KUVEMPU
UNIVERSITY
DEPARTMENT OF CHEMISTRY
SAHYDRI SCIENCE COLLEGE(Autonomous)
SHIMOGA - 577 203
SYLLABUS FOR INTEGRATED M.Sc.(Hons.) COURSE IN CHEMISTRY
VIII – SEMESTER
ANALYTICAL CHEMISTRY
UNIT–I
16 hours
ELECTROMAGNETIC RADIATION
Introduction, nature and interaction of electromagnetic radiation. Classification of
electromagnetic radiation, atomic and molecular transitions, selection rules, factors
influencing, intensity and position of spectral lines.
Electronic spectroscopy
Electronic spectra of diatomic and poly atomic molecules, types of transition and their
theoretical interpretation, ligand field and charge transfer spectra, Beer’s law, Lambert’s
law, Beer’s-Lambert’s law, limitations: Chromophores, auxochromes, effect of
substituents on the position and structure on max , prediction of max for polyenes,
,-unsaturated aldehydes and ketones (Woodward- Fisher rule), aromatic systems and
their derivatives, applications, qualitative and quantitative, spectrometric titration,
simultaneous determination of copper and nickel in a mixture pKa value of an indicators.
IR spectroscopy
Theory, types and number of modes of vibration, selection rules, group frequencies and
their dependence on chemical environment (bond order, conjugation, hydrogen bonding,
ring size, overtones. Fermiresonance, instrumentation, interpretation of IR, application to
structure elucidation of simple molecules, effects of co-ordination and symmetry of donor
molecules of IR spectra).
UNIT–II
Electron spin resonance spectroscopy
16 hours
Basic principle interaction between pin and magnetic field: Origin of spectral lineintensity, width and position of spectral lines. Relaxation process, multiplicity in ESR,
hyperfine splitting, g-value and factor affecting. Rules for interaction of spectra. Zero
field splitting and Krammer’s degeneracy, John-Teller distortion, isotropic and
anisotropic coupling constants, nuclear quartrpole coupling interaction, spin hamitonium,
ESR spectra of radical containing a single set of equivalent protons-methyl,
parabezoquinone, cyclopentadienyl, benzene. ESR spectra of transition metal complexes,
applications.
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Flame photometer and atomic absorption spectroscopy
Introduction, principle, flames and flame spectra variation of emission intensity with
flames, flame background, metallic spectra in flame. Total consumption and premix,
Butters interference, roll on temperature on absorption, atomic absorption spectroscopy,
source, hallow cathode lamps, line sources, comparative studies of AAS and flame
photometer.
UNIT–III
Nuclear magnetic resonance spectroscopy
16 hours
Types of nuclei,(classical and quantum) relaxation process, chemical shift, mechanism of
shielding, factor influencing chemical shift, spin-spin coupling, rules governing the
interpretation of first order spectra. Low and high resolution NMR, Karplus equation,
line broadening, chemical exchange, decoupling technique, shift reagents, functional
molecules, nuclear over Hauser effect COSY-2D NMR. Continuous wave and FT –NMR,
magnetic resonance imagines (MRI) application to structure elucidation of simple organic
molecule. Use of NMR in paramagnetic complexes, FT –NMR, C13NMR ,basic theory,
natural abundance of C13, chemical shift, multiplicity of signal, application, NMR of
solids.
UNIT–IV
Mass spectrometry
16 hours
16 hours
Introduction basic theory, instrumentation, mass spectrometer, method of generation of
positively charged ions, chemical ionization, fast atom bombardment(FAB), mass
analyzer, resolving power, molecular ion peak, meta stable peak, modes of fragmentation,
Mclafferty rearrangement. Retro Diels-Alder reaction, ortho effect, structure elucidation
of some organic compounds, -ve ion mass spectrometer, determination of appearance
potential and ionization potential, determination of molecular weight and molecular
formula. Application of mass spectrophotometer in qualitative and quantitative analysis.
Thermal methods of analysis
Introduction, thermogravimetric analysis (TGA), types of thermogravimetric analysis,
principle and method, automatic thermogravimetric analysis, instrumentation, types of
recording thermobalances, sample holders, factors influencing thermograms and
applications. Isothermal analysis, differential thermal analysis (DTA), principle of
working, theory and instrumentation, simultaneous DTA-TGA curves, factors affecting
results and applications. Differential Scanning Colorimetry (DSC), principle of working,
theory, instrumentation and applications, thermometric titrations.
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REFERENCES
01.
02.
03.
04.
05.
06.
07.
08.
Spectroscopy of organic compounds – P. S. Kalasi, Wiley Eastern Ltd, India
1993.
Organic Spectroscopy – William Kemp, 3rd edition, ELBS 1991.
