UNIT – I: Types of Reactions, Mechanisms and Reaction intermediates                       

 

Types of reactions : Substitutions, Additions, Eliminations, Rearrangements,  Oxidations and Reductions reactions – a general study.

Reaction mechanisms: Types of mechanisms : Heterolytic, Homolytic and Pericyclic mechanisms – a general study.

Reaction intermediates: Formation, stability and structure of carbonium ions, carbanions, carbenes, nitrenes and free radicals. 

Long lived and short lived free radicals, methods of generation and detection of free radicals, free radical reactions: Sandmeyer reaction, Gomberg-Bachmann reaction, Pschorr reaction and Ullmann reaction, mechanism of Hunsdiecker reaction.

 

UNIT – II: Stereochemistry

                                                                                   

Concept of chirality, recognition of symmetry elements and chiral structures, R – S nomenclature, Fischer, Newman and Sawharse projections of erythro and threo forms of organic molecules and their interconversion.  Optical activity in the absence of chiral carbon – biphenyls, allenes and spiranes – R and S notations. Chirality due to helical shape, trans cyclooctene, cyclononene. E – Z isomerism of olefins containing one double bond . Stereochemistry and Conformational Analysis  : Stereospecific and stereoselective synthesis with one suitable example, asymmetric synthesis – Crams rule,  Conformational analysis and stereochemical features of disubstituted cyclohexanes ( 1,2 ; 1,3 ; 1,4 dialkyl cyclo hexanes ), conformation and stereochemistry of cis and trans decalins,

 

 

 

 

 

 

 

 

UNIT – III: Aliphatic Nucleophilic Substitution Reactions                                                

 

The S_N², S_N¹,mixed S_N¹ and S_N², S_Nⁱ and SET mechanisms. The neighbouring group mechanism, neighbouring group participation by p and s bonds, anchimeric assistance. Nucleophilic substitution at an allylic, aliphatic trigonal and vinylic carbon.

Reactivity effects of substrates structure, attacking nucleophile, leaving group and reaction medium, ambident nucleophile, regioselectivity. Substitution at carbon doubly bonded to oxygen and nitrogen, Williamson reaction, Von-braun reaction, hydrolysis of esters, Claisen and Dieckmann condensation.

 

UNIT IV:  Heterocyclic Compounds   

Synthesis and properties of imidazole, oxazole,  thiazole and indole.

General methods of Synthesising Anthocyanidins, Synthesis and Structural elucidation of Cyanidin Chloride,  Synthesis and Structural elucidation of flavones and isoflavones (Daidzein),  Synthesis of pyrimidine and its derivativess, Synthesis of purine, uric acid and caffeine).

 

UNIT V: Aromatic electrophilic, nucleophilic substitution reactions  and Aromaticity     

                                                   

The arenium ion mechanism, typical reactions like nitration, sulphonation, haloganation, Friedal-Crafts alkylation, acylation and diazonium coupling, electrophilic substitution on monosubstituted benzene, orientation and reactivity-ortho, meta and para directing groups,  Gatterman, Gatterman-koch, Vilsmeir, Reimer-Tiemann reaction.

Aromatic nucleophilic substitution reactions, the S_NAr, mechanism, aromatic nucleophilic substitution of activated halides-Ziegler alkylation, Chichibabin reaction.

Aromaticity of benzenoid, heterocyclic and non-benzenoid compounds, Huckel rule, aromatic systems with pi electron compounds other than six pi electrons, non-aromatic (cyclooctatetraene, etc.,) and anti aromatic systems (cyclobutadiene, etc.,), systems with more than 10 pi electrons.

 

Text Books

 

1. Jerry March, Advanced Organic Chemistry- Reactions, Mechanisms and Structure, Fourth Edition, John Wiley & Sons (1992)

2.      Francis A. Carey, Organic Chemistry, Third Edition, The McGraw-Hill 

      Companies, Inc., 1996.

3. P. S. Kalsi, Organic Reactions and Mechanisms, Second Edition, New Age International Publishers, 2002.
4. Ernest L. Eliel, Stereochemistry of Carbon Compounds, T.M.H Edition, Tata McGraw-Hill Publising Company, 1995.
5. P. S. Kalsi, Stereochemistry – Conformation and Mechanism, 6^th Edition, Wiley Eastern Limited, 2005.
6. I.L. Finar, Organic Chemistry, Volume. II, Fifth Edition, First Indian reprint, Pearson Education Asia Pte. Ltd., (2000)

Reference Books

1. P.S. Kalsi, Stereochemistry and Mechanism through solved problems, Second Edition, New Age International Publishers, 1994.
2. D. Nasipuri, Stereochemistry of Organic Compounds, 2^nd Edition, New Age International  Publishers, 1994.
3. S.M.Mukherji and S.P.Singh, Reaction Mechanism in Organic Chemistry, 1^st Edn.,  Macmillan 1976.

4. R.T.Morrison and R.N.Boyd, Organic Chemistry, 6^th Edn., Prentice-
         Hall,1992.

5. R.O.C. Norman, Principles of Organic Synthesis, Second Edition, Chapman
      and Hall, 1978.

6. R.M.Acheson, Introduction to Chemistry of Heterocyclic Compounds, 2^nd Edn.,

     Interscience Publishers, 1967.

