2

DEPARTMENT OF CHEMISTRY

FACULTY OF SCIENCE

THE UNIVERSITY OF RAJSHAHI

Syllabus for

The Degree of Master of Science (M. Sc.) in Chemistry

Session: 2007-2008

Examination 2008


PHYSICAL CHEMISTRY BRANCH:

Courses /

Course Titles

/ Units / Credits / Marks
Chem 511F / Electrolyte solutions and Electrode Processes / 1.0 / 4 / 100
Chem 512F / Advanced Chemical Kinetics / 1.0 / 4 / 100
Chem 513F / Polymer Chemistry / 1.0 / 4 / 100
Chem 514F / Bio-Physical Chemistry / 1.0 / 4 / 100
Chem 515F / Physical Methods in Chemical Analysis / 1.0 / 4 / 100
Chem 516F / Electroanalytical Chemistry / 1.0 / 4 / 100
Chem 517F / Theoretical Chemistry-III / 1.0 / 4 / 100
Chem 511AH / Class Assessment –V / 0.5 / 2 / 50
Chem 511VH* / Viva-voce–V / 0.5 / 2 / 50
Chem 511L** / Physical Chemistry Practical –V
OR / 2 / 8 / 200
Chem 599*** / Thesis / Dissertation on topics of Physical Chemistry
Total Credit Courses available / 8.0 / 32 / 800

Students shall have to choose any five full unit theoretical courses from first seven full unit theoretical courses
(Chem 511 F – Chem 517 F)

* Viva-voce examination includes the assessment of the students through oral examination of all the courses.

** Laboratory courses include 30% (60) marks for continuous Lab. assessment.

*** Thesis includes 30% (60) marks for oral examination on the thesis.

Examination of the theory courses of 100 marks (1.0 unit, 4 credits) shall be of 4 (four) hours duration, and of the practical courses of 200 marks (2.0 unit, 8 credits) shall be of 24 (twenty four) hours duration (4 days). The students shall submit a report after each Lab. class to the Lab. teacher(s) for evaluation. After evaluation the report shall be returned to the students. The lab. teacher(s) shall submit the average marks of all Lab. evaluations in sealed envelopes to the chairman of the relevant examination committee within three weeks from the last lab. held.

The class assessment course includes tutorial, terminal, home assignment, and /or class examinations taken on theoretical courses by the relevant course teacher(s) during the academic year. The class teacher(s) of each course shall submit the average consolidated marks of class assessments in sealed envelope to the Chairman of the relevant examination committee within three weeks from the last class held. The examination committee shall send a copy of the consolidated marks for each of the viva-voce examination, class assessment, lab. evaluation and practical examinations to the controller of examinations

No student having less than 60% class attendance shall be allowed to sit for the examination.

Course: Chem 511F

Electrolyte solutions and Electrode Processes

Examination: 4 Hours

Full Marks : 100 (1 unit, 4 credits)

(80 lectures, 4 lectures per week)

