(Semester – V)

CH5B01 –Chemistry of d and f block elements

 Credits  – 3                                                                                                                   (54 hours)

 Aim

 To improve the level of understanding of the chemistry of transition and inner transition metals, coordination compounds, organometallic compounds, metal carbonyls and bioinorganic chemistry.

 Objectives

• To understand the general characteristics of the d and f block elements To study the physical and chemical properties of d and f block elements
•  To study the Werner’s theory of coordination compounds
• To study isomerism in metal complexes
•  To study the bonding in coordination compounds
•  To understand the applications of coordination compounds
•  To understand the classification, properties and applications of organometallic compounds
• To study the methods of preparation, properties, structure and bonding of metal carbonyls and metal clusters
• To understand the role of metals in biological systems.

1. Chemistry of d and f block Elements (9hrs)

 General characteristics of d-block elements with special reference to electronic configuration, oxidation states, variable valency, metallic character, colour, magnetic properties, catalytic properties and ability to form complexes. Comparison of the properties of second and third transition series with first transition series.

 Chemistry of lanthanides – electronic structure, oxidation states, lanthanide contraction, consequences of lanthanide contraction, magnetic properties, spectral properties and separation of lanthanides by ion exchange and solvent extraction methods (Brief study).

 Chemistry of actinides – electronic configuration, oxidation states, actinide contraction, position of actinides in the periodic table, comparison with lanthanides in terms of magnetic properties and spectral properties (Brief study).

References

1. J.D. Lee, Concise Inorganic Chemistry 5^th edn., Blackwell Science, London.(Chapter 18, 29 and 30).

2. B.R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers, New Delhi (Chapter 21 and 25)

Further Reading

1. J.E. Huheey, E. A. Keiter, R. L. Keiter, O K Medhi, Inorganic Chemistry, Pearson 2006.

2. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry 5^th edn., John Wiley, New York.

3. D.F. Shriver and P.W. Atkins, Inorganic Chemistry 3^rd edn., Oxford University Press.

2. Coordination Chemistry (18hrs)

IUPAC nomenclature, coordination number, geometry of complexes with coordination numbers 4 and 6. Stability of complexes – factors affecting the stability of metal complexes. Chelates, chelate effect, stepwise stability constant and overall stability constant. Isomerism in coordination compounds – structural isomerism and stereo isomerism, stereochemistry of complexes with 4 and 6 coordination numbers.

Bonding theories –Werner’s theory of coordination, EAN, Valence bond theory, geometries of coordination numbers 4-tetrahedral and square planar and 6-octahedral and its limitations, high spin and low spin complexes, inner orbital and outer orbital complexes. Crystal filed theory, splitting of d-orbitals in octahedral, tetrahedral and square-planar complexes – low spin and high spin complexes, strong and weak field ligands, pairing energy, Jahn-Teller distortion, Jahn-Teller distortion in Cu (II) complexes. MO theory, evidence for metal ligand covalency, MO diagram of complexes of octahedral symmetry (sigma bonding only).

Spectral and magnetic  properties  of metal  complexes-Electronic  absorption  spectrum  of 3+

[Ti (H₂O)₆] ion. Types of magnetic behavior, spin-only formula, calculation of magnetic moments.

Reactivity of metal complexes-Labile and inert complexes, ligand substitution reactions – S_N1and,S_N2 substitution reactions of square planar complexes – Trans effect and applications of trans effect.

References

1. J.D. Lee, Concise Inorganic Chemistry 5^th edn., Blackwell Science, London (Chapter 7)

2. R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers, New Delhi (Chapter 26, 27, 28, 29 and 30)

3. G.L. Meissler, D.A Tarr, Inorganic Chemistry, Pearson Education (Chapter 9, 10, 11 and 12)

4. J.E. Huheey, E. A. Keiter, R. L. Keiter, O K Medhi, Inorganic Chemistry, Pearson 2006( Chapter 14, 15, 16, 17)

5. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry 5^th edn., John Wiley, New York (Chapter 2)

Further Reading

1. B. Douglas, D. Mc Daniel, J. Alexander, Concepts and models of Inorganic Chemistry 3^rd edn., John Wiley.
2. M.N. Greenwood and A. Earnshaw, Chemistry of the elements 2^nd edn, Butterworth.