7.      J.A. Joule and G.F. Smith, Heterocyclic Chemistry, Van Notrand Reishord Co.,   London, 1978.  

UNIT  I : Structure and Bonding                                                                             

 

                        Van der Waals bonding, Hydrogen bonding and applications, Hard and Soft acids and bases-classification, Acid-Base strength, hardness, Symbiosis, Theoretical basis of Hardness and Softness, applications of HSAB.

Polyacids - Isopolyacids of V, Cr, Mo and W; Heteropolyacids of Mo and W (only structural aspects).

Inorganic polymers – Silicates – structure, Pauling’s rule, properties, correlation and application; Molecular sieves.

Rings – Phosphazenes – Structure, Craig and Peddock model, Dewar model, polyorganophosphazenes, Polysulphur-nitrogen compounds.

 

UNIT – II: Nuclear Chemistry                                                                                             

                        Nuclear properties - Nuclear spin and moments, origin of nuclear forces, features of the liquid drop and the shell models of the nucleus; Modes of radioactive decay - orbital electron capture, nuclear isomerism, internal conversion; Detection and determination of activity - Cloud chamber, nuclear emulsion, Bubble chamber, GM, Scintillation and Cherenkov counters.

                        Nuclear reactions - Types, reaction cross section, Q-value, threshold energy, compound nuclear theory, high energy nuclear reactions, nuclear fission and fusion reactions as energy sources, direct reactions, photonuclear and thermo nuclear reactions, Stellar energy, synthesis of elements.

                        Applications relating to Nuclear Chemistry - Neutron activation analysis, Radio pharmacology, Radiation protection and safety precautions, Isotope dilution analysis.

Radiation Chemistry - Range of alpha and beta radiations, radiation dosimetry, radiolysis of water, the hydrated electron.

 

UNIT III: Stability and bonding in complexes        

                        Stability of complexes -Factors affecting stability of complexes, thermodynamic aspects of complex formation, Stepwise and overall formation constants, stability correlations, statistical and chelate effects; Determination of stability constant - polarographic, photometric and potentiometric methods.

Stereochemical aspects - Stereoisomerism in inorganic complexes, isomerism arising out of ligand distribution and ligand conformation, chilarity and nomenclature of chiral complexes; application of ORD and CD in the identification of chirality of complexes.

Macrocyclic ligands - types -  porphyrins, corrins, Schiff’s bases, crown ethers and cryptates.  (simple complexes )

Metal-Ligand Bonding  Crystal field theory - Splitting of d- orbitals under various geometries, factors affecting splitting, CFSE, evidences for CFSE (Structural and thermodynamic effects), Spectrochemical series, Jorgensen relation, site preferences; Jahn-Teller distortion - Splitting pattern in trigonal pyramid, square pyramidal and cubic symmetries, Dynamic and Static J.T. effect, Jahn-Teller effect and Chelation; Limitations of CFT; Evidences for metal-ligand overlap; M.O. theory and energy level diagrams, concept of weak and strong fields, sigma and pi bonding in complexes, nephelauxetic eff

 

UNIT IV: Electronic Spectra of Complexes                                                                        

                        Spectroscopic Term symbols for dⁿ ions - derivation of term symbols and ground state term symbol, Hund’s rule; Selection rules – break down of selection rules, spin- orbit coupling, band intensities, weak and strong field limits- correlation diagram; Energy level diagrams; Orgel and Tanabe-Sugano diagrams; effect of distortion and spin orbit coupling on spectra; Evaluation of Dq and B values for octahedral complexes of Nickel; Charge transfer spectra; , magnetic properties of  complexes.

 

UNIT V: Analytical Chemistry                                                                                            

                        Polarography - Theory, apparatus, DME, diffusion, kinetic catalytic currents, current voltage curves for reversible and irreversible systems; qualitative and quantitative applications to Inorganic systems.

                        Amperometric titrations - Theory, apparatus, types of titration curves, successive titrations and two indicator electrodes; applications; Complexometric titrations - Chelating agents; types of EDTA titration - direct and back titrations; replacement titrations - masking and demasking reagents.

                        Chromatography - Gas liquid chromatography – principle; retention volumes; instrumentation; carrier gas; columns preparations; stationary phase; detectors - thermal conductivity, flame ionization, electron capture; applications of GLC.

High performance liquid chromatography – scope; column efficiency; instrumentation; pumping systems; columns; column packing; detectors; applications.

Text Books :

 

1. H.J. Emelius and Sharpe, Modern aspects of Inorganic chemistry, Universal book Stall, New Delhi, 1989.
2. J.E. Huheey, E.A. Keiter and R.L. Keiter, Inorganic Chemistry- Principles of structure and reactivity, 4^th edition, Pearson-Education, 2002.
3. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern, 5^th edition, 1988.
4. F. Basolo and R.G. Pearson, Mechanism of Inorganic Reactions, Wiley Eastern, 1967.
5. S. Glasstone, Source book of Atomic Energy, Van Nonstrand Co., 1969.
6. H.J. Arniker, Essentials of nuclear chemistry, 2^nd edition Wiley eastern Co.,1987.

7.      D.A. Skoog, Principles of Instrumental Analysis, Saunders College Pub.Co, III Edn., 1985.

8.      J.G. Dick, Analytical Chemistry, McGraw Hill Publishers, 1974.

9.      A.I Vogel, Text Book of Quantitative Inorganic Analysis, Pearson V Edn., 2001.

10.  R.C. Kapoor and B.S. Agarwal, Principles of polarography, Wiley Eastern Ltd., 1991.

 

Reference Books

1. K.F. Purcell and J.C. Kotz, Inorganic Chemistry, WB Saunders Co. USA 1977.
2. G.S. Manku, Inorganic Chemistry, TMH Co., 1984.
3. A.K. Srivatsava and P.C. Jain, Elements of Nuclear Chemistry, S. Chand and Co., 1989.
4. G. Friedlander, J.W. Kennedy and J.M. Miller, Nuclear and Radiochemistry, Wiley,

1964.

