfing through search engines.

Unit  II Programming in BASIC

Principles of programming, algorithms and flow charts, elements of the computer language, constants and variables, operations and symbols, expressions, arithmetic assignment statement, input and output format statement, termination statements.

Unit  III Advanced Programming in BASIC

Branching statements such as IF or GO TO statement, logical variables, double precision variables, subscripted variables and dimensions.

Unit  IV Applications in Chemistry- I

Development of small computer codes involving simple formulae in chemistry, such as van der Waals equation, pH titration, kinetics, radioactive decay; evaluation of lattice energy and ionic radii from experimental data.

Unit  V Applications in Chemistry- II

Basic language to calculate the molecular weights of oganic compounds, determination of percentages of element in an organic compound, determination of molecular weights of organic compounds by experimental methods, to calculate wavelength for conjugated dienes and enones.

 

CHY-226 Laboratory Course II

Inorganic Chemistry

Qualitative analysis

Analysis of mixture for eight radicals (cations and anions) including

• Less common metal ions – Mo, W, Ti, Zr, Th, V, U (two metal ions in cationic/anionic forms)
• Insolubles – oxides, sulphates and halides
• Interfering- Oxalate, phosphate, borate, fluoride.

Quantitative analysis: volumetric analysis (any three)

• Determination of chloride ion in water by Mohr’s method or by use of adsorption indicator.
• Analysis of talcum powder by EDTA titration.
• Analysis of hydrogen peroxide by iodometric method.
• Determination of percentage purity of boric acid
• Comparison of an antacid capacity of commercial tablet samples.

Organic Chemistry

Qualitative analysis

Separation, purification and identification of components of a mixture of two organic compounds (one liquid and one solid or two solids) and three organic compounds (one liquid and two solids or three solids) using TLC for checking the purity of separated compounds.

Spectroscopy

Identification of organic compounds by the analysis of their spectral data.

 

CHY-227 Seminar

To enhance communication skill of the M.Sc students seminars have been incorporated in the syllabi in Semester I and II .The candidates will have to choose a topic from the syllabi for seminar preparation. They will be expected to submit a write up pertaining to that topic and at the end of semester, a presentation will have to be made in presence of panel of experts from different fields of chemistry.

 

Semester- III

CHY- 321 Thermal and Photochemical Reactions

Objective

To learn about the importance of light in organic reactions.

Unit  I Basics of Photochemistry

Electromagnetic radiation, photochemical excitation – interaction of electromagnetic radiation with organic molecules, types of excitations (_ _ _*, n _ _* etc.) fate of excited molecules - Jablonskii diagram, intersystem crossing, energy transfer, photosensitization, quenching, quantum yield, Frank-condon principle Stern-Volmer equation.

Unit  II Photochemical Reactions of Carbonyl Compounds

Photochemical reactions of ketones – alpha cleavage or Norrish type I cleavage, gamma hydrogen transfer or Norrish type II cleavage; photo reductions; Paterno-Buchi reactions;  photochemistry of _,_-unsaturated ketones, _,_-unsaturated ketones, cyclohexadienones (cross conjugated and conjugated).

Unit  III Photochemistry of Alkenes and Aromatic Compounds

Photochemistry of alkenes: intramolecular reactions of the olefinic bond – cis-trans isomerisation (stilbene), cyclization reactions, rearrangement of 1, 4 and 1, 5-dienes, di-_ methane rearrangement. Photochemistry of aromatic compounds: photochemical rearrangement, photostationary state, 1, 3, 5 – trimethyl benzene to 1, 2, 4-trimethyl benzene. Miscellaneous Photochemical Reactions: Barton reaction, photo Fries rearrangement of ethers and anilides, singlet oxygen reactions (photo oxygenation).

Unit  IV Pericyclic Reactions -I

General characteristics, classification, molecular orbital symmetry. Electrocyclic reactions: theories of explanation (FMO, Woodword-Hoffmann and PMO approach), frontier orbitals of ethylene, 1, 3-butadiene, 1, 3, 5-hexatriene and allyl systems, valence tautomerism.

Unit  V Pericyclic Reactions –II

Cycloaddtion Reactions: 2+2, 4+2 cycloaddition, 1, 3-dipolar cycloaddition and cheletropic reactions; stereoselectivity (endo, exo), stereospecific and regioselective hydrogen reactions, Lewis-acid catalysis in Diels’ Alder reaction.

Sigmatropic rearrangements: suprafacial and antarafacial shifts of H, sigmatropic shifts involving carbon moieties, 3, 3- and 5, 5-sigmatropic rearrangements; Claisen, Cope and Aza-Cope rearrangements; isomerization of divinyl cyclopropane; fluxional tautomerism (bullvalene); ene reaction.

 

CHY- 322 Organotransition Metal Chemistry

Objective

To learn a know how among the students on the application potential of coordination compounds in catalysis and to acquaint them with the promising future of organotransition metal chemistry in industrial, biological and environmental fields.

Unit  I s - Alkyls and Aryls of Transition Metals

Types, routes of synthesis, stability of organometallic compounds and decomposition pathways; organocopper in organic synthesis, transition metal compound with bonds to hydrogen.

