PG Syllabus MSc Sem-II
PG Syllabus MSc Sem-II

Dr. Hari Singh Gour Vishwavidyalaya, Sagar

M.Sc. CHEMISTRY

2010 - 11

COURSE STRUCTURE AND DISTRIBUTION OF MARKS

 

Semester II

 

 

Semester II

 

Paper Code

Paper Title

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CHE-C-221

Inorganic  Chemistry

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2

4

2

CHE-C-222

Organic     Chemistry

4

0

2

4

3

CHE-C-223

Physical    Chemistry

4

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2

4

4

CHE-C-224

Gr.Th. & Spectroscopy

3

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3

5

CHE-C-225

Computer for Chemists

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2

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6

CHE-C-226

Lab Course - Inorganic

 

 

6

2

7

CHE-C-227

Lab Course – Organic      

 

 

6

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8

CHE-C-228

Lab Course - Physical

 

 

6

2

9

CHE-C-229

Lab Course–Computers   

2

 

 

1

 

 

 

 

 

 

 

 


M.Sc. Chemistry

Semester II

CHE-C 221 : Inorganic Chemistry

                                                                   60 Hours (4 Hr/per Week)

1.      Reaction Mechanism of Transition Metal Complexes         

Energy profile of a reaction, reactivity of metal complexes , inert and labile complexes, kinetic application of valence bond and crystal field theories, kinetics of octahedral substitution, acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidence in favor of conjugate mechanism, anation  reactions, reactions without metal ligand bond cleavage.

2.      Substitution reactions in square planer complexes, the trans effect, mechanism of the substitution reaction; Redox reactions, electron transfer reactions, mechanism of one electron transfer reactions, outer-sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions.

3.      Metal Clusters – Higher Boranes, carboranes, metalloboranes and metallo carboranes, metal clusters (carbonyl and halide) and compound with metal – metal multiple bonds (Binuclear and trinuclear).

4.      Electronic Spectra and Magnetic Properties of Transition Metal complexes

Spectroscopic ground states, correlation, Orgel and Tanabe-Sugano energy diagrams for transition metal complexes (d1to d9 states)  Calculations of Dq. B and b parameters,

Charge transfer spectra, spectroscopic method of assignment of absolute configuration in optically active metal chelates and their stereo-chemical information, anomalous magnetic moments, magnetic exchange coupling and spin crossover.

 


 

M.Sc. Chemistry

Semester II

CHE-C 222 : Organic Chemistry

                                                                   60 Hours (4 Hr/per Week)

  1. Aliphatic Electrophilic Substitution                                             

Bimolecular mechanism-SE2 and SE1. The SE1 mechanism, electrophilic substitution accompanied by double bond shifts.  Effects of substrates, leaving group and the solvent polarity on the reactivity.       

  1. Aromatic Electrophilic Substitution                                             

The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, hipso-attack, orientation in other ring systems.  Quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling.  Vilsmeir reaction, Gattermann-Koch reaction.

  1. Aromatic Nucleophilic Substitution                                    

The SNAr, SN1, benzyne and SRN1 mechanism. Reactivity-effect of substrate structure, leaving group and attacking nucleophile. The Richter, Sommelet- Hauser and Smiles rearrangements.  

  1. Stereochemistry                                                          

Conformational analysis of cycloalkanes, decalins, effect of conformation on reactivity, conformation of sugars, steric strain due to unavoidable crowding.

Elements of symmetry, chirality, molecules with more than one chiral center, threo and erythro isomers, methods of resolution, optical purity, enantiotopic and diastereotopic atoms, groups and faces, stereo specific and stereo selective synthesis. Asymmetric synthesis. Optical activity in the absence of chiral carbon (biphenyls, allenes and spiranes,) chirality due to helical shape. Stereochemistry of the compounds containing nitrogen, sulphur and phosphorus.

