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SEMESTER - V
PAPER – 11
INORGANIC:
d-BLOCK
ELEMENTS,
COORDINATION
LANTHANIDES & ACTINIDES
Unit I: Transition elements
Marks: 150
CHEMISTRY,
THEORY
General group trends with special reference to electronic configuration, colour, variable
valency, magnetic and catalytic properties, and ability to form complexes. Stability of various
oxidation states and e.m.f. (Latimer diagrams). Comparison of 3d elements with 4d & 5d
elements.
Various oxidation states, their oxidizing and reducing nature and stability w.r.t. Ti, V, Cr, Mn,
Fe and Co. Structure and chemical reactivity of following compounds: chromate, dichromate
and chromium trioxide, KMnO4, peroxo compounds of chromium,V2O5, K4[Fe(CN)6],
K3[Fe(CN)6], Na3[Co(NO3)6], Na3[Fe(CN)5NO]
Unit II: Coordination chemistry
IUPAC nomenclature of coordination compounds, isomerism in coordination compounds.
Stereochemistry of complexes with 4 and 6 coordination numbers. Werner’s theory, valence
bond theory (inner and outer orbital complexes), electroneutrality principle and back bonding.
Crystal field theory, measurement of 10 Dq (∆o), CFSE in weak and strong fields, concept of
pairing energies and lattice energy, color and magnetic properties , factors affecting the
magnitude of 10 Dq (∆o, ∆t). Octahedral vs. Tetrahedral coordination, tetragonal distortions
from octahedral geometry Jahn-Teller theorem, square planar geometry. Elementary idea of
Ligand field and MO Theory.
Unit III: Lanthanides and actinides
Electronic configuration, oxidation states, colour, spectral and magnetic properties, lanthanide
contraction. Separation of lanthanoides (ion-exchange method only).
Recommended Texts:
1. Purecell, K.F. & Kotz, J.C. Inorganic Chemistry, W.B. Saunders Co. 1977.
2. Greenwood, N.N. & Earnshaw A. Chemistry of the Elements, ButterworthHeinemann,1997.
3. Lee, J.D. Concise Inorganic Chemistry, ELBS, 1991.
4. Gary L. Miessler, Donald A. Tarr, Inorganic Chemistry, 4/E, Pearson, 2010.
5. Huheey, J.E. Inorganic Chemistry, Prentice Hall 1993
1
PRACTICAL
INORGANIC: GRAVIMETRIC ANALYSIS AND INORGANIC PREPARATION
Gravimetric Analysis:
i.
Estimation of nickel (II) using Dimethylglyoxime (DMG).
ii. Estimation of copper as CuSCN
iii. Estimation of iron as Fe2O3 by precipitating iron as Fe(OH)3.
Inorganic Preparations:
i.
Tetraamminecopper (II) sulphate, [Cu(NH3)4]SO4.H2O
ii. Cis and trans K[Cr(C2O4)2. (H2O)2] Potassium dioxalatodiaquachromate (III)
iii. Tetraamminecarbonatocobalt (III) ion
iv.
Potassium tris(oxalate)ferrate(III)
Spectophotometric estimation:
i.
To draw calibration curve (absorbance at ƛmax vs. Concentration) for various
concentrations of a given coloured compound and to estimate the concentration of
the same in a given solution.
ii. Spectrophotometric estimation of Ferrous ion by using 1,10-phenanthroline
iii. Determination of composition of Fe (III)-salicyclic acid complex by Job’s method.
Recommended Text:
1. Vogel, A.I., Fundamentals of Quantitative Analysis, 5th Ed., Addison Wesley longman.,
1989.
2
PAPER – 12
Marks: 150
ORGANIC: CARBOHYDRATES, SPECTROSCOPY AND DYES
THEORY
Unit I: Carbohydrates
Occurrence, classification, reducing and non reducing sugars, reactions and their biological
importance.
Monosaccharides: Structure elucidation, relative and absolute configuration of glucose and
fructose, co-relation of configuration, characteristic reactions of glucose and fructose, epimers
and anomers, mutarotation, determination of ring size of glucose and fructose, Haworth
projections and conformational structures and conformational analysis (elementary idea,
anomeric effect), configuration on C-1 in glucose, interconversions of aldoses and ketoses,
Kiliani-Fischer synthesis, Ruff’s degradation and Wohl’s method.
Disaccharides: Nomenclature, applications and structural distinction of maltose, lactose and
sucrose; Invert sugar.
Polysaccharides: Elementary treatment of starch, cellulose and glycogen (comparative study
of their structures) and their application.
Unit II: Spectroscopy
Introduction to spectroscopy: Electromagnetic radiation, fundamental definitions,
electromagnetic spectrum, introduction to concepts of absorption and emission spectroscopy,
Beer-Lambert law.
UV spectroscopy: Types of electronic transitions, UV spectrum, λmax, ϵmax, chromophores,
auxochromes, bathochromic shift, hypsochromic shift (definitions and elementary examples)
and solvent effect. Characteristic UV transitions in common functional groups.
General applications of UV spectroscopy including distinction between cis-trans isomers.
Woodward rules for calculating λmax in following systems:
 Conjugated dienes: alicyclic, homoannular, heteroannular.
 α,β-Unsaturated aldehydes and ketones.
 Extended conjugated systems: dienes, aldehydes and ketones.