Unit  II Metal-Carbon Multiple bonded organometallics

Preparation, properties, structure and bonding of -carbene and carbyne complexes( both Fischer and Schrock types) , h2- alkene and alkyne complexes, h3- allyl complexes, fluxionality and dynamic equilibria in compounds such as h2- olefin and h3- allyl complexes.

Unit  III _-Bonded Organometallics

Preparation properties, structure and bonding of h4- diene complexes, h5- dienyl complexes, h6- arene & triene complexes( nucleophilic and electrophilic substitution), fluxionality and dynamic equilibria in dienyl complexes.

Unit  IV Principles and Important Reactions of Transition Metal Organometallics

Co-ordinative unsaturation; oxidative addition, C-H bond activation; reductive elimination; insertion; reactions on co-ordinated ligands.

Unit  V Catalysis by Organotransition Metal Complexes

Pre requisite: Classification, nomenclature and general characteristics of organometallic compounds. Homogeneous catalysis: hydrogenation of alkenes, hydrosilylation of alkenes, metathesis  of alkenes, oligomerization and polymerization of alkenes and alkynes, hydroformylationof alkenes, acetic acid synthesis and other carbonylation reactions, oxidation reactions of alkenes. Heterogeneous catalysis: Fischer Tropsch process, water gas shift reaction.

 

CHY- 323 Electrochemistry and Surface Phenomena

Objective

To understand the behaviour of ions in solution and structure of electrode surface. Surface phenomena including three dimentional concepts of molecules.

Unit  I Ions in solution

Debye-Huckel theory of strong electrolysis (ion-ion & ion-solvent interaction), ionic  strength, Debye- Huckel-Onsager conductance equation, activity coefficient , mean ionic activity coefficient, ionic strength, Debye-Hukel theory of mean ionic activity coefficient, Debye length, The Debye-Huckel limiting law, qualitative tests of the Debye-Huckel limiting law, Bjerrum model of ion-association.

Unit  II Electrochemistry – Electrical Double Layer

Introduction, evidences and structure of electrical double layer- Helmholtz-Perrin, Guoy- Chapman, Stern theory, measurement of zeta potential (electrokinetic phenomena), influence of ions on electrokinetic phenomena, Electro capillary phenomenon: electro capillary curves, Lipmann’s equation.

Unit  III Kinetics of Electrode Reactions

Electrodics of elementary electrode reactions:Determination of anode and cathode potential, decomposition voltage of electrolyte, diffusion over potential, hydrogen and oxygen over voltage, influence of various factors on over voltage; Theoretical investigation of kinetics of an electrode reaction - Butler-Volmer equation, Tafel equation. Electrocatalysis-introduction and influence of various parameters. Semiconductor solution interfaces, effect of light at semiconductor solution interface.

Unit  IV Surface Phenomena

Adsorption by solids, chemoisorption, application of adsorption, adsorption of gases by solids, factors onfluencing adsorption, the Freundlich adsorption isotherm, Langmuir theory of adsorption, derivation of the BET eqiuation , types of adsorption isotherm, adsorption from solution, the Gibbs adsorption isotherm.

Unit  V Collidal Phenomena

Micelle formation: the mass action model and the phase separation model , shape and strucxture of micelles, micellar aggreagation numbers, critical micelle concentration (CMC) , factors affecting CMC in aqueous media , thermodynamics of CMC , thermodynamics of micellization , micelle temperature range (MTR) or Krafft point.

 

CHY- 324 Analytical Methods

Objective: To know the details and application of various instrumental techniques

Unit  I Fundamentals of Analytical Chemistry

Errors in chemical analysis, classification of errors, accuracy and precision, minimization of errors, significant figures : statistical analysis- mean and standard deviation; relative standard deviation; coefficient of variance, sampling in analysis, rejection of results, presentation of data.

Unit  II Separation Techniques: Chromatography - I

Pre requisite: Purification of solids and liquids – simple crystallization, sublimation; distillation, fractional distillation, distillation under reduce pressure. Basic principles, classification Column chromatography: elution chromatogram, methods of improving column performance, migration rates of solutes- distribution constant, retention time, column efficiency, variables that affect column efficiency, column resolution, applications  (separation of methylene blue and fluorescein).Thin layer chromatography: principle, technique and applications (separation of vitamins). Paper Chromatography: principle, Rf value, technique and applications (separation of amino acid mixtures).

Unit  III Separation Techniques: Chromatography -II

Principle, instrumentation, and applications of gas chromatography, high pressure liquid chromatography and ion exchange chromatography.

Unit  IV Optical Methods of Analysis

Pre requisite: Lambert and Beer law, verification, derivation, signification of _max and molar absorptivity, theory of fluorescence and phosphorescence. Spectrophotocolorimetry: single beam and double beam spectrophotometers, functions of the components, applications. Atomic absorption spectroscopy: principle, instrumentation, spectral interferences and chemical interferences in atomic absorption spectroscopy, applications in quantitative  analysis (analysis of Zn2+, Cu2+ and Pb2+).Flame photometry: principle, instrumentation, interferences in flame photometry, applications in quantitative analysis. Comparison of atomic absorption and flame emission spectroscopy

Unit  V Voltammetry

Introduction, basic principles of polarography, apparatus – polarizable dropping mercury electrode (DME), theory – residual current, migration current, diffusion current, Ilkovic equation, generation of polarographic waves, concept of half wave potential, polarographic maxima, applications of polarography, A.C polarography, pulse polarography, amperometric titrations.

