Pt. Ravishankar Shukla University (PRSU), Raipur was established in 1964 and is affiliated with University of grant commission (UGC)

Here I am sharing the PhD Chemistry entrance exam syllabus for Pt. Ravishankar Shukla University (PRSU)

PAPER NO. CH – I Group Theory and Chemistry of Metal Complexes

UNIT - I

SYMMETRY AND GROUP THEORY IN CHEMISTRY: Symmetry elements and symmetry operation, definitions of group, subgroup, relation between orders of a finite group and its subgroup.Conjugacy relation and classes. Point symmetry group. Schonflies symbols, representations of groups by matrices (representation for the Cn, Cnv, Cnh, Dnh etc. groups to be worked out explicitly). Character of a representation. The great orthogonality theorem (without proof) and its importance. Character tables and their use; spectroscopy.

UNIT - II

A. METAL-LIGAND BONDING: Limitation of crystal field theory, molecular orbital theory, octahedral, tetrahedral and square planar complexes, bonding and molecular orbital theory.

B. METAL π-COMPLEXES: Metal carbonyls, structure and bonding, vibrational spectra of metal carbonyls for bonding and structural elucidation, important reactions of metal carbonyls; preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; tertiary phosphine as ligand.

UNIT – III

A. METAL–LIGAND EQUILIBRA IN SOLUTION: Stepwise and overall formation onstants and their interaction, trends in stepwise constants, factors affecting the stability of metal complexs with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin, determination of binary formation constants by pH-metry and spectrophotometry.

B. ISOPOLY ACID AND HETEROPOLYACID: Isopoly and heteropoly acids of Mo and W. Preparation, properties and structure. Classification, Preparation, properties and structures of borides,carbides, nitrides and silicides. Silicates- classification and Structure,Silicones- preparation,properaties and application.

UNIT - IV

A. METAL CLUSTERS: Higher boranes, carboranes, metalloboranes and metallocarboranes. Metal carbnonyl and halide cluster, compounds with metal-metal multiple bonds.

B. CHAINS: catenation, heterocatenation, intercatenation.

C. RINGS: Borazines, phosphazines.

BOOK SUGGESTED:

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

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

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

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

6. Comprehensive Coordination Chemistry Eds. G. Wilkinson, R.D. Gillars and J.A. McCleverty, Pergamon.

FIRST SEMESTER

PAPER NO. CH – I

GROUP THEORY AND CHEMISTRY OF METAL COMPLEXES Max. Marks 100

UNIT - I SYMMETRY AND GROUP THEORY IN CHEMISTRY: Symmetry elements and symmetry operation, definitions of group, subgroup, relation between orders of a finite group and its subgroup.Conjugacy relation and classes. Point symmetry group. Schonflies symbols, representations of groups by matrices (representation for the Cn, Cnv, Cnh, Dnh etc. groups to be worked out explicitly). Character of a representation. The great orthogonality theorem (without proof) and its importance. Character tables and their use; spectroscopy.

UNIT - II A. METAL-LIGAND BONDING: Limitation of crystal field theory, molecular orbital theory, octahedral, tetrahedral and square planar complexes, bonding and molecular orbital theory.

B. METAL π-COMPLEXES: Metal carbonyls, structure and bonding, vibrational spectra of metal carbonyls for bonding and structural elucidation, important reactions of metal carbonyls; preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; tertiary phosphine as ligand.

UNIT – III A. METAL–LIGAND EQUILIBRA IN SOLUTION: Stepwise and overall formation onstants and their interaction, trends in stepwise constants, factors affecting the stability of metal complexs with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin, determination of binary formation constants by pH-metry and spectrophotometry.

B. ISOPOLY ACID AND HETEROPOLYACID: Isopoly and heteropoly acids of Mo and W. Preparation, properties and structure. Classification, Preparation, properties and structures of borides,carbides, nitrides and silicides. Silicates- classification and Structure,Silicones- preparation,properaties and application.