Quantitative chemical analysis – D. C. Harris, W. M. Freeman Et. al NY, USA,
IV edition 1995.
Introduction to instrumental analysis – R. D. Braun, McGraw Hill Book company
1982.
Fundamental of molecular spectroscopy – C. N. Banwell, Tata McGraw Hill
Book Company 1973.
Physical methods in inorganic chemistry – R. Drago East West Pvt. Ltd, 1968.
Instrumental methods of chemical analysis – Chatwal and Anand.
Organic Spectroscopy, 2nd edition– Jag Mohan, Narosa Publishing House New
Delhi
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INORGANIC CHEMISTRY
UNIT-I
16 hours
Co-ordination Chemistry
Interpretation of electronic spectra, calculation of ∆, B and beta, spectrochemical series
and nephelauxetic series, electronic spectra of aqua complexes of divalent 3d-metal ions,
charge transfer spectra, characteristic, types, LMCT and MLCT, electronic spectra of
lanthanides and actinides complexes.
UNIT-II
16 hours
Molecular Symmetry and Group Theory:
Symmetry elements and symmetry operations, rotation axis, plane of symmetry, rotation,
reflection axis, centre of symmetry and identity product of symmetry operations, general
relationship among symmetry elements and operations, general relationship among
symmetry operations.
Group theory, concept of properties of group, definition of point group, procedure for
classification of molecules in to point groups, group multification table, representation of
symmetry operation and matrices, reducible and irreducible tables, orthogonality
theorem, derivation of character table for C2v, C3v and D2h point groups, symmetry and
dipole elements. Application of group theory to IR and Raman spectroscopy (CO2, NH3,
and H2O molecules), detection of selection rules spectroscopy transitions.
UNIT-III
16 hours
Inorganic Chains, Rings and Cages
Silicates and alumino silicates; classification, structure, properties, application.
Silicones; Silicone polymers, Preparation, properties and applications.
Boranes: Structure and bonding, wades rules, Styx code for B2H6, B3H6, B4 H10,B5
H9,B5H11 and B6H10.
Carboranes: Preparation, properties, structure and bonding in borazoles, phosphazenes
(BN)x and (SN)x
Redox potentials, pourbaix diagrams
UNIT-IV
16 hours
Carbon and Alloy Steels
Definition, uses, effects of residual elements on carbon steel, the iron carbon
phase diagram, effect of carbon percentage on structure of carbon steel, types of carbon
steel- classification of low, medium and high alloy steels, properties of different alloys
steels stainless steels, toll and die steels, heat resistant alloys, spring alloys, bearing
alloys, metal for nuclear energy.
Non-Ferrous Metals and Alloys
Phase diagram for light alloys, aluminium and its alloys, effect of alloying
elements, copper and copper alloys.
Titanium and titanium alloys.
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REFERENCES
1. Advanced Inorganic Chemistry, 5th edition, F.A. Cotton and G. Wilkinson, JohnWilley and sons 1988
2. Inorganic Chemistry, principles of structure and reactivity, 3rd ed. James E. Huheey,
Ellen E Keithr and Richard L Keither, Harper Collins college pub, 1993.3
3. Inorganic Chemistry, 3rd ed. D.P.Shriver and P.W.Atkins, Oxford University press,
1999
4. Organometallic Chemistry : A unified approach. R.C.Mehrotra, and A.Singh, Willeyeastern , New Delhi
5. Comprehensive coordination Chemistry. Eds:G.Wilkinson, R.D.Gillers and
J.A.McCleurry, Pergomon Press
6. Synthesis and Characterization of Inorganic Compounds, W.L.Jolly, Prentice Hall
7. Concise Coordination Chemistry, R.Gopalan and V.Ramalingam.
8. Principles of Bioinorganic chemistry Vikas publication, New Delhi, 2001.
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PHYSICAL CHEMISTRY
UNIT-I
16 hours
Statistical Thermodynamics
Introduction to statistical thermodynamics, energy states, quantum mechanical
and statistical aspects, unit cells, microscopic state and macroscopic state, phase space,
system, assembly and ensemble, use of ensemble, Lowville’s theorem, microcononical
ensemble, canonical ensemble, goland canonical ensemble, emfifuration, probability,
distribution, distribution complexion, combination, thermodynamic probability,
combinatory rules, statistical equilibrium, molecular basis of residual entropy.
Classical statistics, Sterling’s approximation, Maxwell Boltzmann distribution
law and its applications. Bose-Einstein statistics, Fermi-direc statistics and their
comparisons. Derive the relationship between entropy and thermodynamic probability,
partition function, thermodynamic functions in terms of partition function (energy, heat
capacity, entropy, Gibb’s free energy, enthalpy Helmholtz free energy). Evaluation of
different types of partition function. i) Translational partition function. Ii) Rotational
partition function iii) vibrational partition function electronic partition function iv)
nuclear partition function, Derive Sacker-Tetrode equation. Equilibrium constant and
partition-function. Study of mono atomic molecules on the basis of partition function.