 

CHY-325 Projects and Work Visit

This has been incorporated, with the aim that a candidate does extensive literature survey on a topic of choice and further take up project or dissertation on the same topic in the subsequent semester.

 

CHY-326 Laboratory Course III

Inorganic Chemistry Practical

Quantitative analysis

• Separation and determination of two metals Ni-Zn, Cu-Fe and Cu-Ag involving volumetric and gravimetric methods.
• Separation and determination of three component mixture (one volumetrically and two gravimetrically, any two)
  • Pb+2, Zn+2, Cu+2
  • Zn+2, Cu+2 Fe+2
  • Cu+2 Fe+2, Ni+2
  • Cu+2, Ni+2 Mg+2

Chromatographic separation

Paper chromatography

Separation, identification and determination of Rf value of the following (Any two)

• Cu and Cd
• Ni and Mn
• Ni and Co

Thin layer chromatography

Separation and determination of Rf value of mixture containing metal ions-nickel, manganese, cobalt and zinc.

Column chromatography (Practice Exercise)

Separation of metal ions by column chromatographic techniques followed by their

quantitative determinations.

Flame Photometric Determinations (Demonstrations)

Combined Applications:

Estimation of three component mixture using different techniques

Synthesis

Preparation of selected inorganic complexes and their study by IR spectra (any four)

• Metal complexes of dimethyl sulphoxide, CuCl2.2DMSO
• Metal oxalate hydrate complexes, Nickel dioxalate
• Phosphine, Ph3P and its transition metal complexes
• Bis acetalacetonate cobalt (II)
• Trisacetylacetonato iron (III)
• Cis and trans bis glycinato copper (II) monohydrate

 

CHY-327 Laboratory Course IV

Organic Chemistry Practical

Quantitative analysis (any five)

• Determination of the percentage and number of hydroxyl groups in an organic compounds by acetylation method.
• Estimation of amines/phenols using bromate bromide solution
• Determination of iodine and saponification value of an oil sample
• Determination of neutralization equivalent of the acid.
• Estimation of sulphur by messenger or fusion method.
• Estimation of halogen by fusion or stepnow’s method.
• Estimation of nitrogen by kjeldahl’s method.

Spectrophotometric Estimations

a) Inorganic Chemistry (any three)

• Manganese/chromium in steel.
• Nickel/Iron by extractive spectrophotometric method.
• Flouride/nitrite/phosphate
• Iron-phenanthroline complex: Job’s methods of continuous variation.
• Zirconium-alizarin Red-S complex: Mole ratio method.

b) Organic Chemistry (any three)

• Protein
• Carbohydrate
• Cholesterol
• Phenol
• Tanin

 

CHY-328 Laboratory Course V

Physical Chemistry Practical

A list of experiments under different heading is given below. Students are required to perform atleast 8-10 experiments.

Thermochemistry

• Determine the partial molal volume of solute (KCl or NaCl) and solvent in a binary mixture at normal temperature and pressure.
• Determine the partial molar volume of ethanol-water system at normal temperature and pressure.

Chemical kinetics

• Determine the rate constant, energy of activation and entropy of activation in the oxidation of benzyl alcohol (C6H5CH2OH) by potassium permanganate in acidic medium
• Determine the formation constant for the (Ce+4-H3PO2)intermediate complex and also its decomposition rate constant at the room temperature.
• Determine the rate constant for the bleaching of malachite green in basic medium at room temperature spectrophotometrically.

Electrochemistry

• Determine equivalent conductance of the strong electrolytes (KCl, HNO3, HCl etc.) at several concentrations and verify the Onsagar’s equation and also find the values of a and b in the equation.
• Determine the equivalent conductance of acetic acid at infinite dilution and calculate its degree of dissociation at different dilutions as well as dissociation constant at the room temperature.

Phase Equilibrium

Determine the solubility diagram for a three component liquid system chloroform, acetic acid an water or toluene, acetic acid in water or benzene ethanol and water. Discuss the diagram in a light of phase, component and degree of freedom.

Potentiometry

Determine the concentration of ferrous ion in the given solution by titrating against N/10 Cr2O7 -- or Ce+4 ion solution. Determine the equivalence point by plotting E v/s V, _E v/s _V and _2E/_V2 v/s _V.

Spectrophotometry

• Determine the acid dissociation constant (pK value) of methyl red.
• Determine the stability constant of FeSCN+2 complex ion keeping ionic strength constant.
• Determine the composition and stability constant of the complex Fe (III)/salicylic acid system by jobs variation method.

Polarography

Determine the half wave potentials of Cd+2 and Zn+2 ions 0.1 M KCl solution and show that half wave potential is independent of the concentration.

 

Semester - IV

CHY 421 Introduction to Green Chemistry

Unit  I Green Chemistry

History, Need and Goals. Green Chemistry and Sustainability and background of Green Chemistry.