3. Organometallic Compounds                                                                                                                          (9hrs)

Definition, classification of organometallic compounds, Ylides, classification on the basis of hapticity, naming of organometallic compounds. Catalytic properties of organometallic compounds – alkene hydrogenation, synthesis of water gas – shift reaction, Zeigler-Natta polymerisation, 18 electron rule, metal-alkene complexes, metal-alkyne complexes, carbene and carbyne complexes. Metallocenes – ferrocene (preparation and structure only). Zeise’s salt – preparation, properties and structure.

References

1. B.R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers, New Delhi (Chapter 33)

2. G.L. Meissler, D. A Tarr, Inorganic Chemistry, Pearson Education (Chapter 13 and 14)

3. J.E. Huheey, E. A. Keiter, R. L. Keiter, O K Medhi, Inorganic Chemistry, Pearson 2006( Chapter 18, 19)

Further Reading

1. R.C. Mehrothra and A. Singh, Organometallic chemistry, New age publishers.

2. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry 5^th edn., John Wiley, New York.

3. A G Sharpe, Inorganic Chemistry, 3^rd Pearson

4. Metal Carbonyls and Metal clusters (9hrs)

Preparation and properties of mononuclear carbonyls. Structures of Mo (CO)₆, Fe (CO)₅ and Ni (CO)₄. Polynuclear carbonyls, bridged carbonyls and bonding in carbonyls. Metal clusters – carbonyl and halide clusters, low nuclearity carbonyl clusters and high nuclearity carbonyl clusters, electron counting schemes for Rh₆(CO)₁₆ and [Os₆(CO)₁₈]^2-, metal only clusters (Zintl ions). Quadruple bond – structure of Re₂CI₈^2-.

References

1. B.R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers, New Delhi (Chapter 31 and 32)

2. J.E. Huheey, E. A. Keiter, R. L. Keiter, O K Medhi, Inorganic Chemistry, Pearson 2006( Chapter 15)

3. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry 5^th edn., John Wiley, New York (Chapter 22 and 23)

Further Reading

1. D.F. Shriver and P.W. Atkins, Inorganic Chemistry 3^rd edn., Oxford University Press.

2. G.S. Sodhi, Organometallic Chemistry, Ane books Ltd, New Delhi, 2009.

5. Bioinorganic Chemistry                                                                                                                                (9hrs)

Essential and trace elements in biological systems, myoglobin and haemoglobin, role of myoglobin and haemoglobin in biological systems, mechanism of oxygen transport, cooperativity, Bohr effect. Vitamin B₁₂ (structure not expected) Metalloenzymes of zinc, inhibition and poisoning of enzymes. Electron carriers – cytochromes. Role of alkali and alkaline earth metals in biological systems, Na/K pump. Biological function and toxicity of metals – Fe, Cu, Zn, Cr, Mn, Ni, Co, Cd, Hg and Pb, treatment of metal toxicity. Anti cancer drugs – cisplatin and carboplatin

References

1. B. R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers, New Delhi (Chapter 36)

2. G. L. Meissler, D. A Tarr, Inorganic Chemistry, Pearson Education (Chapter 16)

3. J.E. Huheey, E. A. Keiter, R. L. Keiter, O K Medhi, Inorganic Chemistry, Pearson 2006( Chapter 20)

4. F.A.Cotton,G.Wilkinson,P.L.Gaus,Basic Inorganic Chemistry,3^rd Edn,John – Wiley,1995

5. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry 5^th edn., John Wiley, New York(Chapter 30)

Further Reading

1. D.F. Shriver and P.W. Atkins, Inorganic Chemistry 3^rd edn., Oxford University Press.

2. G.S. Sodhi, Organometallic Chemistry, Ane books Ltd, New Delhi, 2009

 Practical: CH5 B01-Qualitative Inorganic Analysis

Credit 1                                                                                                (54 hrs)

1. Study of the reactions of the following radicals with a view to their identification and confirmation.

 Ag⁺, Hg²⁺, Pb²⁺, Cu²⁺, Bi²⁺,  Cd²⁺, As³⁺,  Sn²⁺, Sb³⁺,  Fe²⁺,  Fe³⁺, Al³⁺, Cr³⁺,  Zn²⁺,

Mn²⁺, Co²⁺, Ni²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Mg²⁺, Li⁺, Na⁺, K⁺, NH₄⁺.