  1. Addition to Carbon-Carbon Multiple Bonds.              

Mechanistic and stereo chemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, regio- and chemo- selectivity, orientation and reactivity.  Addition to cyclopropane ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings. Hydroboration. Michael reaction. Sharpless asymmetric epoxidation.

  1. Elimination Reactions                                                      

The E2, E1 and E1CB mechanisms and their spectrum. Orientation of the double bond . Reactivity - effects of substrate structures. Attacking base, the leaving group and the medium. Mechanism and orientation in pyrolytic elimination. Claisen and Cope rearrangements. Fluxional tautomerism. Ene reactions.

7.   Pericyclic Reactions                                                                            

Molecular orbital symmetry. Frontier Orbitals of ethylene, 1,3-butadiene, 1,3,5-hexatriene and allyl system. Classification of Pericyclic reactions.  Woodward-Hoffmann correlation diagrams. FMO and PMO approach. Electro-cyclic reactions- con-rotatory and dis-rotatory motions, 4n, 4n+2 systems, Cycloadditions- antra-facial and supra-facial additions, 4n, 4n+2 systems, 2,2+2 addition of ketenes and 1,3 dipolar cyclo-additions,Sigma tropic rearrangements- suprafacial and antarafacial shifts of H-, sigma tropic shifts involving carbon moieties, 3,3- and 5.5. sigma tropic rearrangements. 


M.Sc. Chemistry

Semester II

CHE-C 223 : Physical  Chemistry

                                                                   60 Hours (4 Hr/per Week)

1.   Quantum Chemistry

A   Angular Momentum

Ordinary angular momentum, generalized angular momentum, eigenfunctions for angular momentum, eigenvalues of angular momentum, operators using ladder operators, addition of angular moments, spin, antisymmetry and Pauli exclusion principle.

B   Electronic Structure of Atoms

Electronic configuration.  Russell-Saunders terms and coupling schemes, Slater-Condon parameters, term separation energies of the pn configuration, term separation energies for the dn configurations, magnetic effects: spin-orbit coupling and Zeeman splitting introduction to the methods of self consistent field, the virial theorem.

2.   Phase Equilibria :

Application of phase rule to three component systems: Graphical representation, Solid-liquid equilibrium, Liquid-liquid equilibrium,

Second order phase transitions :

3. Statistical Thermodynamics

A.      Concept of distribution, thermodynamic and probability and most probable distribution. Ensemble averaging, postulates of ensemble averaging. Canonical, grand canonical and micro canonical ensembles, corresponding distribution laws (using Lagrange's method of undetermined multipliers).

B.      Partition functions- translational, rotational, vibrational electronic partition functions, calculation of thermodynamic properties in terms of partition  functions.  Applications of  partition functions.

Heat capacity behaviour of solids- chemical equilibrium constant in terms  of partition. Femi-Dirac statistics, distribution law and applications to metal. Bose-Einstein statistics- distribution law and application to helium.

4.   Non Equilibrium Thermodynamics

Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equations for different irreversible processes (i.e. heat flow, chemical reaction etc.) fluxes and forces, non equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsager's reciprocity relations, electro-kinetic phenomena, diffusion, electric conduction, irreversible thermodynamics for biological systems, coupled reactions.

5.      Chemical Dynamics                                           

A.      Dynamic chain(hydrogen-bromine reaction, pyrolysis of acetaldehyde, decomposition of ethane). Photochemical( Zhabotinsky reaction). Homogeneous catalysis, kinetics of enzyme reactions, general features of fast reactions, study of fast reactions by flow method, relaxation method, flash photolysis and the nuclear magnetic resonance method. Dynamics of molecular motions, probing the transition state, dynamics of barrierless chemical reactions in solution, dynamics of unimolecular reactions           ( Lindemann- Hinshelwood and Rice-Ramsperger- Kassel-Marcus - RRKM theories of unimolecular reactions ).