Basic principles of Green Chemistry :

• Prevention of Waste/By products.
• Maximum Incorporation of the materials used in the process into the final product (Atom Economy)
• Prevention/Minimization of hazardous/toxic products.
• Designing safer chemicals - different basic approaches to do so.
• Selection of appropriate auxiliary substances (solvents, separation agents etc)
• Energy requirements for reactions—use of microwave, ultrasonic energy
• Selection of starting materials—use of renewable rather than depleting
• starting materials.
• Avoidance of unnecessary derivatization—careful use of blocking/protection
• groups.
• Use of catalytic reagents (wherever possible) in preference to stochiometric
• Reagents.
• Designing biodegradable products.
• Prevention of chemical accidents
• Strengthening/development of analytical techniques to prevent and Minimize the generation of hazardous substances in chemical processes.

Development of accurate and reliable sensors and monitors for real time in process monitoring.

Unit  II Green Synthesis

• Green Starting materials
• Green Reagents
• Green Solvents and reaction conditions
• Green Catalysis
• Green Synthesis- Real World Cases

Unit  III Future Trends in Green Chemistry:

Oxidation reagents and catalysts; Biomimetic, multifunctional reagents; Combinatorial green chemistry; Proliferation of solventless reactions; Noncovalent derivatization.

Unit  IV Green Solvents

• Alternative Green Solvents- Introduction
• Aqueous reactions with particular attention to enhancement of selectivity efficiency and industrial applicability compared to those in organic solvents.
• Reactions in ionic liquids
• Reactions in supercritical fluids
• Solvent free neat reactions in liquid phase
• Solvent free solid phase reactions

Non Conventional Energy sources for reactions

• Microwave assisted reactions
• Ultrasound assisted reactions
• Photochemical reactions using sunlight

Unit  V Green Catalysis

• Heterogeneous Catalysis(Zeolites, Silica, Alumina, Clay, Polymer, Cyclodextrin etc. supported catalysts)
• Biocatalysis(enzymes, microbes etc)
• Phase-transfer Catalysis(micellar/ surfactant etc)

 

CHY 422 Research Project / Dissertation

To give an exposure of research to candidates, dissertation has been introduced in semester IV. Candidate is required to carry out minor research project on any topic of choice (based on Semester III Literature Survey Article) under the supervision of an allotted research supervisor. The marking scheme of dissertation is as follows:

 

Group - A

Elective Paper I CHY-423-A Polymers Objective

To learn the kinetics and mechanism of various polymerization reactions and to expose the students with various processing techniques.

Unit  I Polymer Characterization

Pre requisite: Basic concepts of polymer science- monomers, repeat units, degree of polymerization; Classification of polymers, average molecular weight, number-average and weight-average molecular weights; sedimentation and viscosity average molecular weights, polydispersity and molecular weight distribution; practical significance of molecular weight; measurement of molecular weights – end-group, viscosity, light scattering, osmotic and ultra centrifugation methods; analysis and testing of polymers – chemical analysis of polymers, spectroscopic methods, X-ray diffraction study, microscopy.

Unit  II Structure and Properties

Morphology and order in crystalline polymers – configuration of polymer chains, crystal structure of polymers, morphology of crystalline polymers, strain - induced morphology, crystallization and melting; polymer structure and physical properties – crystalline melting point Tm (melting point of homogenous series, effect of chain flexibility and other steric factors, entropy and heat of fusion), the glass transition temperature Tg, relation between Tm and Tg, effects of molecular weight, diluents, chemical structure, chain topology; property requirements and polymers utilization.

Unit  III Polymerization Reaction-I

Pre requisite: Addition and condensation polymerization. Classification of polymerization mechanism, mechanism of stepwise polymerization, kinetics and statistics of linear stepwise polymerization, poly functional step reaction polymerization, ring-opening polymerization.

Unit  IV Polymerization Reaction-II

Chain (addition) polymerization: mechanism and kinetics based on active centers (free readical, anionic, cationic); effects of temperature and pressure on chain polymerization; coordination polymerization : Ziegler Natta . Kinetics and mechanism of copolymerization. Polymerization in homogeneous and heterogeneous system.

Unit  V Polymer Processing

Plastics, elastomers and fibres, compounding, processing techniques- calendaring, die casting, rotational casting, film casting, injection moulding, blow moulding, extrusion moulding, thermoforming, foaming, reinforcing and fibre spinning.

 

Elective Paper II CHY 424-A Environmental Chemistry

Objective

To learn about the environment we dwell in.

Unit  I General Aspects of Environment

Concept of Environmental Chemistry; Environmental Components (Atmosphere, Hydrosphere, Lithosphere and Biosphere); Composition of Air, water, soil; Atmosphere and its interaction with Hydrosphere, Lithosphere and Biosphere.  Vertical temperature and vertical structure of the atmosphere. Environmental pollution-An Introduction, Pollutants, Types & Classification of Pollutants. An introduction to Biogeochemical Cycles in Environment-detailed study of Nitrogen cycle; Biological Control of Chemical factors in the Environment; Production and Decomposition in nature; Bio distribution of elements.

Unit  II Air and Energy

Introduction; Chemical and Photochemical reactions in the atmosphere; Effects and control of air pollutants-Gaseous, Particulates; air pollution meteorology. Climate change in the future: Predictions, Consequences and controls Renewable Energy; Alternative clean fuels- Solar, Hydrogen, Nuclear etc.

Unit  III Water & Soil

Introduction; Chemistry of natural waters; water pollutants; Types of water pollutions; sources of water pollution; Classification of water pollutants; the pollution and purification of water.