UNIT - IV A. METAL CLUSTERS: Higher boranes, carboranes, metalloboranes and metallocarboranes. Metal carbnonyl and halide cluster, compounds with metal-metal multiple bonds.

B. CHAINS: catenation, heterocatenation, intercatenation.

C. RINGS: Borazines, phosphazines.

BOOK SUGGESTED:

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

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

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

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

6. Comprehensive Coordination Chemistry Eds. G. Wilkinson, R.D. Gillars and J.A. McCleverty, Pergamon.

PAPER NO. CH – 2 CONCEPTS IN ORGANIC CHEMISTRY Max. Marks 100

UNIT - I A. NATURE OF BONDING IN ORGANIC MOLECULES: Localized and Delocalized chemical bod, conjugation and cross-conjugation, Bonding in Fullerenes, Bonds weaker than covalent, addition compounds, Crown ether complexes and cryptands. Inclusion compounds, Cyclodextrins, Catenanes and Rotaxanes. B. AROMATICITY: Aromaticity in benzonoid and non-benzenoid compounds, Huckel’s rule, annulenes, anti-aromaticity, homo-aromaticity. PMO approach for Aromaticity, Annulenes.

UNIT - II A. CONFORMATIONAL ANALYSIS: Conformational analysis of cycloalkanes, decalins, effect of conformation on reactivity, conformation of sugars, steric strain due to unavoidable crowding.

B. STEREOCHEMISTRY: Elements of symmetry, chirality, molecules with more than one chiral center, methods of resolution, optical purity, stereospecific and stereoselective synthesis. Asymmetric synthesis. Optical activity in the absence of chiral carbon (Biphenyls, allenes and spiranes), chirality due to helical shape.

UNIT - III A. REACTION INTERMEDIATES: Generation, structure, stability and reactivity of carbocations,carbanions, free radicals, carbenes and nitrenes. Sandmeyer reaction, Free radical rearrangement and Hunsdiecker reaction.

B. ELIMINATION REACTIONS: The E2, E1 and E1cB mechanisms. Orientation of the double bond. Reactivity,effects of substrate structures, attacking base, the leaving group and the medium.

UNIT - IV PERICYCLIC REACTIONS: Classification of pericyclic reactions. Woodward-Hoffmann correlation diagrams. FMO and PMO approach. Electrocyclic reactions - conrotatory and disrotatory motions, 4n, 4n+2 and allyl systems. Cycloadditions - antrafacial and suprafacial additions, 4n and 4n+2 system, 2+2 addition of ketenes, 1,3 dipolar cycloadditions and cheleotropic reactions. Sigmatropic rearrangements - suprafacial and antarafacial shifts of H, sigmatrophic shifts involving carbon moieties, 3,3- and 5,5- sigmatropic rearrangements. Claisen, Cope and Aza-Cope rearrangements. Ene reaction.

BOOKS SUGGESTED: 1. Advanced Organic Chemistry, F. A. Carey and R. J. Sundberg, Plenum.

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

3. Structures and Mechanism in Organic Chemistry, C. K. Ingold, Cornell University Press.

4. Organic Chemistry, R. T. Morrison and R. N. Boyd, Prentice-Hall.

5. Modern Organic Reactions, H. O. House, Benjamin.

6. Principles of Organic Synthesis, R. O. C. Norman and J. M. Coxon, Blackle Academic and Professional.

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

8. Reaction Mechanism in Organic Chemistry, S. M. Mukherji and S. P. Singh, Macmillian.

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

10. Some Modern Methods of Organic Synthesis, W. Carruthers, Cambridge Univ. Press.

11. Rodd’s Chemistry of Carbon Compounds, Ed. S. Coffey, Elsevier.

12. Organic Chemistry, Vol 2, I. L. Finar, ELBS.

13. Stereo selective Synthesis: A Practical Approach, M. Nogradi, and VCH.

14. Organic Chemistry, Paula Yurkanis Bruice, Pearson Education.

PAPER NO. CH – 3 CHEMICAL AND MOLECULAR DYNAMICS – I Max. Marks 100

UNIT - I A. Mathematical Concept in Quantum Chemistry: Vector qualities and their properties Complex numbers and Coordinate transformations. Differential and Integral Calculus, Basis rules of differentiation and Integration Applications..