IR Spectroscopy: Fundamental and non-fundamental molecular vibrations, IR spectrum,
fingerprint and group frequency regions and their significance, Hooke’s law and vibrational
frequency. Factors affecting vibrational frequency in organic compounds.
Characterization of functional groups: alkanes, alkenes, alkynes (only alicyclic systems),
aldehydes, ketones, carboxylic acids and their derivatives, hydroxy compounds and amines.
Study of hydrogen bonding.
PMR spectroscopy: Basic principles of NMR spectroscopy, PMR scale, chemical shifts
(concept of shielding and deshielding), factors influencing chemical shifts, simple spin-spin
1
couplings, coupling constant, chemical shift equivalence, anisotropic effects in alkenes,
alkynes, aldehydes and aromatics. Interpretation of PMR spectra of simple compounds.
Application of UV, IR and PMR in solving structures of simple organic molecules.
Unit III: Dyes
Colour and constitution of dyes: Witt’s theory, quinonoid theory, valence bond theory (VBT)
and molecular orbital theory (MOT).
Classification of dyes with examples on the basis of mode of application: Acidic, basic, direct,
mordant, vat developed and dispersed dyes.
Classification of dyes with examples on the basis of structure: Azo dyes, triphenyl methane
dyes, phthalein dyes, xanthene dyes and natural dyes.
Synthesis and uses of following dyes:
Methyl orange, malachite green, phenolphthalein.
Structure elucidation and synthesis of alizarin and indigo.
Recommended Texts:
1. Morrison, Robert Thornton & Boyd, Robert Neilson Organic Chemistry, Dorling
Kindersley (India) Pvt. Ltd. (Pearson Education), Sixth Edition, 2003.
2. Finar, I. L. Organic Chemistry (Volume 1), Dorling Kindersley (India) Pvt. Ltd.
(Pearson Education), Sixth Edition, 2003.
3. Finar, I. L. Organic Chemistry (Volume 2: Stereochemistry and the Chemistry of
Natural Products), Dorling Kindersley (India) Pvt. Ltd. (Pearson Education), Fifth
Edition, 1975.
4. Graham Solomons, T.W., Craig B. Fryhle Organic Chemistry, Ninth edition John
Wiley & Sons, Inc. 2008.
5. Kemp, W. Organic Spectroscopy, Palgrave Macmillan Education Ltd, Second Edition,
1987.
PRACTICAL
ORGANIC: QUALITATIVE ANALYSIS, PREPARATION AND USE OF IR AND NMR
1. Analysis of Carbohydrate: aldoses and ketoses, reducing and non-reducing sugars.
2. Qualitative analysis of unknown organic compounds containing monofunctional groups
(carbohydrates, aryl halides, aromatic hydrocarbons, nitro compounds, amines and
amides) and simple bifunctional groups, for e.g. salicylic acid, cinnamic acid,
nitrophenols etc.
3. Identification of simple organic compounds by IR spectroscopy and PMR spectroscopy
(Spectra to be provided).
4. Preparation of methyl orange.
Recommended Texts:
1. Mann, F.G. & Saunders, B.C. Practical Organic Chemistry, Pearson Education 2009.
2. Furniss, B.S.; Hannaford, A.J.; Smith, P.W.G.; Tatchell, A.R. Practical Organic
Chemistry, 5th Ed., Pearson 2012.
2
3. Ahluwalia, V.K. & Aggarwal, R. Comprehensive Practical Organic Chemistry:
Preparation and Quantitative Analysis, University Press 2000.
4. Ahluwalia, V.K. & Dhingra, S. Comprehensive Practical Organic Chemistry:
Qualitative Analysis, University Press 2000.
3
PAPER-13
Marks: 150
PHYSICAL: PHASE EQUILIBRIA & BINARY SOLUTIONS
Unit I: Phase equilibria
THEORY
Concept of phases, components and degrees of freedom, derivation of Gibbs Phase Rule for
nonreactive and reactive systems; Clausius-Clapeyron equation and its applications to solidliquid, liquid-vapour and solid-vapour equilibria, phase diagram for one component systems
(water, sulphur, carbon dioxide), with applications.
Phase diagrams for two component systems involving eutectic, congruent and incongruent
melting points and solid solutions.
Three component system: water-chloroform-acetic acid system only.
Unit: II: Binary Solutions
Gibbs-Duhem-Margules equation, its derivation and applications to fractional distillation of
binary miscible liquids (ideal and nonideal), azeotropes, lever rule, partial miscibility of
liquids, CST, immiscible pairs, steam distillation. Nernst distribution law: its derivation and
applications.
Unit III: Solid state:
Nature of the solid state, law of constancy of interfacial angles, law of rational indices, Miller
indices, elementary ideas of symmetry, symmetry elements and symmetry operations, seven
crystal systems and fourteen Bravais lattices; X-ray diffraction, Bragg’s law, a simple account
of rotating crystal method and powder pattern method. Analysis of powder diffraction patterns
of NaCl, CsCl and KCl. Glasses and liquid crystals.
Recommended texts:
1. Atkins, P. W. & Paula, J. de Atkin’s Physical Chemistry 8th Ed., Oxford University
Press 2006.