5.     

UNIT- I: Classical Thermodynamics –I                                                                 

          Maxwell’s relations and thermodynamic equations of state – applications in the evaluation of Cp – Cv for solids and for vanderwaals gases,  Cp – Cv  interms of coefficient of expansion and coefficient of compressibility – Relation between Cp and Cv – Partial molar properties- Gibbs – Duhem equation- Partial molar free energy ( Chemical Potential) – Determination of chemical potential [Direct method  and Method of Intercepts] and partial molar volume – variation of chemical potential with Temperature and Pressure – Thermodynamic derivation of phase rule – application to three component systems involving solids and liquids

(CH₃ COOH – CHCl₃ – H₂O,  NaCl –  Na₂SO₄ - H₂O and  NH₄  NO₃ –( NH₄)₂ SO₄ -H ₂O).

 

UNIT –II: Statistical Thermodynamics                                                      

          Objectives of Statistical Thermodynamics – concept of thermodynamical and mathematical  probabilities – Distribution of distinguishable and non- distinguishable particles.

Maxwell – Bottzmann, Bose – Einstein  and  Fermi – Dirac statistics – comparison and application.

Partition Functions – evaluation of Translational, Vibrational, Rotational and Electronic partition Function – Thermodynamic Functions in terms of partition Function – Application  of Partition Function to monatomic and diatomic gases – Statistical expression for equilibrium Constant – Calculation of Equilibrium Constant from Partition Function – ( isotope exchange equilibrium and dissociation of diatomic molecules) – Heat capacities of Monatomic crystals – Einstein and Debye theory of heat capacities.

 

UNIT –III: Group Theory –I                                                                       

          Symmetry elements and symmetry operations – Point groups – identification and representation of groups – comparison of Molecular symmetry with Crystallographic symmetry – Reducible and irreducible representation – Direct product representation – Great orthogonality theorem and its consequences – Character Table and their uses.

 

UNIT –IV: Group Theory – II                                                  

            Symmetry selection rules for vibrational, Electronic and Raman Spectra – determination of representation of vibrational modes in non- linear molecules such as H2O, CH4, XeF4, SF6 and NH3 – symmetry of Hybrid orbitals in non- linear molecule ( BF3, CH4, XeF4, PCl5, and SF6,) – Electronic spectra of formaldehyde – application of group theory.

 

UNIT –V: Chemical Kinetics 

                                                                                                                                   

          Theories of Reaction rates – Arrhenius theory – effect of temperature on reaction rate – Hard – Sphere collision theory of reaction rates – molecular beams – collision cross section – effectiveness of collisions – Probability factor.

            Transition state theory of reaction rates - Potential energy surface – Partion functions and activated complex – Eyring equation - Comparison of results with Eyring and Arrhenius equations – Estimation of free energy, enthalpy and entropy of activation and their significance.

 

Text Books :

1. S;Glasstone, Thermodynamics for chemists, Affiliated East West press, New Delhi, 1960.
2. J.Rajaram and J.C.Kuriacose, Thermodynamics for students of Chemistry, Lal Nagin chand, New Delhi,1986.
3.  J.Rajaram and J.C.Kuriacose, Kinetics and mechanism of chemical transformation Macmillan India Ltd.,1993.
4. K.J.Laidlar, Chemical kinetics, Harper and Row New york,1987.
5. D.A. Mcquarrie, Quantum chemistry, University science books, Mill Valley, California (1983)
6. R.K.Prasad, Quantum Chemistry, Wiley Eastern, New Delhi,1992.
7. V.Ramakrishnan and M.S. Gopinathan, Group theory in Chemistry, Vishal Publications,1988.
8. K.V.Raman, Group theory and its application to Chemistry, Tata McGraw Hill Publishing Co., 1990.

 

 

 

 

Reference   Books

1. W.J.Moore, Physical Chemistry, Orient Longman, London,1972
2. K.G. Den beigh, Thermodynamics of Steady state, Meklien and Co., London,1951

[

3. L.K.Nash, Elements of Chemical Thermodynamics, Addison Wesley,1962
4. R.G.Frost and Pearson, Kinetics and Mechanism, Wiley Newyork,1961
5. J.W.Moore and R.G. Pearson, Kinetics and Mechanism,1981
6. C.Capellos and B.H.J.Bielski, Kinetic Systems, Willey interscience, Newyork, 1968
7. G.M.Harris, Chemical Kinetics, D.C. Heath and Co,1966
8. I.N.Levine, Quantum Chemistry, Allyn and Bacon, Boston,1983
9. J.Goodman, Contemporary Quantum Chemistry, An Introduction, Plenum Press, Newyork,1977.
10. F.J.Bockhoff, Elements of Quantum Theory, Addision Wesley, Reading , Mass,1976

 

11. P.W.Atkins, Physical Chemistry, Oxford University press, Oxford. 1990.
12. P.W.Atkins, Molecular Quantum Mechanics, Oxford University press, Oxford,1983

 

13. H.Eyring, J,Walter and G.Kimball, Quantum chemistry, John wiley and sons, Newyork,1944.
14. L.S.Pauling and E.B.Wilsob, Introdu

UNIT I: Basic Concepts

                                                                                                                       

                        Monomers, repeat units, degree of Polymerization, Linear , branched and network Polymers.Condensation Polymerization :Mechanism of stepwise polymerisation .Kinetics and statistics of linear stepwise polymerization.Addition polymerization :Free radical , cationic and anionic polymerization. Polymerization conditions. Polymerization in homogeneous and heterogeneous systems.