B. ANGULAR MOMENTUM IN QUANTUM CHEMISTRY – : The Schrodinger equation and postulates of quantum mechanics. Discussion of solutions of the Schrodinger equation to some model systems viz Particle in a box the harmony oscillator, the rigid rotator, the hydrogen atom.

UNIT –II BASICS OF THERMODYNAMICS: Maxwell’s thermodynamic relations and its applications. Reaction isotherm, Vant’s Hoff hypothesis. Partial molar properties; Partial molar free energy, partial molar volume and partial molar heat content. Chemical potential, Gibbs Duhem equation, variation of chemical potential with temperature and pressure. Chemical potential of ideal gases, pure solids, liquids and mixture of ideal gases.

UNIT – III ELECTROCHEMISTRY–I: Electrochemistry of solution. Debye-Huckel Onsager treatment and its extension, ion solvent interactions. Debey-Huckel-Limiting Law. Debye-Huckel theory for activity coefficient of electrolytic solutions. Determination of activity and activity coefficient, ionic strength, Thermodynamics of electrified interface equations. Derivation of electro-capillarity, Lippmann equation (surface excess), methods of determination.

UNIT – IV CHEMICAL DYNAMICS – I: Methods of determining rate laws, collision theory of reaction rates, steric factor, Activated complex theory, kinetic salt effects, steady state kinetics, and thermodynamic and Kinetic control of reactions. Dynamic chain (Hydrogen-bromine and Hydrogen-chlorine reactions) and Oscillatory reactions (Belousov-Zhabotinsky reaction)

BOOKS SUGGESTED :

1. The Chemistry Mathematics Book, E. Steiner, Oxford University Press.

2. Mathematics for Chemistry, Doggett and Sutclilffe, Longman.

3. Mathematical Preparation for Physical Chemistry, F. Daniels, McGraw Hill.

4. Chemical Mathematics, D.M, Hirst, Longman.

5. Applied Mathematics for Physical Chemistry, J.R. Barrante, Prentice Hall.

6. Basic Mathematics for Chemists, Tebbutt, Wiley.

7. Physical Chemistry, P.W. Atkins, ELBS. 8. Introduction to Quantum Chemistry, A.K. Chandra, Tata McGraw Hill. 9. Quantum Chemistry, Ira N. Levine, Prentice Hall.

10. Coulson’s Valence, R. McWeeny, ELBS.

11. Chemical Kinetics, K. J. Laidler, Pearson.

12. Kinetics and Mechanism of Chemical Transformations, J. Rajaraman and J. Kuriacose, McMillan.

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

14. Thermodynamics for Chemists, S. Glasstone EWP.

15. An Introduction to Electrochemistry S. Glasstone EWP.

16. Physical Chemistry, Ira N. Levine McGraw Hill.

17. Physical Chemistry, Silbey, Alberty, Bawendi, John-Wiley.

PAPER NO. CH - 4 MATHEMATICS AND COMPUTERS IN CHEMISTRY Max. Marks 100

UNIT - I A. EVALUTION OF ANALYTICAL DATA: Accuracy and precision,Standard deviation,Variance and coefficient of varitation Student 't' test, Confidence limits,Estimation of detection limit. Error; Classification, distribution, propagation, causes and minimation of errors. Significant figures and computation rules. Correlation analysis; Scatter diagram, Correlation coefficient'r',Calculation of 'r' by the method of least squares.

B. SAMPLING AND SAMPLE TREATMENT : Factor involved in effecting sampling, good samples, representative and homogeneous,the binominal distribution, samples of mixtures physical seperations in sample preparation,preconcentration predilution

UNIT - II A. PROBABILITY : sampling measurement and distribution of attributes; normal posion and binomial distributions; arithmetic geometric and harmonic means; moments; expectations mode, median, skewness, dispersion and kurtosis; statistical inference; planning and analysis of experiments.