2. Ball, D. W. Physical Chemistry Cengage India 2012.
3. Castellan, G. W. Physical Chemistry 4th Ed., Narosa 2004.
4. Mortimer, R. G. Physical Chemistry 3rd Ed., Elsevier: NOIDA, UP 2009.
5. Levine, I. N. Physical Chemistry 6th Ed., Tata McGraw-Hill 2011.
6. Metz, C. R. Physical Chemistry 2nd Ed., Tata McGraw-Hill 2009.
PRACTICAL
PHYSICAL: DETERMINATION OF CRITICAL SOLUTION AND PHASE EQUILIBRIA
I.
Determination of critical solution temperature and composition of the phenol-water
system and to study the effect of impurities on it.
1
II.
III.
IV.
Phase equilibria: Construction of the phase diagram using cooling curves or ignition
tube method:
a. simple eutectic and
b. congruently melting systems.
Indexing of a given powder diffraction pattern of a cubic crystalline system.
Distribution of acetic/ benzoic acid between water and cyclohexane.
Recommended Texts:
1. Khosla, B. D.; Garg, V. C. & Gulati, A. Senior Practical Physical Chemistry, R. Chand
& Co.: New Delhi 2011.
2. Garland, C. W.; Nibler, J. W. & Shoemaker, D. P. Experiments in Physical Chemistry
8th Ed.; McGraw-Hill: New York 2003.
3. Halpern, A. M. & McBane, G. C. Experimental Physical Chemistry 3rd Ed.; W.H.
Freeman & Co.: New York 2003.
4. Sindhu,P.S. Practicals in Physical Chemistry 1st Ed. Macmillan: India 2006.
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SEMESTER-V
PAPER-14
Marks: 150
THEORY
SECTION A-INORGANIC: REACTION RATES & MECHANISM
Unit 1: Reaction Kinetics and Mechanism:
Introduction to Inorganic Reaction Mechanism. Substitution reactions in square planar
complexes, Trans- effect, theories of trans effect, Mechanism of nucleophilic substitution in
square planar complexes, Thermodynamic and Kinetic stability, Kinetics of octahedral
substitution, Ligand field effects and reaction rates, Mechanism of substitution in octahedral
complexes.
Unit II: Introduction to catalysis of chemical reactions by organometallic compounds
Discuss the processes that commonly feature in the mechanism of following reactions:
1. Alkene hydrogenation (Wilkinsons Catalyst)
2. Hydroformylation (Co salts)
3. Wacker Process
4. Synthetic gasoline (Fischer Tropsch reaction)
5. Synthesis gas by metal carbonyl complexes
Reference text:
1. Huheey, J. E.; Keiter, E. A. & Keiter, R.L. Inorganic Chemistry, Principles of Structure
and Reactivity 4th Ed., Harper Collins 1993, Pearson, 2006.
2. Douglas, B. E.; McDaniel, D.H. & Alexander, J.J. Concepts and Models in Inorganic
Chemistry 3rd Ed., John Wiley and Sons, NY, 1994.
3. Basolo, F. & Person, R. Mechanisms of Inorganic Reactions: Study of Metal Complexes
in Solution 2nd Ed., John Wiley & Sons Inc; NY.
4. Purecell, K.F. & Kotz, J.C., Inorganic Chemistry, W.B. Saunders Co. 1977
5. Miessler, G. L. & Donald, A. Tarr, Inorganic Chemistry 4th Ed., Pearson, 2010.
6. Cotton, F.A. & Wilkinson, G. Advanced Inorganic Chemistry 4th Ed., Wiley India.
7. Collman, James P. et al. Principles and Applications of Organotransition Metal
Chemistry. Mill Valley, CA: University Science Books, 1987.
8. Crabtree, Robert H. The Organometallic Chemistry of the Transition Metals. j New
York, NY: John Wiley, 2000.
9. Spessard, Gary O., &Gary L. Miessler. Organometallic Chemistry. Upper Saddle
River, NJ: Prentice-Hall, 1996.
1
SECTION B-ORGANIC: PHARMACEUTICALS, NATURAL PRODUCTS AND
POLYMERS
Unit I: Pharmaceutical Compounds
Structure activity relationship.Classification, structure, mode of action and therapeutic uses of
pharmaceutical compounds belonging to the following classes:
1. Analgesics and antipyretics:Paracetamol (synthesis), Ibuprofen (traditional and green
synthesis).
2. Antibacterial agents: Sulphonamides. sulphadiazine (synthesis).
3. Antimalarials: Chloroquine (synthesis).
4. Antibiotics: Chloramphenicol (synthesis and structure elucidation).
Medicinal values of curcumin ,azadirachtin and vitamin C and antacid (ranitidine)
Unit II: Natural Products: Terpenoids and Alkaloids
Terpenoids: Natural occurrence, classification and biosynthesis of terpenoids (with suitable
examples including carotenoids).
Structure and specific uses of citral, limonene and α- terpineol.
Alkaloids: Natural occurrence, general methods of Isolation and structural features. (Ziesel’s
method, Herzig Meyer’s method, Hofmann’s exhaustive methylation and Emde’s
modification).
Medicinal importance of nicotine, quinine, morphine and reserpine.
Unit III: Polymers
Polymers: Introduction and classifications.
Polymerisation reactions: Addition, condensation and ring opening metathesis.Polymerisation:
Polymerisation: Mechanism of cationic, anionic and free radical addition polymerization,
Ziegler-Natta polymerisation of alkenes, stereochemistry of polymers, role of stabilisers,
plasticisers, antioxidants, telomers and inhibitors in polymer synthesis.