 

UNIT II: Co-ordination Polymerization

                                                                                                                               

                        Kinetics, mono and bimetallic mechanism of co-ordination polymers.. Co-Polymerization : Block and graft co-polymers, Kinetics of copolymerization. Types of co-polymerization. Evaluation of monomer. Reactivity ratio. Rate of Co-Polymerization.

 

UNIT III: Molecular Weight and Properities         

                                                                                                                  

                        Polydispersion – average molecular weight concept, number ,weight and viscosity average molecular weights. Measurement of molecular weights. Gel permeation chromatography, viscosity, light scattering, osmotic and ultracentrifugation methods. Polymer structure and physical properities – crystalline melting point T_m . The glass transition temperature. Determination of T_g . Relationship between T_m  and T_g .

 

UNIT IV: Polymer Processing

                                                                                                                              

                        Plastics, elastomers and fibres. Compounding processing techniques : calendering, die casting , rotational casting, film casting , injection moulding, blow moulding extrusion moulding, thermoforming, foaming , reinforcing and fibre spinning.

 

UNIT V: Properties of  Commercial Polymers

                                                                                                                  

                        Polyethylene, polyvinyl chloride, polyamides, polyesters, phenolic resins, epoxy resins and silicone polymers. Functional polymers – Fire retarding polymers and electrically conducting polymers. Biomedical polymers – contact lens, dental polymers, artificial heart, kidney, skin and blood cells.

 

 

 

 

 

Text Books

 

1.   F.W.Billmeyer, TextBook of Polymer Science, 3^rd Edn., J.Wiley, 2003.

2.        V.R.Gowarker, N.V.Viswanathan and J.Sreedhar, Polymer Science, New Age Int.,1986.

 

Reference Books

 

1.    H.R.Alcock and F.W.Lamber, Contemporary Polymer Chemistry, Prentice Hall,1981.

2.    P.J.Flory, Principles of Polymer Chemistry, Cornell University press, Newe York, 1953.

3.   G.Odian, Principles of Polymerization, 2^nd Edn., John Wiley & Sons, New York,1981.

 

UNIT – I: Microwave Spectroscopy

 

          Interaction of matter with radiation – Einstein’s theory of transition probability – Rotation spectroscopy – Rigid Rotor – Intensity of spectral lines – Molecular parameters from Rotation spectra – Effect of isotopic substitution on the rotation spectra.

 

UNIT-II: IR and Raman Spectra     

 

                        Theory, principle, instrumentation of IR and Raman Spectra. Characteristic group frequencies of organic molecule, Factors influencing vibrational frequencies, interpretation of IR spectra of organic molecules. Raman spectroscopy – Raman effect – Rotational and vibrational Raman Spectra. Applications of   Raman Spectra.

UNIT-III: UV-VIS and Emission Spectra

 

            Theory, principle, instrumentation of UV – VIS and Emission spectra.

 

UV-VIS : Woodward – Fieser  rules for dienes, enones. Calculation of λmax for organic molecules. Chromophores and effect of conjugation, substituents with unshared electrons and their capability of  ? - conjugation . Colour in compounds.

Applications of  UV – VIS and Emission spectra.

 

UNIT-IV: ¹H and ¹³C  NMR  Spectra                                              

                        NMR spectroscopy : Theory, principle, instrumentation,  Chemical shift, factors influencing chemical shift,  spin-spin coupling, NMR of simple AX and AMX type organic molecules, calculation of coupling constants, identification of H in various chemical environments to assign structure to the organic molecules using chemical shift values, resonance coupled and decoupled spectra ¹³C NMR, applications of ¹³C NMR to find the different carbon functional groups.

UNIT-V: Mass spectra

                        Mass spectra – theory, principle, instrumentation and applications. McLafferty rearrangement, fragmentation pattern, Examples of mass spectral fragmentation of organic compounds with respect to their structure determination.

Text Books

1.        Y. R. Sharma, Elimentary Organic Spectroscopy, 1^st Edn., S. Chand & Company Ltd, New Delhi, 1980.

2.     J. Dyer, Application of absorption spectroscopy of organic compounds, Prentice-

           Hall of India Pvt. Ltd., New Delhi, 2005

2.     Raymond chang, Basic principles of Spectroscopy, McGraw Hill Ltd., New York, 1971

3.     C.N.Banwell, Fundamentals of Molecular spectroscopy, Mc Graw Hill, Newyork, 1966.

Reference Books

1.      R.M Silverstein, C.G. Bassler and Monsil, Spectrometric identification of organic 

compounds, 6^th Edn., John Wiley & Sons, New York 2004.

2.      William Kemp, Organic Spectroscopy, ELBS, New Delhi, 1982.

3.      S. Kalsi, Spectroscopy of organic compounds, 5^th Edn., Wiley Eastern Ltd., Madras,

      2002.

4.      C.N.Banwell, Fundamentals of Molecular Spectroscopy, McGraw Hill, New York,1966.

5.      A.Carrigton and A.D.McLachlan, Introduction to Magnetic Resonance, Harper and Row New York 1967.

6.      R.Drago, Physical methods in Inorganic Chemistry, Reinhold, Ny.1968.

7.      G.M.Barrow, Introduction to Molecular Spectroscopy, McGrawHill,

 NewYork,1962.