Unit  IV Enhanced Atmospheric Effects

Green House Effect : Green house gases; Major sources of green house gases; Green house effect and climate change.

Acid Rain: Introduction; acid rain precursor, their aqueous and gas phase atmospheric oxidation reactions; damazing effects on aquatic life, plants, buildings and health; acid rain control strategies.

Ozone depletion : Ozone layer and its chemistry; high absorption by molecules; biological consequences of ozone depletion; creation; non-catalytic and catalytic process of ozone destruction; Aerosols; Smog formation.

Unit  V Environmental Toxicology

Introduction; threshold limiting value (TLV); Toxicity and control of Toxicants-- Non Metallic Compounds, Asbestos, Organic Compounds, Endocrine Disrupters, Persistent Organic Pollutants (POP’s), Polychlorinated Biphenyls (PCB’s), Dioxins, Pesticides, Phthalates, Heavy Metals- As, Hg, Cd, Pb.

 

Elective paper III CHY 425-A Biomolecules and Bio-organic Chemistry

Objective

To learn the basics of biological processes that are required to explain concept of pharmacy.

Unit  I Enzymes

Introduction and historical perspective, chemical and biological catalysis, remarkable prop erties of enzymes like catalytic power, specificity and regulation, nomenclature and classification, extraction and purification. Fischer's lock and key and Koshland's induced fit hypothesis, concept and identification of active site by the use of inhibitors, affinity labeling and enzyme  modification by site-directed mutagenesis, enzyme kinetics, Michaelis-Menten and Lineweaver-Burk plots, reversible and irreversible inhibition

Unit  II Kinds of Reactions Catalyzed by Enzymes

Nucleophilic displacement on a phosphorus atom, multiple displacement reactions and the coupling of ATP cleavage to endergonic processes, transfer of sulphate, addition and elimination reactions, enolic intermediates in isomerization reactions, (_-cleavage and condensation, some isomerization and rearrangement reactions, enzyme catalyzed carboxylation and decarboxylation, examples of some typical enzyme mechanisms for chymotrypsin, ribonuclease, lysozyme and carboxypeptidase A.

Unit  III Carbohydrate Metabolism

Glycolysis, fate of pyruvate under anaerobic conditions, citric acid cycle, oxidative phosphorylation (electron transport system), gluconeogenesis and glucogenolysis, C4 pathway, pentose phosphate pathway and photosynthesis.

Unit  IV Protein Metabolism and Disorders

Degradation of amino acids (C3, C4, C5 family), urea cycle, uric acid and ammonia formation. Proteins (Structure and Functions): primary, secondary, tertiary and quaternary structure; enzymes, active sites, allosteric sites and mechanisms of their actions, e.g., chymotrypsin, carboxypeptidase, lipases, etc; enzyme immobilization and their application, enzyme as target as drug design.

Unit  V Nucleic Acids

Chemical and enzymatic hydrolysis, structure and functions of DNA, RNA (m-RNA, t-RNA, r-RNA), an overview of gene expression (replication, transcription and translation), genetic code (origin, Wobble hypothesis and other important features), genetic errors, carcinogenesis and recombinant DNA technology.

 

Group - B

Elective Paper I CHY 423-B Inorganic Materials

Objective

To develop awareness in students for chemistry in industrial sector and to expose them with the industrial use of commercial polymers.

Unit  I Commercial Polymers

Structure, properties and applications of – natural rubber and other polyisoprenes, rubber copolymers, rubber derived from butadiene, cellulosic polymers, phenolic and amino resins, polymers based on phosphorus and sulphur- polyphosphates, phosphorus sulphide cages, tetrasulphur, tetranitride and related compounds.

Unit  II Cement

Introduction, classification and composition of cements, raw material, manufacturing method- dry process, wet process, chemistry of setting and hardening of cement, various additive used, concrete and reinforced concrete construction.

Unit  III Glasses and Ceramics

Glass- introduction, properties and manufacturing method of glass, glass modifiers, Ceramic- applications. Ceramic, plasticity of clays, clay products. Refractories- characterization, properties and applications.

Unit  IV Organic Solids

Conducting organics, organics superconductors, magnetism in organic materials. Fullerenes- doped, fullerenes as superconductors.

Unit  V Paints and Pigments

Paint - classification, properties and applications of paints, manufacture of paints, pigments-characterization, types and properties.

 

Elective Paper II CHY-424-B Bioinorganic Chemistry

Objective

To learn the importance of metalloenzymes used in biosystems and metals in medicine.

Unit  I Metal Ions in Living System

Pre requisite: Essential and trace elements - a general idea. Metal ions in biological systems: bulk and trace metals with special reference to Na, K, Mg, Fe, Cu; molecular mechanism – ion transport across membranes, active transport of Na-K (ion pumps), chlorophyll and their role in photosynthesis, PS I and PS II system, ATP cycle.

Unit  II Iron and Calcium in Biological Systems

Metal Storage and Transport: Ferritin, Transferrin, Siderophores. Calcium in Biological Systems: calcium in living cells, transport and regulation of Ca2+ ions in higher organisms, molecular aspects of intramolecular processes, extracellular binding proteins.

Unit  III Metalloenzymes

Zinc enzymes-carboxypeptidase and carbonic anhydrase; iron enzymes – catalase,  peroxidase and cytochrome P-450; copper enzymes – superoxide dismutase; vitamin B12 and B12 coenzymes.

