Gauhati University Question Papers for Chemistry 5th Semester

Gauhati University Question Papers for Chemistry 5th Semester

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Third Year

                                  Semester  V

   

PAPER  M 501  :  Quantum Chemistry       

Unit 5.1    Quantum Theory                 

Review of experiments leading to the idea of quantization – (a).  Black body radiation – Planck’s hypothesis (b).  Photoelectric effect – Einstein’s explanation (c).  Compton effect

Electron diffraction, de Broglie hypothesis, Heisenberg’s uncertainty principle. Postulates of Quantum mechanics.

Wave functions, Operators, Eigen functions and eigen values, the Schrodinger postulates of operator transforms and the wave equation boundary conditions, normalization of the wave functions, expectation values. Interpretation of the wave function – orthogonal and orthonormal wave functions.

Model systems – particle in 1D and 3D boxes – particle in a ring, harmonic oscillator and rigid rotator (detailed mathematical treatment not necessary) : coordinate systems – construction.

Hamiltonian – potential function leading to potential energy term – Schrodinger equation, outline of solution, energy expression, wave functions, quantum numbers. Special features like degeneracy, energy level diagrams, plot of wave functions and their squares vs displacement from origin, zero point energy, quantum mechanical tunneling, force constant and bond strength (for harmonic oscillator), moment of inertia in 3D, angular momentum, space quantization of angular momentum (for rigid rotator).

Qualitative discussion of all these topics.

Unit  5.2    Atomic Structure                                   

The Hamiltonian and Schrodinger equation for hydrogen atom, energy levels and quantum numbers, the radial and the angular part of the wave function, construction of two dimensional plots of probability density and calculation of radial probability functions. The orbitals of hydrogen and hydrogen-like atmos, contour diagrams of electron density. Stern-Gerlach experiment, electron spin and spin quantum number – spin orbitals. Electron configuration of many electron atoms, Pauli’s exclusion principle

– illustration by He atom using wave functions.

Spin-orbit interactions, Russel-Saunder’s coupling, Term symbols. Effect of magnetic

field on energy levels. Hund’s rule.

Unit  5.3   The Nature of Chemical Bond                                      

Schrodinger equation for a molecule, Born-Oppenheimer approximation. LCAO-MO theory as applied to H2+ and H2 - drawback of MO theory.  MO energy level diagram of homonuclear (O2, N2) and heteronuclear (HF, LiF, CO) diatomic molecules. Heitler- London theory – wave function and potential energy curve of H2. Concept of resonance and hybridisation from VB theory. Term symbols of diatomic molecules. Huckel theory for ethene and benzene.

PAPER  M 502    Physical Chemistry                                    

Unit  5.4     Molecular Reaction Dynamics                

Collision theory, Activated complex theory;  Erying equation – thermodynamic formulation. Theory of unimolecular reactions (Lindemann) – dynamic molecular collisions – potential energy surfaces – Molecular beam technique and results of molecular beam studies. Reactions in solution,  Bronsted- Bjerrum equation, Kintic salt effect.  Introduction to lasers, flash photolysis.

Unit  5.5    Photochemistry                 

Laws of photochemical equivalence, Quantum yield, chemical actinometry Kinetics of H2-Br2 , H2-Cl2 reactions, Dissociation of HI, Photostationary equilibrium, Dimerisation of  anthracene.

Luminescence phenomenon – fluorescence, phosphorescence, Jablonski diagram, Photosensitised reactions, Quenching of fluorescence. Chemi and bio luminescence.

Photochemistry of air and air pollution.

Unit  5.6   Phase Equilibria                

Definition of phase, meaning of components and degrees of freedom. Derivation of phase rule. Phase diagram of one component system (water). Phase diagram of two component system – eutectics, congruent and incongruent melting points, solid solutions.

Interpretation of liquid-vapour, liquid-liquid and liquid-solid phase diagrams. Distillation of partially miscible liquids.

Clausius Clapeyron equation for different phases. Systems of variable composition, partial molar quantities, Gibbs Duhem equation, Thermodynamics of mixing.

Chemical potential, chemical potential of a component in an ideal mixture – fugacity,

activity coefficients. Dependence of chemical potential on temperature and pressure.

Unit  5.7   Surface Chemistry                 

Introduction to solid surfaces, adsorption on surfaces – physisorption and chemisorption. Adsorption isotherms – Langmuir, Freundlich, BET equation. Determination of surface area, Catalytic activity at surface with examples.

Concept of surface excess, Gibbs equation, surface pressure and surface spreading.