 

 

 

6.      Macromolecules

A.      Polymer-definition, types of polymers, electrically conducting, fire resistant, liquid crystal polymers, kinetics of polymerization, mechanism of polymerization.

B.      Molecular mass, number and mass average molecular mass, molecular mass determination (osmometry, viscometry, diffusion and light scattering methods) sedimentation, chain configuration macromolecules, calculation of average dimension of various chain structures.

7.      Electrochemistry                                                         

A.      Semiconductor interfaces- theory of double layer at semiconductor, electrolyte solution interfaces, structure of double layer interfaces. Effect of light at semiconductor solution interface.

B.      Electrocatalysis- interface  of various parameters. Hydrogen electrode.

Bio-electrochemistry, threshold membrane phenomena, Nernst-Planck equation, Hodges Huxley equations, core conductor models, electrocardiography.

C.      Polarography theory, Ilkovic equation; half wave potential and its significance.

Introduction to corrosion, homogenous theory, forms of corrosion, corrosion monitoring and prevention methods.


M.Sc. Chemistry

Semester II

CHE-C 224 : Spectroscopy and Diffraction Methods

45 Hours (3 Hr/per Week)

1.   Molecular Spectroscopy

Energy levels, molecular orbitals, vibronic transitions, vibrational progression and geometry of the excited states, Frank Condon principle, electronic spectra of polyatomic molecules, emission spectra, radiative and non radiative decay, internal conversion, spectra of transition metal complexes, charge transfer spectra.

2.  Magnetic Resonance Spectroscopy

          A.      Nuclear Magnetic Resonance Spectroscopy

Nuclear spin, nuclear resonance, saturation, shielding of magnetic nuclei, chemical shift, factors influencing chemical shift, deshielding, spin-spin interaction, factors influencing coupling constant ‘J’ , classification, (ABX, AMX, ABC, A2B2 etc.), spin decoupling, basic ideas about instrument, NMR studies of nuclei other than proton, 13C, 19F and 31P. FT-NMR and its advantages, use of NMR in medical diagnostics.

B.      Electron Spin Resonance Spectroscopy

Basic principles, Zero field splitting and Kramer's degeneracy, factors affecting the ‘g’ value. Isotropic and anisotropic hyperfine constant, spin Hamiltonian, spin densities and McConnell relationship, measurement techniques, applications.

C.           Nuclear Quadrupole Resonance Spectroscopy

Quadrupole nuclei, quadrupole moments, electric field gradients, coupling constants, splitting, applications

3.   Photoacoustic spectroscopy

Basic principles of photoacoustic spectroscopy(PAS), PAS gases and condensed systems, chemical and surface applications.

4.   X - RAY Diffraction

A.      Braggs condition, Miller Indices, Laue method, Bragg method, Debye – Scherr method of X-ray structural analysis of crystals, index reflections, identification of unit cell from systematic absences in diffraction pattern. Structure of simple lattices and X-ray intensities, structure factor and its relation to intensity and electron density, phase problem. Description of the procedure for an X-ray structure analysis, absolute configuration of a molecules, Ramchandran diagrams.

B.  Electron Diffraction

Scattering intensity vs scattering angle, Wierl equation, measurement technique, elucidation of structure of simple gas phase molecules, low energy electron diffraction and structure of surfaces.

C.    Neutron Diffraction

Scattering of neutrons by solids and liquids, magnetic scattering, measurement techniques, Elucidation of structure of magnetically ordered unit cell.

 

 
M.Sc. Chemistry

Semester II

CHE-C 225 : Computers for Chemists

                                                                   60 Hours (4 Hr/per Week)
  1. Introduction to computers and computing  

Basic structure and functioning of computers with a PC as an illustrative example. Memory, I/O devices. Secondary storage. Computer languages. Operating systems with DOS as an example. Introduction to Unix and Windows, data processing, principles of programming. Algorithms and flow charts.