Unit  IV Metals in Medicine

Metal deficiency and disease, toxic effects of metals, metals used for diagnosis, chemotherapy with special reference to anticancer drugs.

Unit  V Metal-nucleic acid interactions

basics- nucleic acid structure, fundamental interactions and reactions with nucleic acids, applications of different metal complexes that binds nucleic acids, conformational probes, metal-nucleic acid interactions with special references to zinc finger protein.

 

 

Elective Paper III CHY 425-B Nuclear and Radiation Chemistry

Objective

To learn about nuclear chemistry and to equip students for future career in nuclear industry.

Unit  I Atomic Nucleus

Sub-nucleons, classification of nuclides, nuclear stability, binding energy, nuclear radius, orbital, spin and total angular momentum of nucleons, electric quadrupole moment of nuclides; nuclear models – liquid drop model, fermi gas model, optical model, shell model.

Unit  II Radioactivity

Pre requisite: Properties of _, _ and _ rays. Decay scheme, decay kinetics, parent-daughter decay growth relationship, branching decay, alpha emission, beta emission – type of beta decay, electron capture, neutrino, double beta decay, nuclear deexcitation – gamma emission, gamma transition, internal conversion, auger effect; artificial radioactivity, counters – Geiger counter, scintillation counter, proportional counter, semi conductor detector.

Unit  III Nuclear Reactions

Pre requisite: Nuclear fission and fusion.

Types, special nuclear reaction – evaporation, spallation, fission, fragmentation; reaction cross section; compound nucleus mechanism for nuclear reaction, high energy, photo and thermo nuclear reaction; fission – process and product, fission energy, theory of nuclear fission, nuclear reactor, breader reactor in India, fusion and its scope.

Unit  IV Elements of Radiation Chemistry

Interaction of radiation with matter, radiolysis of water, chemical and biological effect of radiation, units for measuring radiation absorption.

Unit  V Applications of Radio Nuclides

Pre requisite: Radioisotopes

Tracer method, isotope dilution analysis, activation analysis, diffusion studies, structure determination, reaction mechanism, radio pharmaceuticals, dating techniques, neutron activation analysis.

 

Group -  C

Elective Paper I CHY 423-C Heterocyclic Chemistry

Objective

To learn about synthetic organic chemistry and medicinal chemistry for research purposes.

Unit  I Introduction and Nomenclature of Heterocycles

Replacement and systematic nomenclature (Hantzsch-Widman system) for monocyclic, fused and bridged heterocycles.

Self Study: General chemical behaviour of aromatic heterocycles, classification (structural type), criteria of aromaticity (bond lengths, ring current and chemical shifts in 1H NMRspectra, empirical resonance energy, delocalization energy and Dewar resonance energy, diamagnetic susceptibility exaltations), heteroaromatic reactivity and tautomerism in aromatic heterocycles.

Unit  II Conformational Analysis of Non-aromatic Heterocycles

Strain-bond angle and torsional strains and their consequences in small ring heterocycles. Conformation of six-membered heterocycles with reference to molecular geometry, barrier  to ring inversion, pyramidal inversion and 1,3-diaxial interaction; stereo-electronic effects – anomeric and related effects; attractive interactions – hydrogen bonding and intermolecular nucleophilic-electrophilic interactions.

Unit  III Six-Membered Heterocycles

With one heteroatom: synthesis and reactions of pyrilium salts and pyrones and their comparison with pyridinium and thiopyrylium salts and pyridones; synthesis and reactions of quinolizinium and benzopyrylium salts, coumarins and chromones. With two or more heteroatoms: synthesis and reactions of diazines, triazines, tetrazines and thiazines.

Unit  IV Small Ring and Benzo-Fused Five-Membered Heterocycles

Three-membered and four membered heterocycles – synthesis and reactions of aziridines, oxiranes, thiiranes, azetidines, oxetanes and thietanes; synthesis and reactions including medicinal applications of benzopyrroles, benzofurans and benzothiophenes.

Unit  V Meso-Ionic, Seven- and Large-Membered heterocycles

Meso-ionic heterocycles: classification, chemistry of some important meso-ionic heterocycles of type-A and B and their applications. Seven and large membered heterocycles: synthesis and reactions of azepines, oxepines, thiepines, diazepines thiazepines, azocines, diazocines, dioxocines and dithiocines.

 

Elective Paper II CHY 424-C Organic Synthesis and Chemistry of Natural Products

Objective

To learn the retrosynthesis and different classes of natural products for future endeavours in organic chemistry.

Unit  I Disconnection Approach and Protecting Group

An introduction to synthons and synthetic equivalents, disconnection approach, functional group inter-conversions, the importance of the order of events in organic synthesis, one group C-X and two group C-X disconnections, chemoselectivity, reversal of polarity, cyclisation reactions, amine synthesis; principle of protection of alcohol, amine, carbonyl and carboxyl groups.

Self study: Name reactions

Unit  II One and Two Group C-C Disconnections

Alcohols and carbonyl compounds, regioselectivity, alkene synthesis, uses of alkynes and aliphatic nitro compounds in organic synthesis; Diels’ Alder reaction, 1,3-difunctionalised compounds, _,_-unsaturated carbonyl compounds, control in carbonyl condensations, 1,5- difunctionalised compounds; Micheal addition and Robinson annelation.