  1. Structure and properties of electrolyte solutions (15 lectures): Structure and properties of water; intermolecular forces; solubilization process; solvation of ions – theories and energetics, determination of solvation number; Debye-Hückel theory of ion-ion interactions in electrolyte solutions, critical appreciation of Debye-Hückel theory; modification of Debye-Hückel theory; activity coefficient and methods for its determination; theory of ion association, ion association equilibrium. Diffusion in electrolyte solutions: Fick’s laws, application of Fick’s laws to electrolyte solutions, ion-ion interaction during diffusion of electrolytes, diffusion potential.
  2. Interfacial electrochemistry (20 lectures): Origin and thermodynamics of electrode potential: potential differences in electrochemical systems, electromotive force and electrode potentials as the sum of Volta potentials, the nature of potential differences across phase boundaries, the Nernst osmotic theory and the hydration theory of electrode potentials. Theories of double layer formation at the electrode-solution interfaces: formation of the double layer; the parallel plate condenser theory (Helmholtz double layer), the diffuse layer theory (Gouy-Chapman double layer), the adsorption theory (Setern’s treatment) of the double layer; recent developments in double layer theory. Adsorption at electrode surfaces: isotherms and the behaviour of reactant ions and molecules at electrodes – Langmuir isotherm, Temkin isotherm and heterogeneity of interaction effects, electrochemical isotherms for ion adsorption.
  3. Kinetics of electrode processes (15 lectures): Electrode polarization and overpotential; classification of polarization phenomenon, the concept and theory of diffusion overpotential; diffusion-controlled reactions; principles and applications of polarography; basic factors in ion discharge; formulation of overall kinetic rate equation, concentration dependence of rate of a discharge step, net currents and exchange currents; heats of activation and frequency factors; activation controlled reactions; kinetics and mechanism of some simple electrode reactions, viz., hydrogen evolution at the cathode and oxygen evolution at the anode.
  4. Some electrochemical systems of technological importance (10 lectures): Corrosion and passivation of metals, corrosion testing, corrosion industries, theories of corrosion and methods of combating corrosion; electrochemical energy conversion devices, primary and secondary batteries, fuel cells, electroplating of metals, viz., Cu, Ni, and Cr; factors governing the nature of deposits; ornamental and porous deposits
  5. Organic reactions at electrodes (20 lectures): The Electrolysis Cell; choice of working and reference electrodes; selection of solvent and supporting electrolyte. Reduction of functional groups: carbonyl compounds, nitro groups, carbon-halogen bonds, unsaturated compounds, carbon-nitrogen bonds, organosulfur compounds, organometallic compounds, peroxides, reduction of carbon-nitrogen single (s) bonds. Oxidation of functional groups: the Kolbe reaction, mechanism and role in organic synthesis, oxidation of unsaturated compounds, anodic substitution, alkoxylation, acetoxylation, cyanation and acetamidation; oxidation of aromatic alcohols, anhydrides; oxidation of olefins; anodic halogenation. Electrosynthesis of some compounds of commercial importance: propylene oxide, hydroquinone, adiponitrile, tetraethyl lead etc.

Books Recommended:

  1. D. Eisenberg and W. Kauzmann : The Structure and Properties of Water
  2. J.O’M. Bockris and A.K.N. Reddy : Introduction to Electrochemistry
  3. B.E. Conway : Electrode Processes
  4. K.J. Vetter : Electrochemical Kinetics
  5. G. Khortum : Treatise on Electrochemistry
  6. L. Anthrpov : Theoretical Electrochemistry
  7. W. Blum and G.B. Hogaboom : Principles of Electroplating and Electroforming
  8. Kohler and Creighton : Electrochemistry – Principles and Applications
  9. Mars G. Fontans and Greene : Corrosion Engineering
  10. S.N. Banerjee : An Introduction to the Science of Corrosion and Its Inhibition
  11. E. C. Potter : Electrochemistry – Principles and Applications
  12. G. Mantell : Industrial Electrochemistry
  13. M.R. Rifi and Frank H. Covitz : Introduction to Organic Electrochemistry
  14. Demetrios K. Kyriacou : Basics of Electro-organic Synthesis
Course : Chem 512F

Advanced Chemical Kinetics

Examination : 4 Hours

Full Marks : 100 (1 unit, 4 credit)

(80 lectures, 4 lectures per week)

1.  Energy of activation (20 lectures): Statistical distribution of molecular energies: simple statistical expressions; Tolman’s theorem. Potential energy surfaces: ab initio calculations of potential energy surfaces: treatments based on London equation, variational calculations; semiempirical calculations of potential energy surfaces: London-Eyring-Polanyi (LEP) method, Sato method, modified LEP methods, bond-energy-bond-order (BEBO) method; empirical treatments of activation energy.