B. PERMUTATION AND PROBABILITY: Permutations and combinations, probability and probability theorems, probability curves, average, root mean square and most probable errors, examples from the kinetic theory of gases , curve fitting (including least squares fit ) with a general polynomial fit.

UNIT III A. DIFFERENTIAL CALCULUS: Functions, continuity and differentiability, rules for differentiation, applications of differential calculus including maxima and minima (examples related to maximally populated rotational energy levels, Bohr’s radius and most probable velocity from Maxwell’s distribution etc), exact and inexact differentials with their applications to thermodynamic properties.

B. INTEGRAL CALCULUS: basic rules for integration, integration by parts, partial fraction and substitution. Reduction formulae, applications of integral calculus. Functions of several variables, partial differentiation, co-ordinate transformations (e.g. Cartesian to spherical polar), curve sketching.

UNIT - IV A. INTRODUCTION TO COMPUTERS AND BASIC : 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. Elements of the computer language. Constants and Variables. Operations and symbols. Expressions. Arithmetic assignment statement. Input and Output. Format statement. Termination statements. Branching statements such as IF or GO TO statement. LOGICAL -variables. Double precision variables.

B. PROGRAMMING IN CHEMISTRY : Development of small computer codes involving simple formulae in chemistry, such as vander Waals equation, pH titration, kinetics, radioactive decay. Evaluation of lattice energy and ionic radii from experimental data.

BOOKS SUGGESTED :

1. The Chemistry Mathematics Book, E. Steiner, Oxford University Press.

2. Mathematics for Chemistry, Doggett and Sutcliffe, Longman.

3. Mathematical Preparation for Physical Chemistry, F. Daniels, McGraw Hill.

4. Chemical Mathematics, D. M. Hirst, Longman.

5. Applied Mathematics for Physical Chemistry, J.R. Barrante, Prentice Hall.

6. Basic Mathematics for Chemists, Tebbutt, Wiley.

7. Computers and Common Sense, R. Hunt and J. Shelley, Prentice Hall.

8. Computational Chemistry, A.C. Norris.

9. Microcomputer Quantum Mechanics, J.P. Killngbeck, Adam Hilger.

10. Computer Programming in FORTRAN - IV, V. Rajaraman, Prentice Hall.

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

PAPER NO. CH - 5 LABORATORY COURSE – I Max. Marks 100

1. QUALITATIVE ANALYSIS OF MIXTURE CONTAINING EIGHT RADICALS INCLUDING TWO LESS COMMON METAL FROM AMONG THE FOLLOWING BY SEMI MICRO METHOD.

1) Basic Radicals : Ag, Pb, Hg, Bi, Cu, Cd, As, Sb, Sn, Fe, Al, Cr, Zn, Mn, Co, Ni, Ba, Sr, Ca, Mg, Na, K, Ce, Th, Zr, W, Te, Ti, Mo, U, V, Be, Li, Au, Pt. 2) Acid Radicals : Carbonate, Sulphite, Sulphide, Nitrite, Nitrate, Acetate, Flouride. Chloride, Bromide, Iodide, Sulphate, Borate, Oxalate, Phosphate, Silicate, Thiosulphate, Ferrocyanide, Ferricyanide, Sulphocyanide, Chromate, Arsenate and Permanganate.

2. QUANTITATIVE ANALYSIS: Involving separation of two of the following in ores, alloys, or mixtures in solution, one by volumetric and the other by gravimetric methods.

3. ESTIMATION OF: 1) Phosphoric acid in commercial orthophosphoric acid. 2) Boric acid in borax. 3) Ammonia in a ammonium salt. 4) Manganese dioxide in pyrolusite. 5) Available chlorine in bleaching powder. 6) Hydrogen peroxide in a commercial samples.