Study of atomic molecules on the basis of partition function, partition function and third
law of thermodynamics. Standard third law entropies are less than statistical entropies for
CO and N2O whereas it is reverse for (CH3) Cl and CHCl3, residual entropy (problems to
be solved).
UNIT-II
16 hours
Partial molar properties
Partial molar properties, concept of partial molar properties, consequences of
partial molar property concept. Physical significance of partial molar quantities.
Determination of partial molar properties (direct method, intercept method, apparent
molar properties). Chemical potential, physical significance of chemical potential,
variation of chemical potential with pressure and temperature. Gibb’s Duhem equations,
chemical potential of a pure solid or liquid. Chemical properties of pure ideal gas,
activity, fugacity, activity coefficients for solutes and solvents. Determination of activity
coefficient, thermodynamic function of ideal gases i) free energy of ideal mixing (AG
mix) ii) enthalpy of ideal mixing iii) entropy of ideal mixing iv) volume of ideal mixing
v) Helmholtz’s free energy of ideal mixing vi) Duhem-Margoles equation and its
applications. Thermodynamics of ideal and non ideal solutions. Relationship between
chemical potential Kapler-Clausius equation.
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UNIT-III
16 hours
Quantum Chemistry-II
One dimensional simple harmonic oscillator in Clausius mechanics and quantum
mechanics, wave functions of the harmonic oscillators, the applications of Schrödinger’s
equations to the H2 atom (separation of R, θ, φ equations and their solutions). Quantum
number and their characteristics. Hydrogen like wave functions, angular and radial wave
functions, orbital diagram, variations method, linear and non linear variation functions,
perturbation theory, application to the He atom, ant symmetric and exclusion principle,
Slater’s determination wave functions, terms symbols and spectroscopic status.
Approximate methods in quantum mechanics. Need for approximate methods, (i)
variation methods and its application to hydrogen atom, general equation and general
determination, application of variation method to hydrogen molecule, ion and normal and
degenerate states, second order perturbation theory and its application to linear harmonic
oscillation.
UNIT-IV
16 hours
Chemical dynamics
Chemical kinetics in solution, theory of absolute in ideal solutions, influence of
solvents on reaction rates. Frequency factor, primary salt effect, secondary salt effect
(Bronsted-Bisrrum equation), diffusion controlled reactions in solutions (Deby
Slomuchowski equation), merits of fast reactions. I) NMR ii) relaxation methods iii)
pulse method (flash photolysis, flash radiolysis) iv) shock tubes v) stopper flow method
vi) Molecular reactions dynamics, reactions in molecular beams (scattering as a probe of
reaction dynamics), potential energy surfaces (Femtochemistry), absolute rate theory
applied to fast reactions. Molecular momentum of rate of slow reactions. Linear free
energy relationship. Thermodynamic simplications of linear free relationship. Hammett’s
relationship. Derivations of Hammett equation. Taft equation, solvent effects on rates.
REFERENCES:
1. Elements of statistical thermodynamics- E.K.Nash, Wesley, 1974
2. Statistical thermodynamics- M.C.Gupta, Willey Eastern ltd. 1990.
3. Statistical mechanics-Doley.
4. Textbook of polymer science –Billmeyer, Willey Intersection.
5. Elements of statistical thermodynamics- E.K.Nash, Wesley, 1974
6. Statistical thermodynamics- M.C.Gupta, Willey Eastern ltd. 1990.
7. Statistical mechanics-Doley.
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ORGANIC CHEMISTRY
UNIT-I
16 hours
ORGANIC REACTIONS
Named Reactions
Aldol, Stobbe, Dieckemann, Perkin’s reaction, Riemer-tiemann reaction,
Reformatsky reaction, Diel’s alder reaction, Friedel-craft reaction, Wittig reaction,
Michael addition, Robbionson annulations, Oppenuar oxidation, Wolf-kishner reduction,
Birch reduction, Meerwin-pondorf-vereley reduction, Stark enamine synthesiss, Mannich
reaction, Sharpless asymmetric epoxidation, Ene reaction, Barton reaction, HoffamannLoflar-fatyg reaction, Shapiro reaction, Bayer-Villager reaction, Chichibibin reaction.
Rearrangement reactions
Classification and general mechanistic treatment of nucleophilic, electrophilic and
free radical rearrangements, Wagner-meerwein, Benzyl-benzillic acid, wolf, Von-ritcher,
Neber, Sommet-Houser, Hoffmann, Curtius, Lossen, Smidth, Benzidine rearrangement
reaction.