2.  Theories of reaction rates (10 lectures): Conventional transition state theory (STST); derivations of rate equation from CTST; symmetry numbers and statistical factors; applications of CTST to reaction between atoms and reactions between molecules with a few specific examples (e.g., the reaction H + HBr = H2 + Br2); thermodynamic formulation of CTST; assumptions and limitations of CTST; multiple crossing and the equilibrium hypothesis; reparability of the reaction co-ordinate; quantum effects; extensions of transition state theory; variational transitional-state theory; quantum-mechanical transition-state theory; microscopic reversibility and detailed balance.

3.  Theory of unimolecular reactions (10 lectures): Recapitulation of Lindemann-Christiansen and Hinshelwood’s treatments. The Rice-Ramsperger-Kassel (RRK) treatment, Slater’s treatment, Marcus’s extension of RRK treatment (RRKM); influences of foreign gases; intramolecular and intermolecular energy transfer; laser-induced unimolecular reactions; decomposition of ions; combination and disproportionation reactions; mechanism of atom and radical combinations.

4.  Reactions in solution (20 lectures): Effects of solvents on reaction rates; factors determining reaction rates in solution; collision theory in solutions; transition-state theory for reactions in solution: influence of internal pressure of the solvent, influence of solvation of reactants and activated complex; reaction between ions: influence of solvent dielectric constant on rates, pre-exponential factors of ionic reactions, single-sphere activated complex for activated complex, influence of ionic strength, more advanced treatments for ionic reactions in solutions; ion-dipole and dipole-dipole reactions in solutions; influence of hydrostatic pressure on rates; substituent and correlation effects on rates; diffusion controlled reactions: full microscopic diffusion control and partial microscopic diffusion control, reactions involving two ions.

5.  Composite reactions (10 lectures): Rate equations for composite mechanisms: simultaneous and consecutive reactions, rate-determining steps, microscopic reversibility and detailed balance; chain reactions; some inorganic reaction mechanisms: hydrogen-bromine reaction, hydrogen-chlorine reaction, hydrogen-iodine reaction, comparison of hydrogen-halogen reactions formation and decomposition of phosgene, decomposition of nitrogen pentoxide, decomposition of ozone, para-ortho hydrogen conversion; mechanism of organic decomposition reactions: Goldfinger-Letort-Niclause rules, molecular processes, decomposition of ethane and acetaldehyde, inhibition mechanisms; mechanism of gas-phase combustion of hydrogen and hydrocarbons.

6.  Reaction dynamics (10 lectures): Importance of reaction dynamics; molecular-dynamical calculations of chemical reactions: the reaction H + H2, the reaction Br + H2 and more complex reactions; chemiluminesence; features of potential energy surfaces: attractive surfaces for exothermic reactions, repulsive surfaces for exothermic reactions, surfaces of intermediate types for exothermic reactions, selective enhancement of reaction, disposal of excess energy, gradual and sudden surfaces, influence of rotational energy; molecular beams: stripping and rebound mechanisms, state-to-state kinetics.

Books Recommended:

1.  P. W. Atkins : Physical Chemistry

2.  Keith J. Laidler : Chemical Kinetics

3.  S. Glasstone, K.J. Laidler & H. Eyring : The Theory of Rate Processes

4.  K.J. Laidler and J.H. Meiser : Physical Chemistry

Course: Chem 513 F

Polymer Chemistry

Examination : 4 hours

Full Marks : 100 (1 unit, 4 credits)

(80 lectures, 4 lectures per week)

1.  Basic concepts of polymers (10 lectures): Macromolecules; Repeating units of polymers; Monomer; Representation of polymer structures; End groups in polymer chains; History of polymers; Classification of polymers; Polymer nomenclature; Linear, branched and cross linked polymers; Conditions of polymerization; Molar masses and their distribution; Comparison of addition and condensation polymers; Basic ideas of thermoplastics, thermosets, elastomers, fibres and plastics; Isomerisation in polymers; Utility of polymers.

2.  Condensation polymerization (12 lectures): Definition; Types of polycondensation reactions; Kinetics of condensation or step-growth polymerization; Degree of polymerization and extent of reaction; Carothers equation for bifunctional polymers: Molar mass distribution in linear condensation polymerisation; Factors influencing the maximum attainable molar mass of condensation polymers; Techniques of condensation polymerization; Branched and crosslinked condensation polymers.