PAPER M 503     Organic Chemistry      Unit   5.8   Organic Reaction Mechanisms      

A.  Molecular Rearrangements of the types

Nucleophilic or anionotropic  : Whitmore 1,2 Shift, Wagner-Meerwein, Wolff, Hofmann, Lossen, Curtius, Schmidt, Beckman, Favorskii, Benzil- benzilic acid, Baeyer Villiger

Free radical : Wittig

Electrophilic or cationotropic  :   Pinacol

Special  :  Fries rearrangement ( aromatic electrophilic substitution) Stevens (ion pairs in solvent cage/ radical pair)

B.    Oxidation - reduction  : common oxidizing and reducing agents.

i) Direct electron transfer: Clemmensen (Nakabayashi mechanism)

ii)  Hydride transfer

iii) Hydrogen Atom Transfer: Bouveault-Blanc

iv)  Formation of ester intermediate: oxidation by dichromate, permanganate, etc. v)  Displacement mechanism.

vi) Addition- elimination.

Oxidizing agents  : Chromium oxide, selenium dioxide, Chromyl chloride, PCC, and Lead tetraacetate.

Catalytic hydrogenation (Pd, Pt, Raney Ni).  Reduction by LAH, Sodium Borohydride and metals (Birch).  Reduction of nitro group under various condition.  Selective reduction- Rosenmund reduction, Lindlars catalyst.

C.  Pericyclic Reactions

Definition and examples of 2+2 and 2+4 cycloadditions. The conservation of orbital symmetry.  Woodward Hoffman rules. Diels Alder reaction, 1,3 Dipolar Cycloaddition. Sigmatopic rearrangements-Cope and Claisen rearrangements. Electrocyclic reactions- HOMO-LUMO approach.

Unit 5.9   Polynuclear Aromatics, Nitro and amino compounds, Organo S and organo P   Compounds, Active methylene compounds and Heterocyclic compounds

Polynuclear aromatic hydrocarbons

Structure, bonding, properties and reactivity of naphthalene and its derivatives. Anthracene, phenanthrene

and anthraquinone-important methods of synthesis.

Nitro and amino compounds

Synthesis, physical properties and reactivity of nitroalkanes, alkyl nitrates, alkyl nitriles, isonitriles and

aromatic nitro compounds. Synthesis, reactions and basicity of aliphatic and aromatic amines.

Diazotization and its mechanism. Distinction between primary, secondary and tertiary amines,

Quarternary ammonium salts, Hofmann exhaustive methylation and Hofmann degradation of amines.

Organo S and organo P compounds

Synthesis and reactions of thiols, thioethers and aliphatic sulphonic acids.  Phosphines, Phosphorous esters

and phosphorous ylides- Wittig reaction.

Active methylene compounds

The active methylene groups, synthesis of compounds containing active methylene groups      (Ethylacetoacetate, Diethylmalonate and cynaoacetic ester) and their use in organic synthesis.

Heterocyclic compounds

IUPAC nomenclature, Synthesis, structure and bonding, properties (basicity, aromaticity) and reactions of   pyrrole, furan, thiophene, pyridine, indole and quinoline.

PAPER  M 504     Inorganic Chemistry                                              Unit 5.10   Bonding in Coordination Compounds                                      

Symmetry elements and Symmetry operation, Point group classification, Symmetry of octahedron, tetrahedron and square planar complexes, Structure and symmetry of inorganic compounds(coordination 2-8), Shape and symmetry of s,p and d orbital.

Crystal field theory, factors affecting 10 Dq value, crystal field stabilization energy, Magnetic properties from crystal field theory, high spin and low spin complexes, structural and thermodynamic affects of orbital splitting, octahedral coordination in Spinels. Adjusted crystal field (or Ligand field) theory, Molecular orbital theory of octahedral complexes (without and with p bonding).

Metal-metal bonding and quadruple bonds.

Unit  5.11     Organometallic Compounds                                         

Synthesis, structure and bonding of complexes with olefins, acetylene, allyl, cyclopentadiene and arenas. IUPAC nomenclature. Effective Atomic number rule, Transition metal to carbon sigma bonds.

Homogeneous catalysis by transition metal complexes (isomerzation, hydrogenation, hydroformylation and Ziegler-Natta Polymerization).

Synthesis and structure of organomettalic compounds of Sn and Pb, Organometallic compounds of Zn, Cd and Hg.

Unit  5.12    Bioinorganic Chemistry I                                                 

Essential and trace elements and their biological role, Importance of Na/K salts and calcium in biology.

Uptake and storage of iron, Introduction to the structure and function of hemoglobin, Synthetic dioxygen carriers, Dioxygen toxicit