 CO₃² , S²  , SO₄², NO₃ , F , Cl  , Br , BO₂ , C₂O₄^2-, C₄H₄O₆^2-, CH₃COO^–, PO₄^3- ,

AsO₃^3-, AsO₄^3- and CrO₄²

2. Systematic qualitative analysis of mixtures containing two acid and two basic radicals from the above list without interfering radical by Semi-micro method only.

 (Minimum of five mixtures to be analysed)

 References

1. A.I. Vogel ‘A Text Book of Quantitative Inorganic Analysis Including Elementary Instrumental Analysis’: (Third Ed.) (ELBS)

2. G. Svehla, Text Book of Vogel’s Macro and Semi-micro Inorganic Analysis, revised, Orient Longman.

3. V.V. Ramanujam, ‘Inorganic Semi micro Qualitative Analysis’ ,The National Publishing Co., Chennai,

4. W.G. Palmer ‘Experimental Inorganic Chemistry’, Cambridge.

CH5B02- Basic Organic Chemistry-II

Credits    – 3                                                                                                                                                           (54 hours)

Aim

To give the students a thorough knowledge about the mechanisms of reactions of some selected functional groups in organic compounds and also to give an outline of applied organic chemistry and the applications of organic chemistry in various spheres of chemical sciences.

Objectives

• To learn the chemistry of nitro compounds, amines, dyes, organic polymers, soaps, detergents and organic reagents.
• To understand and study mechanism of reactions of nitro compounds and amines.
• To have an elementary idea of chemotherapy, organic spectroscopy and photochemistry
• To identify organic compound using UV, IR and PMR spectroscopic techniques \
• To develop basic skills required for crystallisation, distillation, solvent extraction, TLC and column chromatography.

1. Organic compounds containing Nitrogen (20 Hrs)

Nitro compounds- nitromethane- tautomerism- reduction products of nitrobenzene in acidic, neutral and alkaline media- electrolytic reduction and selective reduction of poly nitro compounds- formation of charge transfer complexes.

Amines- isomerism- stereochemistry of amines. Separation of a mixture of primary, secondary and tertiary amines- Structural features affecting basicity of aliphatic and aromatic amines. Quaternary amine salts as phase-transfer catalysts. Comparative study of aliphatic and aromatic amines.

Preparation of alkyl and arylamines (reduction of nitro compounds, nitriles), reductive amination of aldehydic and ketonic compounds, Gabriel-Phthalimide reaction, Hoffmann bromamide reaction.

Diazonium salts-preparation, synthetic transformations of aryl diazonium salts, azo coupling-. Mechanisms of Sandmeyer’s and Gatterman reactions- Schiemann and Gomberg reactions

 Preparation and uses of Phenyl hydrazine.

 Diazomethane and diazoacetic ester – preparation, structure and synthetic uses.-Arndt Eistert synthesis- mechanism –Wolff rearrangement

References

1. I.L. Finar Organic Chemistry -, 6^th Edition. Vol.- I, Pearson. (Chapters-13,22,23,24)

2. R.T. Morrison and R.N Boyd, ‘Organic Chemistry’, 6^th Edition – Prentice Hall of India, (Chapter- 22,23,)

3. M.K.J ain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing  Company Co. (Chapter-22)

4. K.S. Tewari and N. K. Vishnoi ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter- 22,23,24)

5. B.S. Bahl ‘Advanced organic Chemistry’, S. Chand

Further Reading

1. P.Y. Bruice, ‘Organic Chemistry’ -3^rd Edn. Pearson Education Asia.
2. John Mc Murry, ‘Organic Chemistry’ – Vth Edition -Thompson Asia Pvt Ltd
3. C.N. Pillai‘OrganicChemistry’ Universities Press.

4. J. Clayden, N. Greeves, S. Warren and P. Wothers, Organic Chemistry, Oxford University Press

2. Dyes (5 Hrs)

Theory   of   colour   and   constitution.   Classification    –   according   to   structure   and  method of application.

 Preparation and uses of 1) Azo dye-methyl orange and Bismark brown 2) Triphenyl methane dye -Malachite green. 3) Phthalein dye – phenolphthalein and fluroescein 4) Vat dye – indigo 5) Anthraquinone dye – alizarin.