  1. Computer programming in FORTRAN/ C/ BASIC

(The language features are listed here with respect to FORTRAN. The instructoir may choose another language such as BASIC or C and the features mey be replaced appropriately). Elements of the computer language. Constants and variables. Operations and symbols. Expresion. Arithmetic assignment ststement. Input and Out put . Format statement. Termination statement. Branching statements such as IF or GO TO statements. LOGICAL variables. Double precision variables. Subscripted variables and DIMENSION. DO statement. FUNCTION and SUBROUTINE. COMMON and DATA ststements.(Note:  Students learn these programming logics by “hand on ” experience on a personnel computer ).

3.       Programming in Chemistry :

Development of small computer codes involving simple formulae in  chemistry, such as van der Waal equation, pH titration, kinetics, radioactive decay. Evaluation of lattice energy and ionic radii from experimental data. Linear simultaneous equation to solve secular equation with Huckel theory. Elementary structural features such as bond lengths, bond angles, dihedral angles etc of molecules extracted from a data base such Cambrige data base.

a.                                    Use of Computer Programmes :

The students will learn to how to operate a PC and how to run stsndard programmes and packages. Execution of linear regression such as X Y plot, numerical integration and differentiation as wel as differential equation solution programmes. Monte Carlo and molecular dynamics. Programmes with data  preferably from physi9cal chemistry laboratory. Further, the students will operate one or two or more packages such as MATLAB, EASYPLOT, EXCEL, FOXPRO and Word Processing software – MS Word and Powerpoint.

 


 

M.Sc. Chemistry

Semester II

CHE-C 226 : Laboratory Exercise : Inorganic

Chromatography

Separation of Cations and Anions by

(a).     Paper Chromatography

(b).     Column chromatography – ion exchange.

Preparations :

Preparation of selected inorganic compounds

1.   VO(acac)2

2.   TiO(C9H8NO)2. 2(H2O)

3.   cis- K[Cr(C2O4)2(H2O)2]

4.   Na [Cr(NH3)2(SCN)4]

5.   Mn(acac)3

6.   K3[Fe(C2O4)3]

7.   Co(NH3)6][Co(N)2)6]

8.   cis – [Co(trien)(NO2]Cl.H2O

9.   Hg[Co(SCN)4]

10.        [Co(Py)2Cl2]

11.        [Ni(NH)6)Cl2

12.        Ni(dmg)2

13.        [Cu(NH3)4]SO4.H2O

Interpretation of pre recorded spectra of complexes – electronic, IR, ESR, Thermograms (TGA)

 

 

M.Sc. Chemistry

Semester II

CHE-C 227 : Laboratory Exercise :ORGANIC  CHEMISTRY

Organic Synthesis :

Acetoacetic acid ester condensation: Synthesis of ethyl n-butylacetonatoacetate by AEE condensation.

Cannizziro reaction : 4-Chlorobenzaldehyde as substrate,

Friedel Crafts Reaction ; b-benzoylpropionic acid from succinic anhydride and benzene, Aromatic electrophilic substitutions : Synthesis of p-nitroaniline and p-bromoaniline.

The products may be Characterized by Spectral Techniques.

Quantative Analysis

Determination of the precentage or number of hydroxyl groups in an organic compound by acetylation method.

Estimation of amines / phenols using bromate solution / or acetylation method.

 

 

 

 

 

 

 

M.Sc. Chemistry

Semester II

CHE-C 228 : Laboratory Exercise : PHYSICAL CHEMISTRY           

                                               

INSTRUMENTAL : ELECTROCHEMISTRY

A. Conductometry :

1.           Determination of the Velocity constant, order of reaction and energy of activation for soponification of ethylacetate by sodium hydroxide conductometrically.

2.         Determination of solubility and solubility product of sparingly soluble salts (e.g. PbSO4, BaSO4) conductometrically.