4. PREPARATIONS:- Preparation of selected inorganic compound and their studies by I.R. electronic spectra, Mössbauer, E.S.R. and magnetic susceptibility measurements. Handling of air and moisture sensitive compounds (1) VO (acac)2 (2) TiO(C9H8NO)2. 2H2O (3) cis-K [Cr(C2O4)2 (H2O)2] (4) Na [Cr (NH3)2 (SCN)4] (5) Mn (acac)3(6) K2[Fe(C2O4)3] (7) Prussian Blue, Turnbull’s Blue. (8) [Co (NH3)6] [Co (NO2)6] (9) cis-[Co(trien) (NO2)2] Cl.H2O (10) Hg [Co (SCN)4] (11) [Co (Py)2Cl2] (12) [Ni (NH3)6] Cl2 (13) Ni (dmg)2 (14) [Cu (NH3)4] SO4. H2O

BOOKS SUGGESTED

1. Vogel’s Textbook of Quantitative Analysis, revised, J. Bassett, R.C. Denney, G.H. Jeffery and J. Mendham, ELBS.

2. Synthesis and Characterization of Inorganic Compounds, W.L. Jolly, Prentice Hall.

PAPER NO. CH – 6 LABORATORY COURSE – II Max. Marks 100

ADSORPTION/SURFACE CHEMISTRY 1. To Study Surface Tension - Concentration relationship for solutions (Gibbs equation). 2. To Verify the Freundlich and Langmuir Adsorption isotherms using acetic acid/Oxalic acid and activated charcoal. 3. Determination of CMC of surfactants.

PHASE EQUILIBRIA 1. To Construct the Phase diagram for three component system (e.g., chloroform-acetic acid-water).

CHEMICAL KINETICS 1. Determination of the effect of (a) Change of temperature (b) Change of concentration of reactants and catalyst and (c) Ionic strength of the media on the velocity constant of hydrolysis of an ester/ionic reactions. 2. Determination of the velocity constant of hydrolysis of an ester/ionic reaction in micellar media. 3. Determination of the rate constant for the decomposition of hydrogen peroxide by Fe+++ and Cu++ ions. 4. Determination of the primary salt effect on the kinetics of ionic reactions and testing of the Bronsted relationship (iodide ion is oxidized by persulphate ion).

SOLUTIONS/MOLECULAR WEIGHTS 1. Determination of molecular weight of non-volatile substances by Landsberger’s Method. 2. Determination of Molar masses of Naphthelene/acetanilide by Rast’s method. 3. Molecular weight of polymers by viscosity measurements.

CONDUCTOMETRY 1. Determination of the velocity constant, order of the reaction and energy of activation for saponification of ethyl acetate by sodium hydroxide conductometrically. 2. Determination of solubility and solubility product of sparingly soluble salts (e.g., PbSO4, BaSO4) conductometrically. 3. Determination of pKa of Acetic acid and verification of Ostwald dilution law.

POTENTIOMETRY/pH METRY 1. Determination of the strength of strong and weak acids in a given mixture using a potentiometer/pH meter. 2. Determination of the dissociation constatnt of acetic acid in DMSO, DMF, acetone and dioxane by titrating it with KOH. 3. Determination of the dissociation constant of monobasic/dibasic acid by Albert-Serjeant method. 4. Determination of Redox potential of Fe++/Fe+++ system.

POLARIMETRY 1. Determination of rate constant for hydrolysis/inversion of sugar using a polarimeter. 2. Enzyme kinetics – inversion of sucrose. 3. Determine the specific and molecular rotation of optically active substances.

BOOKS SUGGESTED

1. Experiments and Techniques in Organic Chemistry, D.Pasto, C. Johnson and M.Miller, Prentice Hall.

2. Macroscale and Microscale Organic Experiments, K.L. Williamson, D.C. Heath.

3. Systematic Qualitative Organic Analysis, H. Middleton, Adward Arnold. Handbook of Organic Analysis – Qualitative and Quantitative, H. Clark, Adward Arnold.

4. Vogel’s Textbook of Practical Organic Chemistry, A.R. Tatchell, John Wiley.

5. Practical Physical Chemistry, A.M. James and F.E. Prichard, Longman.

6. Findley’s Practical Physical Chemistry, B.P. Levitt, Longman. Experimental Physical Chemistry, R.C. Das and B. Behera, Tata McGraw Hill.