 References

1. I.L. Finar Organic Chemistry -, 6^th Edition. Vol.- I, Pearson. (Chapter-31)
2. M.K.J ain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

3. K.S Tewari and N. K. Vishnoi ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter-38).

4. B.S. Bahl, ‘Advanced organic Chemistry’, S. Chand.

 Further Reading

1. John Mc Murry, ‘Organic Chemistry’ – Vth Edition -Thompson Asia Pvt Ltd
2. C.N. Pillai‘OrganicChemistry’ Universities Press.

3. Organic photochemical reactions (3 Hrs)

Introduction- Photochemical versus Thermal reactions

 Reactions: Norrish reactions of acyclic Ketones.  Patterno-Buchi, Photo-Fries

 References

1. I.L. Finar Organic Chemistry -, 6^th Edition. Vol.- I, Pearson. (p.-901-904).
2. M.K. Jain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

 Further Reading

1. March, ‘Advanced Organic Chemistry’, IV Edn, John Wiley & Sons, NY,
2. N. Pillai‘OrganicChemistry’ Universities Press
3. John Mc Murry, ‘Organic Chemistry’, Vth Edition, Thompson Asia Pvt Ltd

4. Organic Polymers                                                                                                                                           (4 hrs)

Synthesis and applications of the following polymers- Polyesters- terephthalates, polyamides- Nylon 6 and Nylon 6,6, phenol formaldehyde resins, urea formaldehyde resins, epoxy resins and polyurethanes, PVC and Teflon. Synthetic rubbers –SBR and Nitrile rubber.

References

1. M.K. Jain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

2. K.S. Tewari and N. K. Vishnoi, ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter-37)

3. R.T. Morrison and R.N Boyd, ‘Organic Chemistry’, 6^th Edition – Prentice Hall of India, (Chapter- 31)

4. Billmeyer F.W., Text book of polymer science, Jr.John Wiley and Sons, 1994.

5. Gowariker V.R., Viswanathan N.V. and Jayader Sreedhar, Polymer Science, Wiley Eastern Ltd., New Delhi.

Further Reading

1. B.S. Bahl ‘Advanced organic Chemistry’, S. Chand
2. B.K. Sharma Polymer Chemistry, Goel Publishing House, Meerut, 1989.

5. Some important aliphatic hydrocarbons (2 hrs)

Cycloalakanes- relative stabilities

 Butadiene – structure and stability, 1,4 addition,

 References

1. I.L. Finar Organic Chemistry , 6^th Edition. Vol.- I, Pearson. (Chapter-19 and p-127-129)

2. M.K.J ain and S. C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

3. K.S. Tewari and N. K. Vishnoi, ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter-8 and p.293).

 Further Reading

 B.S. Bahl ‘Advanced organic Chemistry’, S. Chand

6. Soaps and Detergents (3 hrs)

Composition of soaps- detergent action of soap-Synthetic detergents- – their functions – comparison between soaps and detergents- Environmental aspects. LAS and ABS detergents

References

1. I.L. Finar Organic Chemistry , 6^th Edition. Vol.- I, Pearson. (p.-323)
2. M.K. Jain and S.C. Sharma, ‘Modern Organic Chemistry’, 3^rd Edition, Vishal Publishing Company Co. (Chapter-22)

3. K.S. Tewari and N. K. Vishnoi ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter-36).

Further Reading

1. B.S. Bahl ‘Advanced organic Chemistry’, S. Chand

2. John Mc Murry, ‘Organic Chemistry’ – Vth Edition -Thompson Asia Pvt Ltd

7. Chemotherapy (5 Hrs)

Drugs- introduction –classification –mode of action

Elementary idea of the structure and mode of action of the following drugs

Sulphanilamide, Amphicillin and Chloramphenicol,

Elementary idea of the structure and application of Chloroquine, Paracetamol and Analgin.

Drugs in cancer therapy- Chlorambucil.

References

1. I.L. Finar Organic Chemistry -, 6^th Edition. Vol.- I, Pearson. (Chapter-18)
2. M.K. Jain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

3. K.S. Tewari and N. K. Vishnoi ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House (Chapter-39)

Further Reading

1. B.S. Bahl ‘Advanced organic Chemistry’, S. Chand
2. John Mc Murry, ‘Organic Chemistry’, V^th Edition, Thompson Asia Pvt Ltd.