3.           Determination of the strength of strong and weak acids in a given solution by conductometry.

4.           To study the effect of solvent on the conductance of AgNO3 /acetic acid and to determine the degree of dissociation and equilibrium constant in different solvents and their mixtures (DMSO, DMF, dioxane, acetone, water) and to test the validity of Debye-Huckel-Onsager theory.

5.           Determination of activity coefficient of Zn ions in the solution of 0.002 M ZnSO4 using Debye-Huckel’s limiting law.

B. Potentiometry / pH metry

i.             Determination of strengths of halides in a mixture potentiometrically.

ii.           Determination of valency of mercurous ions potentiometrically.

iii.          Determination of the strength of strong acid and weak acids in a given mixture using potentiometer / pH meter.

iv.          Determination of the temperature dependence of EMF of a cell.

v.            Determination of the formation constant of silver-ammonia complex and stoichiometry of the complex potentiometerically.

vi.          Acid-base titration in a non-aqueous media using a pH meter.

vii.         Determination of activity and activity coefficient of electrolytes.

viii.       Determination of dissociation constant of acetic acid in DMSO, DMF, acetone and dioxane by titrating it with KOH.

ix.          Determination of thermodynamic constants DG, DH, DS for the reaction by e.m.f. method.

Zn+ H2SO4 à ZnSO4 + 2H .

M.Sc. Chemistry

Semester II

ICH -C 229 Lab Course – Computers

                                                                                                                        15 Hrs (1 period  per week)

The students will learn to how to operate a PC and how to run standard programmer and packages – for chemistry applications.

Execution of linear regression such as X Y plot, numerical integration and differentiation as well as differential equation solution programmer .

Monte Carlo and molecular dynamics – PC Model, Programming with data preferably from physical chemistry laboratory-Basic/C/Fortran.

Operation of one or two or more packages such as EXCEL, Word Processing software – MS Word and Powerpoint,  MATLAB, EASYPLOT, FOXPRO.


 