Unit  III Terpenoids and Carotenoids

Classification, nomenclature, occurrence, general methods of structure determination, isoprene rule; structure determination, stereochemistry and synthesis of the following representative molecules – Citral, Geraniol, Menthol and _-Carotene.

Unit  IV Alkaloids

Definition, nomenclature, physiological action, occurrence, general methods of structure elucidation, degradation, classification based on nitrogen heterocyclic ring. Structure, stereochemistry and synthesis of the following – Ephedrine, (+)-Nicotine and Morphine.

Self Study: Role of alkaloids in plants.

Unit  V Steroids

Occurrence, nomenclature, basic skeleton, Diels’ hydrocarbon and stereochemistry. Structure determination and synthesis of Cholesterol, Androsterone, Testosterone, Estrone.

 

Elective paper III CHY 425-C Biomolecules and Bio-organic Chemistry

Objective

To learn the basics of biological processes that are required to explain concept of pharmacy.

Unit  I Enzymes

Introduction and historical perspective, chemical and biological catalysis, remarkable properties of enzymes like catalytic power, specificity and regulation, nomenclature and classification, extraction and purification. Fischer's lock and key and Koshland's induced fit hypothesis, concept  and identification of active site by the use of inhibitors, affinity labeling and enzyme modification by site-directed mutagenesis, enzyme kinetics, Michaelis-Menten and Lineweaver-Burk plots, reversible and irreversible inhibition

Unit  II Kinds of Reactions Catalyzed by Enzymes

Nucleophilic displacement on a phosphorus atom, multiple displacement reactions and the coupling of ATP cleavage to endergonic processes, transfer of sulphate, addition and elimination reactions, enolic intermediates in isomerization reactions, (_-cleavage and condensation, some isomerization and rearrangement reactions, enzyme catalyzed carboxylation and decarboxylation, examples of some typical enzyme mechanisms for chymotrypsin, ribonuclease, lysozyme and carboxypeptidase A.

Unit  III Carbohydrate Metabolism

Glycolysis, fate of pyruvate under anaerobic conditions, citric acid cycle, oxidative phosphorylation (electron transport system), gluconeogenesis and glucogenolysis, C4 pathway, pentose phosphate pathway and photosynthesis.

Unit  IV Protein Metabolism and Disorders

Degradation of amino acids (C3, C4, C5 family), urea cycle, uric acid and ammonia formation. Proteins (Structure and Functions): primary, secondary, tertiary and quaternary structure; enzymes, active sites, allosteric sites and mechanisms of their actions, e.g., chymotrypsin, carboxypeptidase, lipases, etc; enzyme immobilization and their application, enzyme as target as drug design.

Unit  V Nucleic Acids

Chemical and enzymatic hydrolysis, structure and functions of DNA, RNA (m-RNA, t-RNA, r-RNA), an overview of gene expression (replication, transcription and translation), genetic code (origin, Wobble hypothesis and other important features), genetic errors, carcinogenesis and recombinant DNA technology.

 

Elective paper IV CHY 426-C Computational Chemistry

Unit  I The Theoretical Background

The Schrodinger reaction, moleculer Hamiltonian, atomic unit, Born-Oppenheimer approximation Hartee-Fock theory, molecular orbitals, basis sets, the variation principle, Rootham-Hall equation, open shell methods, electron correlation methods, configuration interaction, full CI, limited configuration interaction, M_ller-Plesset perturvation theory, density functional theory, hybrid functionals, integration grids and DFT calculations complete basis set extrapolation.

Unit  II Computational Method and Model Chemistries

An overview of computational chemistry, molecular mechanics, electronic structure method, semi-empirical, ab initio and density functional methods, principle of model chemistry, desirable features of a model chemistry, different theoretical levels and basis sets, open shell and closed shell models.

Unit  III Geometry Optimization and Frequency Calculations

Introduction to potential energy surface(PES), local minimum, global minimum, and saddle point, locality minima, convergence criteria, locality transition structures, frequency calculations, zero-point corrections, thermochemistry, some illustrative examples: ethylene, 1,3-butadirne, 1-fluoropropane, vinyl alcohol

Unit  IV Basis Set Effects

Minimal basis sets, split vaence basis sets, polarized basis sets, diffuse functionshigh angular momenture basis sets, some illustrative examples of the selection of appropriate basis set for a particular calculation : HF bond length, M-C band length, in M(CO)6 (M= G , MO, W)

Unit  V Theoretical Study of Some Simple Reactions

Butane- isobutane, isomerzation energy, rotational barrier between staggered and eclipsed, forms of ethane, different conformers of butane ( anti, anticlinal and gauche), acetaldehyde-ethylene oxide isomerization energy, different molecular orbital(( HOMO, HOMO-1, LUMO) of enthylene and 1,3-butadirne.

 

Group -  D

Elective Paper I CHY 423-D Biophysical and Corrosion Chemistry

Objective

To acquaint the students with corrosion chemistry and liquid state and also to aware with statistical mechanics of biopolymers.