8. Chemistry of Organic Reagents (4Hrs)

Analytical reagents – Tollens reagent, Fehling solution, Schiff’s reagents, Borsche’s reagent, Benedict solution, Barford’s reagent

Synthetic reagents –NBS, Lead tetra acetate, Periodic acid, OsO₄ , Ozone, LDA, Raney Nickel, Ziegler –Natta Catalyst, Selenium dioxide, DCC (elementary idea)

References

1. A.I. Vogel, ‘A Text Book of Practical Organic Chemistry’, Longman.

2. F.G. Mann and B.C. Saunders, ‘Practical Organic Chemistry’, 4^th edn. Pearson Education

3. N.K. Vishnoi, ‘Advanced Practical Organic Chemistry’, Vikas Publishing House.

4. M.K. Jain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Visal Publishing Company Co. (Chapter-22)

Further Reading

1. J. March, ‘Advanced Organic Chemistry’, IV Edn, John Wiley & Sons, NY
2. John Mc Murry, ‘Organic Chemistry’ – Vth Edition, Thompson Asia Pvt Ltd
3. C.N. Pillai‘OrganicChemistry’, Universities Press.

9. Structure elucidation (8 Hrs)

IR,UV and NMR spectral characteristics of simple molecules such as

ethylene,butadiene,benzene,acetaldehyde,acetone,acetophenone,crotonaldehyde, ethanol ethyl acetate,acetic acid,aniline,acetamide

Problems pertaining to the structure elucidation of simple organic compounds using IR and PMR spectroscopic techniques

Mass spectrometry- Introduction-EI ionisation- Determination Molecular mass by MS (elementary idea- fragmentation study not required)

References

1. R.T. Morrison and R. N. Boyd, ‘Organic Chemistry’, 6^th Edition – Prentice Hall of India. (Chapter-17).

2. I.L. Finar Organic Chemistry, Vol.- I, 6^th Edition, Pearson education (Chapter-1).
3. M.K. Jain and S.C. Sharma ‘Modern Organic Chemistry’, 3^rd Edition, Vishal Publishing Company Co. (Chapter-44)

4. K.S. Tewari and N. K . Vishnoi ‘Organic Chemistry’, 3^rd Edition, Vikas Publishing House,(Chapter-26).

Further Reading

1. W. Kemp, ‘Organic Spectroscopy’, Longman, 1995.
2. D.L.Pavia,G.M.LampmanandG.S. Kriz ‘ Introduction to Spectrosopy’ Thomson Brooks Cole.
3. Paula Y. Bruice, ‘Organic Chemistry’, 3^rd Pearson Education Asia

 Practical CH5 B02: Preparation and Basic Laboratory skills 

Credit 1                                                                                                (36 hrs)

A. Basic Laboratory Skills

a. Solvent extraction – aniline from water – methyl benzoate from water – using ether-Record the yield recovery- (Any two experiments shall be done)

b. Crystallisation – Any four compounds using ethyl acetate, ethanol, and water – Record the yield recovery.

B. Preparations

1. Organic preparations involving.–

1. Oxidation (benzaldehyde to benzoic acid).
2. Hydrolysis (methyl salicylate or ethyl benzoate to the acid).
3. Nitration (m-dinitrobenzene and picric acid).
4. Halogenation (p-bromoacetanilide from acetanilide).
5. Diazocoupling (methyl orange or benzene azo –β-naphthol ).

References

1. F.G Mann and B.C. Saunders, ‘Practical Organic Chemistry’ Fourth Edition, Pearson Education.
2. A.I.Vogel, ‘Vogel’s Textbook of Practical Organic Chemistry’ Pearson Education
3. Brauer ‘Handbook of Preparative Inorganic chemistry’, Vol – I & II, Academic Press.

CH5B03-States of matter

Credits    – 2                                                                                       (36 hours)

Aim

 To understand the general characteristics of different states of matter

 Objectives

• To study the intermolecular forces in gases and liquids
•  To understand the dynamics of the molecules in the gases and liquids To study liquefaction of gases
•  To learn the structure of solids To study defects in crystals To study adsorption.

1. Gases (12 hours)

 Kinetic molecular model of gases: pressure of an ideal gas, derivation of gas laws, Maxwell’s distribution of velocities – molecular velocities (average, root mean square and most probable velocities)

 Collision diameter, mean free path, viscosity of gases – temperature and pressure dependence. Relation between mean free path and coefficient of viscosity. Barometric distribution law, Law of equipartition of energy, degrees of freedom and molecular basis of heat capacities.