Preparation from appropriate monomers and applications of following polymers: Polythene,
polyvinyl chloride (PVC), polymethylmethacrylate, polyacrylonitrile, polyamides, polyesters,
buna-S, neoprene, bakellite and polyurethanes polymers.
Process of vulcanization and its importance.
Introduction to biodegradable, conducting sol-gel and liquid crystal polymers with their
importance in day to day life.
2
Recommended Texts:
1. Morrison, Robert Thornton & Boyd, Robert Neilson Organic Chemistry, Dorling
Kindersley (India) Pvt. Ltd. (Pearson Education), Sixth Edition, 2003.
2. Finar, I. L. Organic Chemistry (Volume 1), Dorling Kindersley (India) Pvt. Ltd.
(Pearson Education), Sixth Edition, 2003.
3. Finar, I. L. Organic Chemistry (Volume 2: Stereochemistry and the Chemistry of
Natural Products), Dorling Kindersley (India) Pvt. Ltd. (Pearson Education) ,Fifth
Edition, 1975.
4. Graham Solomons, T.W., Craig B. Fryhle Organic Chemistry, Ninth edition John
Wiley & Sons, Inc. 2008.
5. Kalsi, P. S. Textbook of Organic Chemistry 1st Ed., New Age International (P) Ltd.
Pub. Delete this text
6. Billmeyer, F. W. Textbook of Polymer Science, John Wiley & Sons, Inc.
7. Gowariker, V. R.; Viswanathan, N. V. & Sreedhar, J. Polymer Science, New age
International,First Edition, 1986
8. Clayden, J.; Greeves, N.; Warren, S.; Wothers, P.; Organic Chemistry, Oxford
University Press , First Edition, 2001.
9. Singh, J.; Ali, S.M. & Singh, J. Natural Product Chemistry, Pragati Parakashan 2010.
PRACTICAL
SECTION A-INORGANIC: PREPARATION OF SELECTED
COMPOUNDS AND USE SPECTROSCOPIC TECHNIQUES
i.
ii.
iii.
iv.
v.
INORGANIC
Measurement of 10 Dq by spectrophotometric method
Verification of spectrochemical series.
Controlled synthesis of two copper oxalate hydrate complexes: kinetic vs
thermodynamic factors.
Preparation of acetylacetanato complexes of Cu2+/Fe3+. Find the λmax of the complex.
Synthesis of ammine complexes of Ni(II) and its ligand exchange reactions (e.g.
bidentate ligands like acetylacetone, DMG, glycine) by substitution method.
Recommended Texts:
1. Marr. G & Rockett, B.W. Practical Inorganic Chemistry, John Wiley & Sons, 1972.
SECTION-B ORGANIC: EXTRACTION OF NATURAL PRODUCTS, SYNTHESIS
OF SELECTED DRUGS AND POLYMERS
1.
2.
3.
4.
Extraction of caffeine from tea leaves.
Preparation of sodium polyacrylate
Preparation of urea formaldehyde.
Extraction of active pharmaceutical ingredient from commercial tablet, acetylsalicylic
acid from aspirin, its synthesis in laboratory and comparison of the two samples by
melting point and TLC.
5. Isolation of ibuprofen and p-acetylaminophenol by solvent extraction from combiflam
and their purity analysis by melting point and TLC.
6. Estimation of Vitamin C by titrating it against a solution of 2, 6-dichlorophenol
indophenol dye.
7. Quantitative estimation of glucose using Fehling’s solution method.
3
Recommended Texts:
1. Vogel, A.I. Quantitative Organic Analysis, Part 3, Pearson 2012.
2. Mann, F.G. & Saunders, B.C. Practical Organic Chemistry, Pearson Education 2009.
3. Furniss, B.S.; Hannaford, A.J.; Smith, P.W.G.; Tatchell, A.R. Practical Organic
Chemistry, 5th Ed., Pearson 2012.
4. Ahluwalia, V.K. & Aggarwal, R. Comprehensive Practical Organic Chemistry:
Preparation and Quantitative Analysis, University Press 2000.
5. Ahluwalia, V.K. & Dhingra, S. Comprehensive Practical Organic Chemistry:
Qualitative Analysis, University Press 2000.
4
SEMESTER-VI
PAPER-15
Marks: 150
INORGANIC: ORGANOMETALLIC, BIO-INORGANIC CHEMISTRY
THEORY
Unit I: Theoretical Principles in Inorganic Qualitative Analysis (H2S Scheme)
Basic principles involved in analysis of cations and anions and solubility products, common
ion effect. Principles involved in separation of cations into groups and choice of group
reagents. Interfering anions (fluoride, borate, oxalate and phosphate) and need to remove them
after Group II.
Unit II: Organometallic Compounds
Definition and classification of organometallic compounds on the basis of bond type. Concept
of hapticity of organic ligands.
Metal carbonyls: 18 electron rule, electron count of mononuclear, polynuclear and substituted
metal carbonyls of 3d series. General methods of preparation (direct combination, reductive
carbonylation, thermal and photochemical decomposition) of mono and binuclear carbonyls of
3d series. Structures of mononuclear and binuclear carbonyls of Cr, Mn, Fe, Co and Ni using
VBT. -acceptor behaviour of CO (MO diagram of CO to be discussed), synergic effect and
use of IR data to explain extent of back bonding.