8.      W.Kemp, NMR in Chemistry, MacMillan Ltd,1986.

9.      G.W.King, Spectroscopy and Molecular structure, Holt, Rienehart and winston

1964.

10. C.N.R.Rao, J.R.Ferraro, Spectroscopy in Inorganic Chemistry, Methven Co.,

       London. 1968.

11.Raymond Chang, Basic Principles of Spectroscopy, Mc Graw Hill Ltd., New York,     

UNIT-I: Introduction to Nanotechnology         

             Definition, classification, a historical perspective, nanoparticles, nanocrystal, quantum dot, nanometer., new properties of nanomaterials, nanomaterials in medicine, information storage, sensors, new electronic devices, environmental remediation, clean catalysts. Metal nanoparticles, Chemical bonding and properties of bulk metals as well as metal nanoparticals. Gas phase and chemical synthetic methods to metal nanoparticles, nanoelectrons, conductivity of nanoelectrons.

UNIT-II:  Properties and Applications of Nanocrystals  

            Nanotubes, Nanocrystal shape, Sequestration of gases, destructive adsorption of environmental toxins, Optical properties, Magnetic properties of nanoscale materials – diamagnetism, paramagnetism, ferromagnetism, and supermagnetism.  Size dependent properties such as coercivity ( magnetic memory ) and saturation magnetization,  nanoparticles in polymers, inks, fluids, dyes and catalysis. Nanocrystals as colorants, ultraviolet absorbers, electronics and in biomedical applications.

UNIT-III: Green Chemistry Basics                 

            The need for green chemistry and eco-efficiency, environmental protection laws, challenges and green chemistry education, pollution control and pollution prevention – green methods, green products, recycling of waste.

Twelve principles of green chemistry, inception of green chemistry, awards for green chemistry and international organizations promoting green chemistry.

 

UNIT-IV:    Solvent Free Organic Synthesis         

            Solvent free microwave assisted organic synthesis – microwave activation, microwave heating, advantages of microwave exposure and specific effects of microwaves. Organic synthesis under microwaves – benefits, limitations, equipments.

Reactions on solid supports, phase transfer catalysis, solvent free esters saponification, reactions without support or catalyst, examples – microwave assisted reactions in water – oxidation of toluene to benzoic acid, microwave assisted reactions in organic solvent Diels Alder reaction.

 

 

 

 

UNIT-V:   Designing  Green Synthesis     

Designing  Green Synthesis – choice of starting materials, choice of reagents, choice of catalysts – bio catalysts, polymer supported catalysts, choice of solvents. 

Synthesis involving basic principles of green chemistry – examples – synthesis of adipic acid, methyl methacrylate,  paracetamol.

Ultrasound assisted reactions – esterification, reduction, coupling reactions. Strecker synthesis and reformatsky reaction.   

 

 

Text Books

1.  Kenneth . Klabunde, Nanoscale Materials in Chemistry,  John Wiley & Sons, 

      Inc. 2002

2.  Rashmi Sanghi, M. M. Srivastava, Green Chemistry, Environment Friendly 

      Alternatives,  Narosa Publishing House, 2007

3.  V. Kumar, An Introduction to Green Chemistry, Vishal Publishing CO.  Jalandhar, 2007

I. Identification of components in a two component mixture and preparation of their derivatives. Determination of boiling point/melting point for components and melting point for their derivatives.

 

 

II. Preparation

 

1.      Beta naphthyl methl ether from beta naphthol

2.      s–Benzyl isothiuronium chloride from benzylchloride

3.      Beta glucose penta acetate from glucose

4.      ortho- Benzoyl benzoic acid from phthalic anhydride

5.      Resacetophenone from resorcinol

6.      para- Nitrobenzoic acid from para nitrotoluene

7.      meta-Nitroanilline from meta dinitrobenzene

8.      Methyl orange from sulphanillic acid

9.      Anthraquinone from antracene

10.  Benzhydrol from benophenone

Reference: Laboratory Manual of Organic Chemistry – B. B. Dey, M. V. Sitaraman

Part – I

 

                        Semimicro qualitative analysis of mixtures containing two common and two rare cations. The following are the care to be included: W, Tl, Mo, Te, Se, Ce, Th, Be, Zr, V, U and Li.

 

 

Part – II

 

a)      Colorimetric analysis: visual and photometric; determination of iron, nickel, manganese and copper.

b)      Preparation of the following:

                                 i.            Potassium trioxalatoaluminate (III) trihydrate

                               ii.            Tristhioureacopper (I) chloride

                              iii.            Potassium trioxalatochromate (III) trihydrate

                             iv.            Sodium bis (thiosulphato) cuprate (I)

                               v.            Tetramminecopper (II) sulphate

                             vi.            Potassium Tetrachlorocuprate (II)

c)      Separation of mixture of two metal ions by paper chromatography.

Experiments in chemical kinetics, phase rule, Chemical equilibrium and Conductivity measurements:

 

DETAILED LIST OF EXPERIMENTS

                       

                        Typical list of possible experiments are given. Experiments of similar nature and other experiments may also be given. The list given is only a guideline. A minimum of 15 experiments have to be performed in a year.

 

1. Study the kinetics of  acid hydrolysis of an ester, determination of the temperature coefficient of the reaction and determination of the activation energy of the hydrolysis of ethylacetate.