 Real gases: compressibility factor z, van der Waals equation of state – derivation and application in explaining real gas behaviour. Virial equation of state, van der Waals equation expressed in virial form – calculation of Boyle temperature, Isotherms of real gases, continuity of states. Critical phenomena.

 Liquefaction of gases (based on Joule-Thomson effect)

 References

4. B.R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical chemistry, Vishal Pub. Co. Jalandhar, Chapters 1,2
5. K.L. Kapoor, A Textbook of Physical chemistry, Volumes 1, Macmillan India Ltd Chaper 1
6. P. Atkins and J Paula, The elements of Physical chemistry, 7^th edn., Oxford University Press, Chapter 1
7. F.A. Alberty and R J Silby, Physical Chemistry, 3^rd Edn, John Wiley, Chapter 17
8. Liquids                                                                                                                                                                       (3hrs)

 Intermolecular forces in liquids (qualitative idea only)- viscosity, the viscometer method-surface tension – structure of liquids. Unusual behaviour of water.

 References

1. K.L. Kapoor, A Textbook of Physical chemistry, Volumes 1, Macmillan India Ltd Chaper 2,3

2. B.R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical chemistry, Vishal Pub. Co., Chapter 3.

3. Symmetry and Solid state (21 hours)

Symmetry of molecules-symmetry elements and symmetry operations – centre of symmetry, plane of symmetry, proper and improper axes of symmetry, combination of symmetry elements, molecular point groups, Schoenflies symbol, crystallographic point groups

The nature of the solid state- anisotropy- the law of constancy of interfacial angles, law of rational indices – Miller indices. Seven crystal systems and fourteen Bravais lattices. X-ray diffraction, Bragg’s law, detailed study of simple, face centred and body centred cubic systems – Bragg’s x-ray diffractometer method and powder pattern method. Analysis of powder diffraction patterns of NaCl and KCl, density of cubic crystals, identification of cubic crystal from crystallographic data

Close packing of spheres, ccp and hcp arrangements .Structure of ionic compounds of the type AX (NaCl, CsCl, ZnS) and AX₂ (CaF₂, Na ₂O) .Defects in crystals – stoichiometric and non-stoichiometric defects, extrinsic and intrinsic defects. Electrical conductivity, semiconductors, n-type, p-type, Superconductivity – an introduction.

 Liquid crystals thermographic behaviour. Classification, structure of nematic and cholestric phases.

 Adsorption – types, adsorption of gases by solids – factors influencing adsorption – Freundlich adsorption isotherm – Langmuir adsorption isotherm (derivation). The BET theory (no derivation) – use of BET equation for the determination of surface area.

 References

1. K.L. Kapoor, A Textbook of Physical chemistry, Volume 1, Macmillan India Ltd Chapers 2,3

2. P. Atkins and J. Paula, The elements of Physical chemistry, 7^th edn., Oxford University Press, Chapter 23

3. A. McQuarrie, J. D. Simon, Physical Chemistry – A molecular Approach, Viva Books Pvt. Ltd, Chapter 29

4. B.R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical Chemistry, Vishal Publishing Co, Chapter 5

Further reading

1. A.R. West, Solid State Chemistry and its applications, John Wiley.

2. G.W. Castellan, Physical Chemistry, 3^rd edn., Narosa Publishing House, New Delhi.

3. P.W. Atkins, The elements of Physical chemistry, 8^th edn., Oxford University Press (2006).

4. S.H. Marron and J. B. Lando, Fundamentals of Physical Chemistry, Macmillan Ltd. (1996)

5. D K Chakrabarty, Adsorption and Catalysis by Solids, New Age India.
6. R E Hummel, Understanding materials science 2^ndedn, Springer.
7. G.M. Barrow, Physical Chemistry, 5^th edn., Tata McGraw Hill.
8. G.K. Vemulapalli, Physical Chemistry, Prentice-Hall India Pvt. Ltd.
9. W.J. Moore, Basic Physical Chemistry, Orient Longman.
10. W. Adamson and A P Gast, Physical Chemistry of surfaces, John Wiley sons.

11. http://www.iupac.org/dhtml_home.html
12. K.J Laidler, John H.Meiser, Physical Chemistry,2^nd edn.