Zeise’s salt: Preparation and structure, evidences of synergic effect and comparison of synergic
effect with that in carbonyls.
Metal Alkyls: Important structural features of methyl lithium (tetramer) and trialkyl aluminium
(dimer), concept of multicentre bonding in these compounds. Role of triethylaluminium in
polymerisation of ethene (Ziegler – Natta Catalyst). Species present in ether solution of
Grignard reagent and their structures, Schlenk equilibrium.
Ferrocene: Preparation and reactions (acetylation, alkylation, metallation, Mannich
Condensation). Structure and aromaticity. Comparison of aromaticity and reactivity with that
of benzene.
Unit III: Bioinorganic Chemistry
Metal ions present in the biological system and classification on the basis of action (essential,
non-essential, trace, toxic). Classification of metallobiomolecules (enzymes, transport and
storage proteins and non proteins). Na – K pump, a brief idea of ionophores. Importance of Zn
as a biocatalyst. Metalloenzymes involving Zn – carbonic anhydrase, and carboxypeptidase A.
Structure of the active site and function of these enzymes in brief.
Importance of iron in the human system with reference to haemoglobin and myoglobin. Role
of haemoglobin as an oxygen carrier, Perutz Mechanism for oxygenation of haemoglobin,
1
Cooperative Effect, Bohr Effect, comparison of oxygen saturation curves of haemoglobin and
myoglobin. Storage and transport of iron in humans – Ferritin and Transferrin.
Chelating agents in medicine: Use of chelating agents like EDTA, BAL and D- penicillamine
in metal poisoning. Anticancer activity of Cisplatin.
Recommended Texts:
1. Vogel, A.I. Qualitative Inorganic Analysis, Longman, 1972
2. Svehla, G. Vogel's Qualitative Inorganic Analysis, 7th Edition, Prentice Hall, 1996-0307.
3. Cotton, F.A. G.; Wilkinson & Gaus, P.L. Basic Inorganic Chemistry 3rd Ed.; Wiley
India,
4. Huheey, J. E.; Keiter, E.A. & Keiter, R.L. Inorganic Chemistry, Principles of Structure
and Reactivity 4th Ed., Harper Collins 1993, Pearson,2006.
5. Sharpe, A.G. Inorganic Chemistry, 4th Indian Reprint (Pearson Education) 2005
6. Douglas, B. E.; McDaniel, D.H. & Alexander, J.J. Concepts and Models in Inorganic
Chemistry3rd Ed., John Wiley and Sons, NY, 1994.
7. Greenwood, N.N. & Earnshaw, A. Chemistry of the Elements, Elsevier 2nd Ed, 1997
(Ziegler Natta Catalyst and Equilibria in Grignard Solution).
8. Lee, J.D. Concise Inorganic Chemistry 5th Ed., John Wiley and sons 2008.
9. Powell, P. Principles of Organometallic Chemistry, Chapman and Hall, 1988.
10. Shriver, D.D. & P. Atkins, Inorganic Chemistry 2nd Ed., Oxford University Press, 1994.
11. Bertini, I.; Gray, H.B.; Lippard, S.J. & Valentine, J.S. Bioinorganic Chemistry, Viva
Books Pvt. Ltd., 1998.
12. Lippard, S.J. & Berg, J.M. Principles of Bioinorganic Chemistry, Panima Publishing
Corporation, 1997.
13. Hughes, M.N. Inorganic Chemistry of Biological Processes, John Wiley and Sons,
London, 1981.
PRACTICAL
INORGANIC: QUALITATIVE SEMIMICRO ANALYSIS
Qualitative semimicro analysis of mixtures containing 3 anions and 3 cations. Emphasis should
be given to the understanding of the chemistry of different reactions. The following radicals
are suggested:
CO32-, NO2-, S2-, SO32-,S2O32-, CH3COO-, F-,Cl-, Br-, I-, NO3-, BO33-, C2O42-, PO43-, NH4+, K+,
Pb2+, Cu2+, Cd2+, Bi3+, Sn2+, Sb3+, Fe3+, Al3+,, Cr3+, Zn2+, Mn2+, Co2+, Ni2+, Ba2+,Sr2+, Ca2+,
Mg2+
Mixtures should preferably contain one interfering anion, or insoluble component (BaSO4,
SrSO4, PbSO4, CaF2 or Al2O3) or combination of anions e.g. CO32-and SO32-, NO2-and NO3-,
Cl- and Br-, Cl- and I-, Br-and I-, NO3- and Br-, NO3- and I-.
Spot tests should be done whenever possible.
Recommended Text:
1. Svehla, Vogel, A.I. Qualitative Inorganic Analysis, Longman, 1972
2. G. Vogel's Qualitative Inorganic Analysis, 7th Edition, Prentice Hall, 1996-03-07.
2
PAPER-16
PHYSICAL: QUANTUM
CHEMISTRY
Unit I: Quantum Chemistry
CHEMISTRY,
PHOTOCHEMISTRY
Marks: 150
&
SURFACE
THEORY
Postulates of quantum mechanics, quantum mechanical operators, Schrödinger equation and its
application to free particle and “particle-in-a-box” (rigorous treatment), quantization of energy
levels, zero-point energy and Heisenberg Uncertainty principle; wave functions, probability
distribution functions, nodal properties, Extension to two and three dimensional boxes,
separation of variables, degeneracy. Qualitative treatment of simple harmonic oscillator model
of vibrational motion: Setting up of Schrödinger equation and discussion of solution and wave
functions. Vibrational energy of diatomic molecules and zero-point energy.