Unit  I Corrosion Science

Theories of corrosion, kinetics of corrosion, Evan’s diagram thermodynamics of corrosion- Pourbaix diagram, forms of corrosion, prevention of corrosion- modification of materials, corrosion inhibitors, cathodic and anodic protection

Unit  II Biological Cell and Bioenergetics

Biological cell, structure and functions of proteins, enzymes, Standard free energy change in biochemical reactions, exergonic, endergonic.

Unit  III Statistical Mechanics in Biopolymers

Evaluation of size, shape, molecular weight and extent of hydration of biopolymers by various experimental techniques. Sedimentation equilibrium, hydrodynamic methods, diffusion, sedimentation velocity, viscosity, electrophoresis and rotational motions. Chain configuration of macromolecules, statistical distribution end to end dimensions, calculation of average dimensions for various chain structures. Polypeptide and protein structures, introduction to protein folding problem.

Unit  IV General Properties of Liquids

Liquids as dense gases, liquids as disordered solids, some thermodynamic relations, internal pressure and its significance in liquids. Equations of state, critical constants. Diferent types of intermolecular forces in liquids, different potential functions for liquids, additivity of pair potential approximation.

Unit  V Supercooled and Ionic liquids

Supercooled and Ionic liquids, theories of transport properties, non-arrhenius behaviour of transport properties, Cohn-Turnbull free volume model, configurational entropy model, glass transition in supercooled liquids.

 

Elective Paper II CHY 424-D Solid State and Supramolecular Chemistry

Objective

To learn the students with the fascinating area of solid state chemistry and super conductors and to appreciate the use of various diffraction methods in structural analysis and to understand the importance of co-ordinaiton compounds in the emerging field of supramolecular chemistry.

Unit  I Solid State Reactions and Preparative Methods of Inorganic Solids

General principles, experimental procedures, co-precipitation as a precursor to solid state reactions, kinetics of solid state reactions. Preparative methods of inorganic solids (solgel and MOCVD processes) – crystallization of solutions, glasses, gels and melts, vapour phase transport methods, electrochemical reduction methods, preparation of thin films, growth of single crystals, high pressure and hydrothermal methods.

Unit  II X-ray diffraction

Laue method, Bragg method, Debye-Scherrer method of X-ray structural analysis of crystals, Miller indices, index reflections, identification of unit cells from systematic absences in diffraction pattern, structure of simple lattices and X-ray intensities, structure factor and its relation to intensity and electron density, phase problem; procedure of X-ray structure analysis, absolute configuration of molecules. Electron and Neutron Diffraction ( brief idea)

Unit  III Electronic Properties and Band Theory

Semiconductors: influence of doping on band gap; applications – p-n junction, photovoltaic cell and solar conversion. Optical properties: optical reflectance, photoconduction-photoelectric effects. Superconductivity: Meissner effect, critical temperature and critical magnetic field – type I and II superconductors; ternary oxides – structure of 123 oxides (Y-Ba-Cu-O); BCS theory of superconductivity – Cooper Pair Electron.

Unit  IV Supramolecular Chemistry-I

Molecular recognition: molecular receptors for different types of molecules including arisonic substrates, design and synthesis of coreceptor molecules and multiple recognition;

Unit  V Supramolecular Chemistry-II

Supramolecular reactivity and catalysis: Transport processes and carrier design. Supramolecular devices- supramolecular photochemistry, supramolecular electronic, ionic and switching devices.

 

Elective Paper III CHY 425-D Physical Organic Chemistry

Objective

To learn the physical aspects of organic reactions, which are studied earlier.

Unit  I Principle of Reactivity and Isotope Effect

Mechanistic singnificance of entropy, enthalpy and Gibb’s free energy, Arrhenius equation, transition state theory, uses of activation parameters, Hammond’s postulate, Marcus theory of electron transfer, reactivity and selectivity principles, theory of isotope effects, primary and secondary kinetic isotop effects, heavy atom isotop effects, tunneling effect, solvent effects.

Unit  II Structural Effects on Reactivity

Linear free energy relationships (LFER), the Hammett equation, substituent, constants, theories of substituent effects, interpretation of _ values, reaction constant , deviations from Hammett equation, dual-parameter corrections, inductive substituent constant, the Taft model _I - and _R – scales.

Unit  III Steric and Conformational Properties

Various type of steric strain and their influence on reactivity, steric acceleration, molecular, measurements of steric, effects upon rates, steric LFER, conformational barrier to bond. Rotation-spectroscopic detection, of individual conformers , acyclic and monocyclic, systems, rotation around partial double bond, Winstein-Holness and Curtin-Hammett principle.

Unit  IV Acids, Bases, Electrophiles, Nucleophiles and Catalysis

Acid-base dissociation, electronic and structural effects and basicity, acidity functions and their applications, hard and soft acids and bases, nucleophilicity, scalesl nucleofugacity, the _- effect , ambivalent nucleophiles, acid-base catalysis- specific and general catalysis, Bronsted catalysis, nucleophilic catalysis, catalysis by non-covalent-micellar catalysis.

Unit  V Molecular Dynamics

Principle of molecular association and organization as exemplified in biological macromolecules like anzymes, nucleic acids, membranes and model systems like micelles and vesicles, molecular receptors and design principle, cryptands, cyclophanes, calixeranes, cyclodextrines, supramolecular reactivity and catalysis, molecular channels and transport processes, molecular devices and nanotechnology.