SECOND SEMESTER PAPER NO. CH - 7 TRANSITION METAL COMPLEXES Max. Marks 100

UNIT - I 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, anation reactions, reactions without metal ligand bond cleavage. Substitution reactions in square planar complexes, the trans effect. 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.

UNIT - II ELECTRONIC SPECTRA AND MAGNETIC PROPERTIES OF TRANSITION METAL COMPLEXES:

Spectroscopic ground states, Correlation, Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1-d9 states), Selection rules, mechanism for break down of the selection rules, intensity of absorption, band width, spectra of d-d metal complexes of the type [M (H2O)] n+, spin free and spin paired ML6 complexes of other geometries, Calculations of Dq, B and parameters, spin forbidden transitions, effect of spin-orbit coupling, Spectrochemical and Nephelouxetic series. Magnetic properties of complexes of various geometries based on crystal field model, spin free-spin paired equillibria in octahedral stereochemistry.

UNIT - III A. TRANSITION METAL COMPLEXES: Tranisition metal complexes with unsaturated organic molecules,alkanes ,allyl ,diene dienyl,arene and trienyl complex,preparations,properties,nature of bonding and structure features.Imporant reaction relating to nucleophilic and electrophilic attack on ligands and organic synthesis.

B. TRANSITION METALS COMPOUND WITH BOND TO HYDROGEN: Transition Metals Compound with Bond to Hydrogen.

UNIT-IV A. ALKYLS AND ARYLS OF TRANSITION METALS: Types, routes of synthesis, stability and decomposition pathways,organocopper in organic synthesis.

B. COMPOUNDS OF TRANSITION METAL - CARBON MULTIPLE BONDS : Alkylidenes, low valent carbenes nature of bond and Structural characteristics.

C. FLUXIONAL ORGANOMETALLIC COMPOUNDS: Fluxionality and dynamic equilibria in compounds such as olefin, -allyl and dienyl complexes.

BOOKS SUGGESTED :

1. Pinciples and application of organotransition metal chemistry, J.P.Collman, L.S.Hegsdus, J. R. Norton and R.G. Finke, University Science Books.

2. The Organometallic chemistry of the Transition metals, R. H. Crabtree, John Wiley.

3. Metallo - organic chemistry, A.J. Pearson, Wiley.

4. Organometallic chemistry, R. C. Mehrotra and A.Singh, New age International.

PAPER NO. CH - 8 REACTION MECHANISMS Max. Marks 100

UNIT - I A. ALIPHATIC NUCLEOPHILIC SUBSTITUTION:

The SN2, SN1, mechanisms.The neighbouring group mechanism, neighbouring group participation by π and σ bonds, anchimeric assistance. Reactivity effects of substrate structure, attacking nucleophile, leaving group and reaction medium, phase transfer catalysis, ambident nucleophile and regioselectivity.

B. AROMATIC NUCLEOPHILIC SUBSTITUTION: The SNAr, SN1, and benzyne mechanisms. Reactivity - effect of substrate structure, leaving group and attacking nucleophile. The von Richter, Sommelet-Hauser, and Smiles rearrangements.

UNIT - II A. ALIPHATIC ELECTROPHILIC SUBSTITUTION:

Mechanisms of- SE2 SE1, electrophilic substitution accompanied by double bond shifts. Effect of substrates, leaving group and the solvent polarity on the reactivity.

B. AROMATIC ELECTROPHILIC SUBSTITUTION: The arenium ion mechanism, orientation and reactivity. The ortho/para ratio, ipso attack, orienation in other ring systems.Θ Reactivity- Effect of substrates and electrophilles. Vilsmeir reaction and Gattermann-Koch reaction.

UNIT - III ADDITION TO CARBON-CARBON MULTIPLE BONDS: Mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, regio- and chemoselectivity. Addition to cyclopropane ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings Hydroboration, Micheal reaction. Shrapless asymetric epoxdation.