 Practical: CH5 B03-Physical Chemistry Practicals

Credits 2                                                                                            (54hrs)

1. Viscosity – percentage composition of a mixture.
2. Heat of solution – KNO₃, NH₄Cl
3. Heat of neutralization
4. Determination of equivalent conductance of an electrolyte
5. Conductometric titration – strong acid strong base, weak acid-strong base

6. Determination of partition coefficient of non-volatile solute between two immiscible solvents. E.g. I₂ between CCl₄ and water.

7. Transition temperature of salt hydrates. (Sodium thiosulphate, sodium acetate)

References

1. W.G. Palmer: ‘Experimental physical chemistry’, Cambridge University Press.
2. J.B. Yadav: Advanced Practical Physical Chemistry Goel Publishing House.
3. R.C. Das and B. Behra; ‘Experiments in Physical Chemistry’ , Tata McGraw hill.

4. K.K. Sharma : ‘An Introduction of Practical Chemistry’: Vikas Publishing House, New Delhi.

CH5B04-Quantum Mechanics and Spectroscopy

Credits     – 3                                                                                      (54hours)

Aim

To understand the fundamentals of quantum mechanics and its applications in the study of structure of atoms, bonding in molecules and molecular spectroscopy

Objectives

• To differentiate between classical and quantum mechanics
• To study the postulates of quantum mechanics and the quantum mechanical model of the hydrogen atom
• To study valence bond and molecular orbital theory
• To study the principle and applications of microwave, infra red, Raman, electronic and magnetic resonance spectroscopy.
• To study the fundamentals of mass spectrometry To study the fundamentals of

           photochemistry

1. Quantum mechanics (18hrs)

 Classical mechanics: concepts, failure of classical mechanics, qualitative idea about the energy distribution in black body radiation. Plank’s radiation law, Compton effect.

 Binding energy of an electron in hydrogen atom, radius of the hydrogen atom, de Broglie hypothesis, dual nature of electrons – Davisson and Germer’s experiment. Heisensberg’s uncertainty principle and its significance. Sinusoidal wave equation (no derivation needed). Wave function – physical interpretation, concept of operators, eigen functions, eigen values.

 Postulates of quantum mechanics, Particle in one-dimensional box – derivation for energy, application to linear conjugated polyene (butadiene). Introductory treatment of Schrödinger equation for hydrogen atom. Quantum numbers and their importance, hydrogen like wave functions – radial and angular wave functions, radial distribution curves.

 Molecular orbital theory: basic ideas – criteria for forming MO from AOs, construction of molecular orbital by LCAO method, H₂⁺ ion (elementary idea only), physical picture of bonding and anti bonding wave functions, concept of , *, , * orbitals and their characteristics. Introduction to valence bond model of hydrogen molecule, comparison of MO and VB methods.

References

1. K.L. Kapoor, A Textbook of Physical chemistry, Volume 4, Macmillan India Ltd Chaper 1,2

2. Mc Quarrie, J. D. Simon, Physical Chemistry – A molecular Approach, Viva Books Pvt. Ltd, Chapters 1,2,3,4,6

3. I.N. Levine, Physical Chemistry, Tata Mc Graw Hill, Chapter18

4. A. Bahl, B. S. Bahl, G. D. Tuli, Essentials of Physical Chemistry, S. Chand and Company, chapter 1,2

5. K.J. Laidler, John H.Meiser, Physical Chemistry,2^nd edn, Chapters 11,12

Further reading

1. P Atkins, J Poula, Physicl Chemistry, 8 th edn,OUP
2. Mc Quarrie, Quantum Chemistry, Viva Books
3. I.N. Levine, Quantum Chemistry 5^th edn, Pearson.

4. R.K. Prasad, Quantum Chemistry, New Age.

2. Molecular spectroscopy I                                                                                                                          (15hrs)

Introduction: electromagnetic radiation, regions of the spectrum, interaction of electromagnetic radiation with molecules, various types of molecular spectroscopic techniques, Born-Oppenheimer approximation.

Rotational spectrum: diatomic molecules, energy levels of a rigid rotator, selection rules, determination of bond length.

Vibrational spectrum: the simple harmonic oscillator – energy levels, force constant, selection rules. Anharmonic oscillator – pure vibrational spectra of diatomic molecules, selection rules, fundamental frequencies, overtones, hot bands. Degrees of freedom for polyatomic molecules, concept of group frequencies – frequencies of common functional groups in organic compounds.

Raman spectrum: quantum theory of Raman Effect (elementary idea), concept of polarizability, qualitative treatment of pure rotational and pure vibrational Raman spectra of diatomic molecules, selection rules, rule of mutual exclusion.