Rigid rotator model of rotation of diatomic molecule.
Qualitative treatment of hydrogen atom and hydrogen-like ions: setting up of Schrödinger
equation in spherical polar coordinates, radial part, quantization of energy (only final energy
expression), radial distribution functions of 1s, 2s, 2p, 3s, 3p and 3d orbitals. Average and most
probable distances of electron from nucleus.
Setting up of Schrödinger equation for many-electron atoms (He, Li). Need for approximation
methods. Statement of variation theorem and application to simple systems (particle-in-a-box,
harmonic oscillator, hydrogen atom).
Chemical bonding: Covalent bonding, valence bond and molecular orbital approaches, LCAOMO treatment of H2+. Bonding and antibonding orbitals. Qualitative extension to H2.
Comparison of LCAO-MO and VB treatments of H2 (only wave functions, detailed solution
not required) and their limitations. Refinements of the two approaches (Configuration
Interaction for MO, ionic terms in VB, only wave functions, detailed solution not required).
Qualitative description of LCAO-MO treatment of second row homonuclear and heteronuclear
diatomic molecules (HF, LiH, NO, CO). Qualitative MO theory and its application to AH2 type
molecules. Simple Hückel Molecular Orbital (HMO) theory and its application to simple
polyenes (ethene, butadiene).
Introduction to molecular modelling and geometry optimization (elementary ideas).
Unit II: Photochemistry
Characteristics of electromagnetic radiation, Lambert-Beer’s law and its limitations, physical
significance of absorption coefficients. Laws of photochemistry, quantum yield, actinometry,
examples of low and high quantum yields, photochemical equilibrium and the differential rate
of photochemical reactions, photosensitized reactions, quenching.
Role of photochemical reactions in biochemical processes, photostationary states,
chemiluminescence.
1
Unit III: Surface chemistry
Physical adsorption, chemisorption. Freundlich adsorption isotherm, Langmuir adsorption
equation, BET isotherms. Determination of surface area of adsorbent. Gibbs adsorption
equation.
Recommended texts:
1. Chandra, A. K. Introductory Quantum Chemistry, Tata McGraw-Hill 2001.
2. House, J. E. Fundamentals of Quantum Chemistry 2nd Ed., Elsevier: USA 2004.
3. Lowe, J. P. & Peterson, K., Quantum Chemistry, Academic Press 2005.
4. Atkins, P. W. & Paula, J. de Atkin’s Physical Chemistry 8th Ed., Oxford University
Press 2006.
5. Ball, D. W. Physical Chemistry, Cengage, India 2012.
6. Castellan, G. W. Physical Chemistry 4th Ed., Narosa 2004.
7. Laidler, K. J. Chemical Kinetics, Pearson Education: New Delhi 2004.
PRACTICAL
PHYSICAL: MOLECULAR MODELLING
i.
ii.
iii.
iv.
v.
vi.
vii.
viii.
ix.
Compare the optimized C-C bond lengths in ethane, ethene, ethyne and benzene.
Visualize the molecular orbitals of the ethane σ bonds and ethene, ethyne, benzene and
pyridine π bonds.
(a) Perform a conformational analysis of butane. (b) Determine the enthalpy of
isomerization of cis and trans 2-butene.
Visualize the electron density and electrostatic potential maps for LiH, HF, N2, NO and
CO and comment. Relate to the dipole moments. Animate the vibrations of these
molecules.
(a) Relate the charge on the hydrogen atom in hydrogen halides with their acid
character. (b) Compare the basicities of the nitrogen atoms in ammonia, methylamine,
dimethylamine and trimethylamine.
(a) Compare the shapes of the molecules: 1-butanol, 2-butanol, 2-methyl-1-propanol,
and 2-methyl-2-propanol. Note the dipole moment of each molecule. (b) Show how the
shapes affect the trend in boiling points: (118 ºC, 100 ºC, 108 ºC, 82 ºC, respectively).
Build and minimize organic compounds of your choice containing the following
functional groups. Note the dipole moment of each compound: (a) alkyl halide (b)
aldehyde (c) ketone (d) amine (e) ether (f) nitrile (g) thiol (h) carboxylic acid (i) ester
(j) amide.
(a) Determine the heat of hydration of ethylene. (b) Compute the resonance energy of
benzene by comparison of its enthalpy of hydrogenation with that of cyclohexene.
Arrange 1-hexene, 2-methyl-2-pentene, (E)-3-methyl-2-pentene, (Z)-3-methyl-2pentene, and 2,3-dimethyl-2-butene in order of increasing stability.
(a) Compare the optimized bond angles H2O, H2S, H2Se. (b) Compare the HAH bond
angles for the second row dihydrides and compare with the results from qualitative MO
theory.
2
Note: Software: ChemSketch, ArgusLab (www.planaria-software.com), TINKER 6.2
(dasher.wustl.edu/ffe), WebLab Viewer or any similar software.