UNIT - IV ADDITION TO CARBON-HETERO MULTIPLE BONDS: Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids and esters, nitriles.Addition of Grignard Reagents, Organo-Zinc and Organo-lithium to carbonyls and unsaturated carbonyl compounds, Wittig reaction. Mechanism of condensation reactions involving enolates - Aldol, Knoevenagel and Stobbe reactions. Hydrolysis of esters and amides, ammonolysis of esters.

BOOKS SUGGESTED :

1. Advanced Organic Chemistry-Reactions, Mechanism and Structure, Jerry March,Johan Wiley.

2. Modern Organic Reactions, H. O. House, Benjamin.

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

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

5. Structures and Mechanism in Organic Chemistry, C. K. Ingold, Cornell University Press.

6. Reaction Mechanism in Organic Chemistry, S. M. Mukherji and S. P. Singh, Macmillian

PAPER NO. CH – 9

CHEMICAL AND MOLECULAR DYNAMICS – II Max. Marks 100

UNIT – I A. APPLICATION OF MATRICES IN QUANTUM CHEMISTRY : Addition and multiplication, inverse and transpose of matrices. Determinants, in quantum Chemistry.

B. ANGULR MOMENTION IN QUANTUM CHEMISTRY: Angular momentum, angular momentum Operators. Eigen functions and Eigen values Angular momentum, ladder operators.

C. APPROXIMATE METHODS: The variation theorem, linear variation principle. Perturbation theory (first order and non-degenerate). Applications of variation method and perturbation theory to the Helium atom.

UNIT – II A. THERMODYNAMICS OF NON IDEAL GASES : Activity and Fugacity, Determination of Fugacity, Variation of Fugacity with Temperature and Pressure.

B. NON EQUILIBRIUM THERMODYNAMICS : Fundamental concepts, Forces and Fluxes, Entropy production, Phenomenological Laws and Onsager’s reciprocity relations, Irreversible thermodynamics for biological systems, coupled reactions.

UNIT – III ELECTROCHEMISTRY – II: Structure of electrified interfaces. Gouy-Chapman, Stern, Over potentials and exchange current density, Derivation of Butler – Volmer equation, Tafel plot.Semiconductor interfaces, Theory of double layer at semiconductor, electrolyte solution interfaces, structure of double layer interfaces. Effect of light at semiconductor solution interfaces. Electro catalysis influence of various parameters. Hydrogen electrode.

UNIT – IV CHEMICAL DYNAMICS – II: General features 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 barrier less chemical reactions in solutions, dynamics of unimolecular reaction. [Lindemann – Hinshelwood and Rice-Ramsperger-Kassel-Marcus {RRKM}] theories of unimolecular reactions.

BOOKS SUGGESTED :

1. The Chemistry Mathematics Book, E. Steiner, Oxford University Press.

2. Mathematics for Chemistry, Doggett and Sutclilffe, Longman.

3. Mathematical Preparation for Physical Chemistry, F. Daniels, McGraw Hill.

4. Chemical Mathematics, D.M, Hirst, Longman.

5. Applied Mathematics for Physical Chemistry, J.R. Barrante, Prentice Hall.

6. Basic Mathematics for Chemists, Tebbutt, Wiley.

7. Physical Chemistry, P.W. Atkins, ELBS.

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

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

10. Coulson’s Valence, R. McWeeny, ELBS.

11. Chemical Kinetics, K. J. Laidler, Pearson.

12. Kinetics and Mechanism of Chemical Transformations, J. Rajaraman and J. Kuriacose, McMillan.

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

14. Thermodynamics for Chemists, S. Glasstone EWP.

15. An Introduction to Electrochemistry S. Glasstone EWP.

16. Physical Chemistry, Ira N. Levine McGraw Hill.

17. Physical Chemistry, Silbey, Alberty, Bawendi, John-Wiley.

Rest of the syllabus is attached in below file which is free of cost

**Address:**
Pandit Ravishankar Shukla University

G.E.Road, Amanaka,

Raipur, Chhatisgarh, 492010

077 12 262857

**Map:**