3.  Addition polymerization (18 lectures): Definition; Types of addition polymerization (free-radical, cationic, anionic and coordination); Monomers and initiators; Effect of substituents on the polymerization mechanism of vinyl polymers; Overall scheme of free-radical polymerization: Methods of radical production; Efficiency of initiators; Chain propagation, chain transfer and chain termination; Kinetics of free radical polymerization; Average kinetic chain length and average degree of polymerization; Chain transfer and its effects on ideal free radical polymerization; Chain transfer constant; Initiation and retardation; Techniques of free radical polymerization.

Ionic and coordination polymerization: Mechanism of anionic polymerization; Living polymers; Mechanism of cationic polymerization; Mechanism of coordination polymerization; Ring opening polymerization; Comparison of coordination and addition polymerization.

4.  Copolymerization (12 lectures): Copolymerization types (block, random and graft copolymerizations); Simple copolymer equation (kinetics and mechanism of binary free radical copolymerization); Monomer reactivity ratios; Significance and determination; Copolymerization behaviour and reactivity ratio; Q-e scheme; Reactivities of radicals and monomers: Resonance effects, polar effects, steric effect; Effect of reaction condition (temperature, pressure, medium, complex formation); Rates of free radical copolymerization; Ionic copolymerization; Copolycondensation; Technical significance of copolymerization; Important copolymers.

5.  Rheology of polymers (10 lectures): Mechanical behavior of polymers; Stress and strain; Ideal elastic solid (Hookian model); Ideal fluid (Newton or dash pot model); Maxwell model for viscoelasticity ; Voigt model for viscoelascity; deformation behaviour of polymeric materials; Non-Newtonian fluid; Stress relaxation; Increase of strain under constant stress; Rheological measurements; Hysteresis.

6.  Structure-property relation of polymers (10 lectures): Crystallinity of polymers; Factors influencing the formation of crystallite in polymers, Change of polymer property at crystalline melting point; Factors influencing the crystalline melting point; Orientation of crystalline polymers; Size of crystallite and degree of crystallinity; Glass transition in polymers.

7.  Molar mass, shape and size of polymers (8 lectures): Determination of molar mass of polymers by light scattering, colligative properties, end group analysis, ultracentrifuge and viscosity methods; Shapes of linear chain polymers in solution; Shapes of polymers molecules and viscosity; Effect of concentration, temperature and solvent on viscosity of polymer solutions.

Recommended Books:

1.  Alfred Rudin : The elements of Polymer Science and Technology

2.  George Odian : Principles of Polymerization

3.  Premamoy Ghosh : Polymer Science and Technology of Plastics and Rubbers

4.  Paul C. Hiemenz : Polymer Chemistry the Basic Concepts

5.  P.J. Flory : Principles of Polymer Chemistry

Course : Chem 514F

Biophysical Chemistry

Examination: 4 hours

Full marks : 100 (1 unit, 4 credits)

(80 lectures, 4 lectures per week)

1.  Noncovalent bonding and pH buffering (10 lectures): Water the biological solvent, stabilizing and organizing forces of nature, acid base equilibria, principle of pH buffering, buffering of blood, laboratory use of buffers, ionic strength..

2.  Biomolecules (12 lectures): Building block molecules of biomolecules, amino acid structures, polypeptides, ionic properties of amino acids and polypeptides, nucleotides and nucleic acids, base composition and base sequence of nucleic acids, simple idea about carbohydrates and lipids.

3.  Proteins (15 lectures): Classifications, primary, secondary, tertiary and quarternary structure of globular proteins, salting in and salting out of proteins, chemistry of ion exchange and chromatographic technique in isolation/purification of protein characterization of proteins, molecular weight determination of proteins by PAGE and get filtration techniques. Proteins binding and phermercodynamics, complexation and drug action, metal complexation in biological systems.