UNIT-II
HETEROCYCLIC CHEMISTRY
16 hours
Definition, Classification, general nomenclature, synthesis and reactions of Furan,
Thiophene, Pyrrole, Imidazole, Pyrazole, Oxazole, Isoxazole, Pyridine, Pyradazine,
Pyrimidine, Pyrazine, Quinoline, Isoquinoline, Indole, Benzothiophene and Benzofuran
UNIT-III
PHOTOCHEMISTRY
16 hours
Bonding and anti-bonding orbital’s, singlet and triplet states, relative energies of
excited states, Jablonski diagrams, photo reduction of ketones, photo
oxidation,photoisomerisation,photosenstitisation,photolysis,Norrish type-1 and Norrish
type-2 reactions, di-pi-methane rearrangement, Patterno-Buchi reaction and
photochemistry of arenes, carbonyl compounds.
PERICYCLIC REACTIONS
Classification of pericyclic reactions, FMO and PMO approach to the following
reactions, Electro cyclic reactions- conrotatory and disrotatory of 4n, 4n+2,4n-2 and
allylic systems. Cycloaddition reactions: Antrafacial and suprafacial additions.
Sigmatropic rearrangements: antrafacial and suprafacial shifts involving C and H,
Woodward and Hoffmann selection rules for pericyclic reactions, Ene, Claisen and Cope
rearrangements.
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UNIT-IV
16 hours
DISCONNECTION APPROACH
Introduction to disconnection approach, basic principles and terminologies used in
disconnection approach. Synthons and synthetic equivalents. One group C-X and two
groups C-X disconnections.
RETRO SYNTHESIS
Retro synthesis of benzocaine, Paramethoxy acetophenone, Saccharine,
Bisbolaene, Cubane. Estrone, Catharidine, Lycorane and Multistriatin.
SYNTHETIC DESIGN
Starting material for synthesis, molecular characteristics, serial syn synthesis and
parallel synthesis, advantages of parallel synthesis, carbon skeleton complexibility,
functionality and stereo chemical consideration.
REFERENCES
01. Jerry Mrach
02. Morrison Boyd
03. Stuart Warren
04. Dyer
05. Joule Mills
06. Mukharjee and Singh
07. Joule smidth
08. Peter sykes
09. Ahluwalia
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VIII SEMESTER CHEMISTRY PRACTICALS
INORGANIC EXPERIMENTS
01. Analysis of Bronze
a) Analysis of tin by gravimetrically.
b) Analysis of copper volumetrically.
02. Analysis of white lead pigment
c) Analysis of lead as lead chromate - gravimetrically.
d) Analysis of lead volumetrically by EDTA method.
03. Analysis of lithophone pigment
e) Analysis of Barium sulphate by gravimetrically.
f) Analysis of zinc sulphide volumetrically by EDTA.
04. Analysis of Zinc oxide pigment
g) Analysis of zinc-oxinate - gravimetrically.
h) Analysis of zinc volumetrically by potassiumferrocyanide method.
05. Estimation of nickel in steel.
-analysis of nickel as Ni(DMG)2 gravimetrically.
06. Analysis of fertilizers
i) Nirtogen present as ammonium nitrogen by volumetric method (Kjaldahl’s
method ).
j) Phosphate phosphorous gravimetrically as ammonium phosphomolybdate
method.
07. Analysis of Al-Mg alloy.
k) Analysis of aluminium as aluminium oxide by gravimetrically.
l) Analysis of magnesium volumetrically by EDTA method.
08. Analysis of red lead pigment
m) Analysis of lead as lead chromate - gravimetrically.
n) Analysis of lead volumetrically by EDTA method.
09. Preparation and analysis of lead tetra acetate.
10. Colorimetric estimation of chromium.
ORGANIC EXPERIMENTS
Systematic qualitative analysis of binary mixture(solid+solid, solid+ liquid)
Chemical equations to be discussed for all tests.
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PHYSICAL EXPERIMENTS
01. PH titrations
a. HCl v/s NaOH
b. Acitic acid v/s NaOH
c. CuSO4 v/s NaOH
02. Conductometric titration
a. BaCl2 v/s Na2SO4
b. AgNO3 V/S KCl
03. Potentiometric titrations
a AgNO3 V/S KCl
b. AgNO3 V/S KBr
c. AgNO3 V/S KI
d. AgNO3 V/S KCl+KI
e. AgNO3 V/S KCl+KBr+KI
04. Partial molar volume of
a. Ethanol –Water system
b. Methanol –Water system using density method
05. Determination of molecular weight of polystyrene using Wolt’swar viscometer
method
06. Kinetics of oxidation of KI by K2S2O8
07. Catalytic variation
08. Oxidant variation
09. Substrate variation
10. Solvent variation alcohol or methanol
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