 

2. Study the kinetics of the reaction between acetone and iodine in acidic medium by half life method and determine the order with respect to iodine and acetone.

 

3. Study of the saponification of ethylacetate by sodium hydroxide conductometrically and determine the order of the reaction.

 

4. Determination of association of ethylacetate by sodium hydroxide conductomertically and determine the order of the reaction.

 

5. Study the phase diagram for m-toluidine and glycerine system.

 

6. Construction of phase diagram for a simple binary system (naphthalene-phenanthrene and benzophenone-diphenylamine).

 

7. Construction of the phase diagram of the three component of partially immiscible liquid systems (DMSO-Water-Benzene; Water-Benzene-Acetic acid; Ethyl alcohol-Benzene-Water; Acetone-Chloroform-Water; Chloroform-Acetic acid-Water).

 

8. Determination of the equilibrium constant of the reaction between Iodine and KI by partition method.

 

9. Determination of equivalent conductance of a weak acid at different concentrations and verify Ostwald’s dilution law and calculation of the dissociation constant of the acid.

 

10. Determination of equivalent conductivity of a strong electrolyte at different concentrations and examine the validity of the Onsager’s theory as limiting law at high dilutions.

 

11. Conductometric titrations of a mixture of HCL and CH₃COOH against Sodium hydroxide

 

12. Compare the relative strength of acetic acid and monochloroacetic acid by conductivity method.

UNIT I   Molecular Rearrangements                                  

A detailed study of the mechanism of the following rearrangements: Nucleophilic, Electrophilic and Freeradical rearrangements- memory effects, migratory aptitudes,  Pinacol-Pinacolone, Wagner-Meerwin, Demyanov, Dienone-Phenol, Favorski, Baeyer-Villiger, Wolff, Stevens,  Von-Richter, Clasien, Hofmann, Schmidt, Lossen, Curtius,  Beckmann and Fries rearrangements (a few examples in each rearrangement are to be studied).

UNIT II    Reagents in Organic Synthesis                          

 

Synthesis of simple organic molecules using standard reactions like acylation and alkylation of enamines and active methylene compounds. Sulphur ylides, Robinson annulation,  protection and deprotection of functional groups (R-OH, R-CHO, RCOR, R-NH₂ and R-COOH)  Reagents and their uses: DCC, trimethyl silyl iodide, trimethyl silyl chloride, 1,3-dithiane (umpolung), diisobutylaluminium hydride (DIBAL), 9BBN.

UNIT III    Oxidation and Reduction Reactions   

 

Study of the following oxidation reactions with mechanism: Oxidation of alcohols by CrO₃, DMSO alone, DMSO in combination with DCC; acetic anhydride and oxalyl chloride, oxidation of arylmethane, oxidation of methylene alpha to carbonyl, allylic oxidation of olefins, oxidative cleavage of glycols, oxidative cleavage of double bonds by ozonolysis.

Study of the following reduction reactions with mechanism: Reduction of carbonyl compounds by hydrides, selectivity in reduction of 4-ter-butyl cyclohexanone using selectrides, Clemmensen and Wolff Kishner reductions, Birch reduction, MPV reduction.

UNIT  IV Elimination and Addition Reactions             \

Elimination Reactions : E1, E2, E1cB mechanisms, Orientation of the double bond - Hofmann and Saytzeff rule, dehydration and dehydrohaloganation reactions, stereochemistry of E2 eliminations in cyclohexane ring systems, mechanism of pyrolytic eliminations, Chugaev reaction and Cope elimination.

Addition Reactions : Addition of halogen and nitrosyl chloride to olefins, hydration of olefins and acetylenes, hydroboration, Michael addition, 1,3 dipolar addition, Diels-Alder reaction. Mechanism and reactivity. Mannich, Stobbe, Darzen Glycidic ester condensation, Peterson olefination( Silyl Wittig reaction ), Strecker synthesis,  Perkin , Thorpe , Ritter , Prins reactions.

 

 

UNIT V    BioOrganic Chemistry

                                                                                                           

Proteins, polypeptides and their synthesis (upto a tripeptide), solid phase synthesis (Merrifield synthesis), determination of primary structure of proteins (end group assay), discussion on secondary and tertiary structure of proteins.

Structure and role of (genetic code) DNA and RNA.(Determination of structure is not required) Biosynthesis of  amino acids (phenylalanine, tyrosin, 3,4-dopa, praline only) and cholesterol.

Text Books

1. Jerry March, Advanced Organic Chemistry- Reactions, Mechanisms and Structure, Fourth Edition, John Wiley & Sons, 1992.
2. Francis A. Carey, Organic Chemistry, Third Edition, The McGraw-Hill Companies,          Inc, 1996.
3. P. S. Kalsi, Organic Reactions and Mechanisms, Second Edition, New Age International Publishers, 2000.
4. I.L. Finar, Organic Chemistry, Volume. II, Fifth Edition, First Indian reprint, Pearson Education Asia Pte. Ltd., 2000.

Reference Books

1. S.H.Pine, J.B. Hendrickson, D.J.Cram and G.S.Hammond, Organic Chemistry, IV Edn. McGraw-Hill Company 1980.
2. S.M. Mukherji and S.P.Singh, Reaction Mechanism in Organic Chemistry, III Edn. 1984, MacMillan.
3. R.T.Morrison and R.N.Boyd, Organic Chemistry, Prentice-Hall, 6^th Edn.,1992.
4. R.O.C. Norman, Principles of Organic Synthesis, Second Edition, Chapman and Hall, 1978.
5. Neil Issac, Physical  Organic Chemistry, J.Wiley, New York, 1987.
6. Paul de Mayo, Molecular Rearrangements, Vol.I, Vol. II, Interscience, NY, 1963.