Books Suggested

Inorganic Chemistry

1.   Advanced Inorganic Chemistry, F.A. Cotton and Wilkinson, John Wiley.

2.   Inorganic Chemistry, J.E.Huhey, Harpes & Row.

3.   Chemistry of Elements, N.N. Greenwood and A Earnshow, Pergamon.

4.   Inorganic Electronic Spectroscopy, A.B.P. Lever, Elsevier

5.   Magnetochemistry, R.L.Carlin, Springer Verlag.

6.   Comprehensive Coordination Chemistry eds., G. Wilkinson, R.D.gillars and J.A.McCleverty, Pergamon.

7.   Coordination Chemistry, D.Banerjee, TMH,N.Delhi,1995

8.   Coordination Chemistry, M.Satake, Discovery Publication House N.Delhi.

9.   Essential Trends in Inorganic Chemistry, D.M.P. Mingos, Oxford Univ. Press, N.Delhi 1995.

10.Structural Inorganic Chemistry, A.F.Wells, ELBS

11.Modern Aspects of Inorganic Chemistry, H.J.Emeleus, UBSID,           N.Delhi

Organic Chemistry

1.   Advanced Organic Chemistry-Reactions. Jerry March, John Wile

2.   Advanced Organic Chemistry, F.A. Carey and n J.Sundberg, Plenum

3.   A Guide Book to Mechanism in Organic Chemistry, Peter Sykes, Longman.

4.   Structure and Mechanism in Organic Chemistry, C.K.Ingold, Cornell University Press.

5.   Organic Chemistry, R.T. Morrison and R.N.Byd. Prentice Hall.

6.   Modern Organic reactions, H.O. House, Benjamin.

7.   Principles of Organic Synthesis, R.O.C. Norman and J.M.Coxon, Blackie Academic & Professional

8.   Pericyclic Reactions, S.M.Mukherji, Macmillan, India.

9.   Reaction Mechanism in Organic Chemistry, S.M. Mukherji and S.P.Singh, Macmillan.

10 Stereochemistry of Organic Compounds D. Nasipuri, New Age        International

11  Setereochemistry of Organic Compounds, P.S.Kalsi, New Age          International

12  Basic Stereochemistry of Organic Molecules, S.Sengupta, Book,  Syndicate Pvt.Ltd. Kolkata, 1987.

13  Organic Photochemistry and Pericyclic Reactions, M.G.Arora, Anmol Publications, N.Delhi, 1994.

Physical Chemistry

Physical Chemistry; P.W. Alkins, ELBS

Introduction to Quantum Chemistry, A.K. Chandra, Tata McGraw Hill,1995

Quantum Chemistry, Ira N. Levine, Prentice Hall, 1975

Coulson's Valence, R.McWeeny, ELBS.

Chemical Kinetics, K.J.Laidler, McGraw Hill.

Kinetics Mexchanism of Chemical Transformations, J.Rajaram and J. Kuriacose, McMillan.

7.  Micelles, Theoretical and Applied Aspects. V.Moroi, Plenum.

8   Modern Electrochemistry Vol. 1 and II J.O.M. Bockris and A.K.N. Reddy,  Plenum.

9   Introduction to Polymer Science, V.R. Gowarikar, N.V. Vishwanathan and    J.Sridhar, wiley Eastern.

10. Electroanalyutical Chemistry, R.T.Sane, Quest Publications,Mumbai,

      1999.

11. Introduction to Electrochemistry, S.Glasstone, Affiliated East West Press    N.Delhi, 1995.

12. Chemical kinetics, G.L. Agrawal, TMH, N.Delhi

13. Physical Chemistry for Macromolecules, D.D. Deshpande, Vishal

      Publications.

14.  Quantum Chemistry, R.K. Prasad, New Age Intl., N.delhi.

15.  Physical Chemistry for Macromolecules, D.D.Deshpande Vishal  Publications.

16.  Introductory Polymer Chemistry, G.S.Misra, New Age Intl., N.Delhi.

17.  Introduction to Chemical Thermodynamics, R.P. Rastogi, Vikas, Pub. House, N.Delhi. 1997.

18.  Statistical Thermodynamics, M.C.Gupta, New Age Intl., N.Delhi.

19.  Thermodynamics, Kinetic Theory and Statistical Thermodynamics, Sears and Salinger. Narosa Publishing House, New Delhi.

20.  Physical Chemistry, G.W.Narosa Publ.H.,N.Delhi,1994.

21.  Statistical Thermodynamics (in Hindi) Farid Khan, M.P.Hindi Grantha Academy, Bhopal, 2001.

22.  Irreversible Thermodynamics (in Hindi), Farid Khan, M.P.Hindi Grantha Academy, Bhopal, 2001.

Analytical Chemistry

1. Modern spectroscopy, J.M.Hollas, John Eiley.

2. Applied Electron Spectroscopy for Chemical Analysis Ed. H.Windai and F.L. Ho Wiley Interscience.

3. NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, R.V.parish, Ellis Harwood.

4. Physical Methods in Chemistry, R.S.Drago, Saunders College,

5. Chemical Application of Group Theory, F.A.Cotton.

6. Introduction to Molecular Spectroscopy, G.m.Borrow, MsGraw Hill.

7. Basic Principles of Spectroscopy, R.Chang, McGraw Hill.

8. Theory and Applications of UV Spectroscopy, P.K.Gosh, John Wiley.

9. Introduction to Magnetic Resonance, A. Carrington and A.D.Maclachalan, Harper & Row.

Computers

1.           Computers and Common Sense, R.Hunt and J.Wiley, Prentice Hall.

2.           Computational Chemistry, A.C.Norris,

3.           Microcomputers Quantum Mechanics, J.P.Lillingbeck, Adam Hilger.

4.           Computer Programming in FORTRAN IV,V.Rajaraman, Prentice Hall,

5.           An Introduction to Digital Computer Design, V.Rajaraman and T.Radhakrishnan, Prentice Hall.