Recommended Texts:
1. Lewars, E. G. Computational Chemistry 2nd Ed., Springer (India) Pvt. Ltd. 2011, Ch. 1
& 2.
2. Engel, T. & Reid, P. Physical Chemistry 3rd Ed., Prentice-Hall 2012, Ch. 26.
3. Rogers, D. W. Computational chemistry using PC 3rd Ed., John Wiley & Sons.
3
SEMESTER-VI
PAPER-17
Marks: 150
THEORY
SECTION
A-
INORGANIC: CHEMISTRY
NANOMATERIALS
OF
INORGANIC
SOLIDS,
Unit I: Synthesis and modification of inorganic solids
Conventional heat and beat methods, Co-precipitation method, Sol-gel methods, Hydrothermal
method, Ion-exchange and Intercalation methods.
Unit II: Inorganic solids of Technological Importance
Solid electrolytes – Cationic, anionic, mixed Inorganic pigments – coloured solids, white and
black pigments
Molecular material and fullerides, molecular materials & chemistry – one-dimensional metals,
molecular magnets, inorganic liquid crystal.
Unit III: Nanomaterials
Preparation of gold and silver metallic nanoparticles, self assembled nanostructures-control of
nanoarchitecture-one dimensional control. Carbon nano tubes and inorganic nanowires. Bioinorganic nanomaterials, DNA and nanomaterials, natural and antisical nanomaterials, bionano
composites.
Recommended Texts:
1. Shriver & Alkins. Inorganic Chemistry, Peter Alkins, Tina Overton, Jonathan Rourke,
Mark Weller and Fraser Armstrong, 5th Edition, Oxford University Press (2011-2012)
2. Adam, D. M. Inorganic Solid; An introduction to concepts in solid-state structural
chemistry.
SECTION B-PHYSICAL: MOLECULAR SPECTROSCOPY
Unit I: Molecular Spectroscopy:
Interaction of electromagnetic radiation with molecules and various types of spectra; BornOppenheimer approximation.
Rotation spectroscopy: Selection rules, intensities of spectral lines, determination of bond
lengths of diatomic and linear triatomic molecules, isotopic substitution.
Vibrational spectroscopy: Classical equation of vibration, computation of force constant,
amplitude of diatomic molecular vibrations, anharmonicity, Morse potential, dissociation
1
energies, fundamental frequencies, overtones, hot bands, degrees of freedom for polyatomic
molecules, modes of vibration, concept of group frequencies.
Vibration-rotation spectroscopy: diatomic vibrating rotator, P, Q, R branches.
Raman spectroscopy: Qualitative treatment of Rotational Raman effect; Effect of nuclear spin,
Vibrational Raman spectra, Stokes and anti-Stokes lines; their intensity difference, rule of
mutual exclusion.
Electronic spectroscopy: Franck-Condon principle, electronic transitions, singlet and triplet
states, fluorescence and phosphorescence, dissociation and predissociation, calculation of
electronic transitions of polyenes using free electron model.
Recommended Texts:
1. Banwell, C. N. & McCash, E. M. Fundamentals of Molecular Spectroscopy 4th Ed.,
Tata McGraw-Hill: New Delhi 2006.
2. Brown, J. M. Molecular Spectroscopy, Oxford Science Publications, New York 1998.
PRACTICAL
SECTION-A INORGANIC: DETERMINATION OF CATION EXCHANGE AND
PREPARATION OF NEWER MATERIALS
1. Synthesis of silver nanoparticles and their spectroscopic characterization
2. Preparation and characterization of polyacrylamide hydrogels by the co precipitation
method
3. To determine the percentage of tin and lead present in the given amount of solder by
complexometric titrimetric procedures.
4. Spectrometric determination of manganese in steel.
Recommended Text:
1. Fahan, Materials Chemistry, Springer 2004.
SECTION-B PHYSICAL: UV-VISIBLE SPECTROSCOPY, COLOURIMETRY AND
ADSORPTION
UV/Visible spectroscopy
I.
II.
Study the 200-500 nm absorbance spectra of KMnO4 and K2Cr2O7 (in 0.1 M H2SO4)
and determine the λmax values. Calculate the energies of the two transitions in different
units (J molecule-1, kJ mol-1, cm-1, eV)
Record the 200-350 nm UV spectra of the given compounds (acetone, acetaldehyde, 2propanol, acetic acid) in water. Comment on the effect of structure on the UV spectra
of organic compounds.
Colourimetry
I.
Determination of dissociation constant of phenolphthalein indicator.
2
II.
Study the kinetics of interaction of crystal violet/phenolphthalein with sodium
hydroxide colourimetrically.
Adsorption
I.
Verify the Freundlich and Langmuir isotherms for adsorption of acetic acid on
activated charcoal.
Recommended Texts:
1. Khosla, B. D.; Garg, V. C. & Gulati, A., Senior Practical Physical Chemistry, R.
Chand & Co.: New Delhi 2011.
2. Garland, C. W.; Nibler, J. W. & Shoemaker, D. P. Experiments in Physical Chemistry
8th Ed.; McGraw-Hill: New York 2003.
3. Halpern, A. M. & McBane, G. C. Experimental Physical Chemistry 3rd Ed.; W.H.
Freeman & Co.: New York 2003.