 

UNIT I     Boron compounds and Clusters                                                                          

 

Boron hydrides - polyhedral boranes, hydroborate ions-a general study of preparation, properties and structure, styx numbers , Wade’s rules.

Carboranes - types such as closo and nido-preparation, properties and structure. Metallo carboranes - a general study.

Metal clusters - Chemistry of low molecularity metal clusters only-structure of Re₂Cl₈; multiple metal-metal bonds.

UNIT  II     Solid - State Chemistry                                                                                                 

 

 Structure of Solids; comparison of X-ray, neutron and electron diffractions; Structure of NiAs, CdI₂, Pervoskite, spinels and inverse spinels; defects in solids - point defects, line defects and surface defects; Non-stoichiometric compounds; Use of X-ray powder data in identifying inorganic crystalline solids; details for cubic systems.                                                   

 

Electrical properties of solids - Band Theory, semiconductors, super conductors, solid state electrolytes; Magnetic properties - dia, para, ferro, antiferro and ferrimagnetism; hysterisis; ferrites; garnets; Optical properties – solid - state lasers and Inorganic phosphors.

Reactions in solid state and phase transitions - diffusion coefficient, diffusion mechanism, vacancy and interstitial diffusions, formation of spinels; solid solutions, order-disorder transformations and super structure.

 

UNIT III    Reaction mechanisms in Complexes                                                                

 

Electron transfer reactions - Outer and inner sphere processes; atom transfer reaction, formation and rearrangement of precursor complexes, the bridging ligand, successor complexes; Cross reactions and Marcus-Hush theory; Application of electron transfer reactions in synthesis.

Reaction mechanism of coordination compounds - Substitution reactions, Labile and inert complexes; Kinetic application of V.B and C.F.Theories.

Substitution in square planar complexes - General mechanism; reactivity of Platinum complexes; influences of entering and leaving groups; the trans effect - theories, trans influence.

Substitution in octahedral complexes - general mechanism, discussion of A, D, I_A, I_D and DC_B mechanism; replacement of coordinated water; mechanism of acid hydrolysis and base hydrolysis - Conjugate base mechanism; direct and indirect evidences in favour of the mechanism; application of substitution reaction in the synthesis of Platinum and Cobalt complexes.

 

UNIT – IV       Organometallic Chemistry &     Catalysis 

 Carbon donors - Alkyls and Aryls-preparation and properties; Carbonyls -18 electron rule, isolobal concept - application to structure of carbonyls (simple and polynuclear); Nitrosyls - bridging and terminal nitrosyls, bent and linear nitrosyls; dinitrogen complexes; Chain Carbon donors - Olefins, acetylene and allyl complexes - synthesis, structure and bonding; Cyclic Carbon donors  -  Metallocene - synthesis, structure and bonding (Ferrocene only).

Reactions - Association reaction - Only ligand protonation; substitution - electrophilic and nucleophilic attack on ligands; addition and elimination; carbonylation and decarbonylation; oxidative addition to organometallics; fluxional isomerism.                                                                                                                          

Hydrogenation of olefins (Wilkinsons catalyst); hydroformylation of olefins using Cobalt or Rhodium catalysts (oxo process); Oxidation of olefins to aldehydes and ketones (Wacker process); polymerization (Zeigler-Natta catalyst); Cyclo oligomerization of acetylene using Nickel catalyst (Reppe’s catalyst); polymer bound catalysts.

 

UNIT –V    Bioinorganic Chemistry 

                                                                                                                                   

Metal ions in biological systems - essential and trace metals, Na⁺/K⁺  Pump; Biologically important complexes of Iron (transport proteins) - haemoglobin, myoglobin, iron-sulphur proteins, cytochrome-C, Magnesium (chlorophyll), Cobalt (vitamin B₁₂), Zinc (carbonic anhydrase, carboxy peptidase);  macrocyclic effect; fixation of Nitrogen.

 

 

 

Text books

1. J.E. Huheey, E.A. Keiter and R.L. Keiter, Inorganic Chemistry- Principles of structure and reactivity, 4^th edition, Pearson-Education, 2002.
2. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern, 5^th

edition, 1988.

3.   E.A.V. Ebsworth, D.WH. Rankine and  S. Craddock, Structural methods in Inorganic Chemistry, Black well Scientific Publ., 1987.

4. R.S. Drago, Physical Methods in Chemistry, Reinhold, New York, 1968.
5. Charles A. Depuy and Orville L. Chapman, Molecular reactions and photochemistry, Prentice Hall, 1992.
6. A.W. Adamson and P. Fleischauer, Concepts of Inorganic Photochemistry, Wiley, 1975.

7.      D.A.Skoog and D.M.West, Fundamentals of Analytical Chemistry, Holt Rinehart and Winston Publications, IV Edn, 1982.