References

1. Mc Quarrie, J. D. Simon, Physical Chemistry – A molecular Approach, Viva Books Pvt. Ltd
2. C.N. Baanwell and E M Mc Cash, Fundamentals of molecular spectroscopy 4^thedn, TataMc Graw Hill,Chapters I- 4.

3. K.L. Kapoor, A Textbook of Physical chemistry, Volumes 4, Macmillan India Ltd Chaper 4

4. I.N. Levine, Physical Chemistry, Tata Mc Graw Hill, Chapter 21

5. R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical chemistry, Vishal Pub. Co., Chapter 21

6. K.J. Laidler, J. H.Meiser, Physical Chemistry,2^nd edn, Chapter 13

Further reading

1. D.L. Pavia, G. M. Lampman, G. S. Kriz, Introduction to spectroscopy 3^rd edn, Thomson Brooks/Cole, 2001.

2. D.N .Satyanarayana, Electronic absorption spectroscopy and related techniques, Universities Press.

3. Molecular spectroscopy II                                                                                                                          (15 hrs)

Electronic spectrum: concept of potential energy curves for bonding and anti-bonding molecular orbitals, electronic transition, the Frank-Condon principle, dissociation energy. Polyatomic molecules – qualitative description of -, – and n- molecular orbitals, their energy levels and the respective transitions.

NMR spectroscopy: basic principles of NMR spectroscopy – nuclear spin, Larmor precession. Proton magnetic resonance (¹H NMR or PMR) – nuclear shielding and deshielding, chemical shift and molecular structure. Spin-spin splitting and coupling constant. First order spectra – interpretation of PMR spectra of simple organic molecules such as ethyl bromide, ethanol, acetaldehyde, ethyl acetate, toluene, acetophenone.

 Mass spectrometry: Basic principle-ionization, fragmentation, separation of ions and representation of the spectrum, application in molecular mass determination

 References

1. Mc Quarrie, J. D. Simon, Physical Chemistry – A molecular Approach, Viva Books Pvt. Ltd,

2. C.N. Baanwell and E M Mc Cash, Fundamentals of molecular spectroscopy 4^thedn, TataMc Graw Hill,Chapters 6,7

3. K.L. Kapoor, A Textbook of Physical chemistry, Volumes 4, Macmillan India Ltd Chapter 4

4. I.N. Levine, Physical Chemistry, Tata Mc Graw Hill, Chapter 21

5. R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical chemistry, Vishal Pub. Co., Chapter 21

6. K.J. Laidler, John H.Meiser, Physical Chemistry,2^nd edn, Chapter 14

Further reading

1. P Atkins, J Poula, Physical Chemistry, 8 th edn , OUP

2. D.L. Pavia, G. M. Lampman, G. S. Kriz, Introduction to spectroscopy 3^rd edn, Thomson Brooks/Cole, 2001.

3. D.N. Satyanarayana, Electronic absorption spectroscopy and related techniques, Universities Press.

4. G.K. Vemulapalli, Physical Chemistry, Prentice-Hall of India Pvt. Ltd.

4. Photochemistry ( 6 hrs)

Interaction of radiation with matter: Laws of photochemistry – Grothus-Draper law, Stark-Einstein law, examples of photochemical reactions. Beer law and Beer-Lambert’s law. Jablonsky diagram, qualitative description of fluorescence, phosphorescence, non-radiative processes (internal conversion, intersystem crossing).

Quantum yield , primary and secondary processes. Basic concepts of photosensitized reactions – photosynthesis, dissociation of hydrogen molecule, isomerization of 2-butene, and chemiluminescence. 6 hrs

 References

1. K.L. Kapoor, A Textbook of Physical chemistry, Volumes 4, Macmillan India Ltd, Chaper 7

2. I.N. Levine, Physical Chemistry, Tata Mc Graw Hill, Chapter 21

3. R. Puri, L. R. Sharma, M. S. Pathania, Elements of Physical chemistry, Vishal Pub. Co., Chapter 22

4. K.K. Sharma, L R Sharma, A text book of Physical Chemistry, Vikas Publishing house Chapter 24

 Further reading

1. K.K. Rohatgi-Mukherjee , Fundamentals of Photochemistry, New Age.

2. K.K. Sharma, L. R. Sharma, A text book of Physical Chemistry, Vikas Publishing house