4. Sindhu,P.S. Practicals in Physical Chemistry 1st Ed. Macmillan: India 2006.
3
PAPER-18
Marks: 150
ORGANIC: CHEMISTRY OF BIOMOLECULES
THEORY
Unit I: Amino acids, Peptides and Proteins
Amino acids: Classification, relative and absolute configuration.
Synthesis of α-Amino acids: Phthalimide synthesis, Strecker synthesis, phthalimidomalonic
ester synthesis and azalactone synthesis.
Ionic properties and reactions: Zwitter ions, pKa values, isoelectric point, application of
electrophoresis (gel and paper) and ion exchange chromatography in separation and
purification of amino acids and proteins.
Peptides: Peptide linkage, determination of their primary structures, end group analysis
(Edmans, Sanger‘s and Dansyl chloride method only), application of partial hydrolysis
(chemical, enzymatic). Peptide synthesis: using N-protecting groups (Boc and
benzyloxycarbonyl methods only), C-protecting group, C-activating groups (acid chloride, acid
azide, activated esters and DCC methods only) and Solid-phase synthesis.
Proteins: classification, tests in laboratory and biological importance, primary, secondary(αhelix and β- pleated sheets), tertiary and quaternary structures of proteins.
Unit II: Enzymes
Introduction, classification and characteristics of enzymes. Salient features of active site of
enzymes.
Mechanism of enzyme action(taking trypsin as example), factors affecting enzyme action,
coenzymes and cofactors and their role in biological reactions, specificity of enzyme action
(including stereospecificity), enzyme inhibitors and their importance, phenomenon of
inhibition (competitive , uncompetitive and non-competitive inhibition including allosteric
inhibtion).
Unit III: Lipids
Lipids: Introduction and classification.
Oils and fats : Common fatty acids present in oils and fats, essential fatty acids and their
importance, omega fatty acids, trans fats, hydrogenation, saponification value, iodine number,
acid number, drying, rancidity (hydrolytic and oxidative) and reversion.
Biological importance of triglycerides, phospholipids, glycolipids, sphingolipids and steroids
(cholesterol). Liposomes and their biomedical applications.
1
Unit IV: Nucleic Acids
Components of nucleic acids: Nitrogenous bases (adenine, guanine, thymine, uracil and
cytosine), sugar and phosphate; nucleosides, nucleotides and their nomenclature;
Phosphodiester linkage and structure of polynucleotides; structure of DNA (Watson-Crick
model) and RNA(types of RNA), genetic code.
Biological roles of DNA and RNA: Introduction to replication, transcription and translation.
Unit V: Concept of Energy in Biosystems
Cells obtain energy by the oxidation of foodstuff (organic molecules).
Introduction to metabolism (catabolism, anabolism).
ATP: The universal currency of cellular energy, ATP hydrolysis and free energy change.
Agents for transfer of electrons in biological redox systems: NAD+, FAD.
Conversion of food to energy: Outline of catabolic pathways of carbohydrate- glycolysis,
fermentation, Krebs cycle.
Overview of catabolic pathways of fat and protein.
Interrelationship in the metabolic pathways of protein, fat and carbohydrate.
Caloric value of food, standard caloric content of food types.
Recommended Texts:
1. Morrison, Robert Thornton & Boyd, Robert Neilson Organic Chemistry, Dorling
Kindersley (India) Pvt. Ltd. (Pearson Education), Sixth Edition, 2003.
2. Finar, I. L. Organic Chemistry (Volume 1), Dorling Kindersley (India) Pvt. Ltd.
(Pearson Education), Sixth Edition, 2003.
3. Finar, I. L. Organic Chemistry (Volume 2: Stereochemistry and the Chemistry of
Natural Products), Dorling Kindersley (India) Pvt. Ltd. (Pearson Education), Fifth
Edition, 1975.
4. Graham Solomons, T.W., Craig B. Fryhle Organic Chemistry, Ninth edition John
Wiley & Sons, Inc. 2008.
5. Clayden, J.; Greeves, N.; Warren, S.; Wothers, P.; Organic Chemistry, Oxford
University Press, First Edition, 2001.
6. Nelson, D. L. & Cox, M. M. Lehninger’s Principles of Biochemistry, Fifth Edition,
2010., W. H. Freeman.
7. Berg, J. M.; Tymoczko, J. L. & Stryer, L. Biochemistry, Seventh Edition, 2012., W. H.
Freeman.
PRACTICAL
ORGANIC: ISOLATION AND ESTIMATION OF SELECTED BIOMOLECULES
AND PREPARATION OF ORGANIC COMPOUNDS
1. Estimation of phenol and aniline by bromination with potassium bromated-potassium
bromide method.
2. Estimation of glycine by Sorenson’s formalin method.
3. Study of the titration curve of glycine.
4. Estimation of proteins by Lowry’s method.
5. Study of the action of salivary amylase on starch at optimum conditions.
6. Effect of temperature on the action of salivary amylase.
7. Saponification value of an oil or a fat.
8. Determination of Iodine number of an oil/fat.
9. Isolation and characterization of DNA from onion/cauliflower/peas.
2
Recommended Texts:
1. Mannual of Biochemistry Workshop, 2012, Department of Chemistry, University of
Delhi.
2. Arthur, I. V. Quantitative, Organic, Analysis s Pearson.
3. Cooper, T.G. The Tools of Biochemistry, John Wiley and Sons, N.Y. USA. 16 (1977).
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