8.      D.A. Skoog, Principles of Instrumental Analysis, Saunders College Pub.Co, III Edn., 1985.

9.      J.G. Dick, Analytical Chemistry, McGraw Hill Publishers, 1974.

10.  A.I Vogel, Text Book of Quantitative Inorganic Analysis, Pearson V Edn., 2001.

 

Reference Books

1.   E.L. Mutteri, Polyhedral boranes, Acadamic press, NY, 1975.

2.   N.H. Ray, Inorganic polymers, Academic press, NY,  1975.

3. K.F. Purcell and J.C. Kotz, Inorganic Chemistry, WB Saunders Co. USA 1977.
4. G.S. Manku, Inorganic Chemistry, TMH Co., 1984.
5. N.J. Turro, Modern molecular photochemistry, Benjamin/Cummings, Menlo Park, California, 1978.

 

6. C.N.R.Rao and J.R. Ferraro, Spectroscopy in Inorganic Chemistry, Vol I and Vol II, Academic Press, 1970.

 

7. H.A.O. Hill and P. Day, Physical methods in advanced Inorganic Chemistry, Joh

UNIT – I   Quantum Chemistry –I                                              

Photoelectric effect – De Broglie equation – Heisenberg uncertainty principle – Compton effect – operators and commutation relations – quantum mechanical postulates – Schordinger equation and its solution to the problem of a particle in one , three dimensionel boxes  and  harmonic oscillator. Schrodinger equation for the rigid rotator and Hydrogen atom – arriving solution for energy and wave function – the orgin of quantum numbers and their physical significance – Probability distribution of electrons.

 

UNIT –II   Quantum Chemistry –II             

Born – Oppenheimer approximation, Approximation methods – Perturbation and Variation methods – application to Hydrogen and Helium atom – Spin- orbit interaction- LS coupling and JJ coupling- Term symbols and spectroscopic states. Concept of Hybridisation – sp, sp² and sp³  hybridisation , Huckel Molecular orbital ( HMO) theory for conjugated π - system , application to simple systems such as  Ethylene, butadiene and benzene, Self consistant field approximation – Hartree’s and Hartree- Fock Self Consistent  field theory,  Slater type orbitals – Slater rules.

 

UNIT-III   Electrochemistry –I                             

Ions in solutions – Debye – Huckel theory of strong electrolytes – Debye-Hückel- onsager equation – verification and limitation – Debye – Hückel limiting law and its extension. Electrode – Electrolyte interface adsorption at electrified interface – electrical double layers – Electro capillary phenomena – Lippmann capillary equation – structure of double layers – Helmholtz Perrin, Guoy Chappman and Stern models of electrical double layers-electro kinetic  Phenomena - Tiscelius method of separation of proteins – membrane potential.

 

UNIT –IV   Electrochemistry –II                          

Mechanism of electrode reactions –the Butler Volmer  equation for one step electron transfer reaction – significance of  equilibrium exchange current density and symmetry factor – transfer coefficient and its significance – Cyclic voltametry – Principles and applications. Mechanism of Hydrogen and Oxygen evolution reactions. Corrosion and Passivation of metals – construction of Pourbaix and Evans diagrams – Prevention of Corrosion. Electrochemical energy systems – Primary and Secondary batteries – ( dry cells, lead acid – storage batteries, silver - zinc cell, nickel - cadmium battery, mercury cell) – Fuel cells.

 

UNIT –V   Surface Chemistry and Catalysis      

Kinetics of surface reactions : Physical and chemical adsorption – adsorption isotherms – types of adsorption isotherms – Langmuir adsorption isotherm – B.E.T. theory for multilayer adsorption – application of transition state theory to adsorption – measurement of surface area – Mechanism of heterogeneous catalytic reactions – the adsorption coefficient and its significance.

Acid – Base catalysis – mechanism – Bronsted catalysis Law – catalysis by enzymes – rate of enzyme catalysed reactions – effect of substrate concentration, pH and temperature on enzyme catalysed reactions – inhibition of enzyme catalyzed reactions.

 

Text Books

1. Gurudeep raj, Advanced Physical chemistry, Goel Publishing House, Meerut.
2. R.K.Prasad, Quantum Chemistry, Wiley Eastern, New Delhi, 1992.
3. M.W.Hanna, Quantum Mechanics in Chemistry, W.A.Benjamin Inc, London 1965.
4. D.A.McQuarrie, Quantum Chemistry, University Science Books, Mill Valley, California, 1983

     5. S. Glasstone, Introduction to Electrochemistry, Affiliated East West press, New         Delhi,1960

6.  D.R. Craw, Principles and Applications of Electrochemistry, Chapman and  Hall,             1991

1. J.Rajaram and J.C.Kuriacose, Kinetics and mechanism of chemical transformation, Macmillan India Ltd., (1993)
2. K.J.Laidlar, Chemical kinetics, Harper and Row, New york (1987)

UNIT - I   Organic Photochemistry                                      

Photochemical reactions: fate of excited molecules, Jablonski diagram, Norrish Type I and Norrish Type II reactions,  photoreduction of ketone, photoaddition reactions, Paterno Buchi reaction, di-pi methane rearrangement, photochemistry of arenas, Photooxidation (Formation of peroxy compounds), Photoisomerization ( Cis-trans isomerization ), Photo addition of olefins and amines to aromatic compounds, Photo rearrangements: Photo-Fries rearrangement and Photo rearrangement of 2,5-Cyclohexadienones.

UNIT –II   Inorganic  Photochemistry

Photosubstitution, Photoredox, photoisomerisation and photo rearrangementreactions in inorganic complexes.  Photovoltaic and Photogalvanic cells – Photoelectrochemical cells – photoassisted electrolysis of water – aspects of solar energy conversion. Application of metal complexes in solar energy conversion

UNIT –III   Physical Photochemistry

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