Download DISTANCE EDUCATION M.Sc. (Chemistry) DEGREE

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DISTANCE EDUCATION
M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2011.
ORGANIC CHEMISTRY – I
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
Each question carries 20 marks.
(5  20 = 100)
1.
(a)
Write a note on
(i)
Inductive effect
(ii)
Mesomeric effect
(iii) Field effect
(b)
2.
3.
(iv)
Steric inhibition of resonance
(v)
Steric enhancement of resonance
(i)
Classify the organic reactions
(ii)
Write the principle of microscopic reversibility.
(5+5 =10)
(5  2 = 10)
(a)
Discuss kinetic and non-kinetic methods of determining organic
reactions. (10)
(b)
Explain the concept of aromaticity and homoaromaticity.
(10)
(a)
Illustrate with suitable examples.
(i)
Nucleophile
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(ii)
Ambident nucleophile
(iii) Hard and soft acids
(iv)
(b)
(4  2 = 8)
Phase transfer catalyst
Discuss the following
(i)
Ortho/para ratio
(ii)
Benzyne mechanism
4.
Explain
5.
(a)
Discuss
(b)
Write a note on orientation of double bond in elimination reactions.
(5)
6.
7.
8.
briefly
SN1,
(2  6 = 12)
briefly
SN2,
E1,
SE1
E2
and
SE2
(4  5 = 20)
mechanisms.
and
E1CB
(3  5 = 15)
mechanisms.
Explain the following reactions.
(a)
Michael addition
(b)
Diels-Alder reaction
(c)
Dickmann Condensation
(d)
Reformatsky Condensation.
(4  5 = 20)
Draw the structure and give the synthesis of following:
(a)
Indole
(b)
Oxazole
(c)
Morphine
(d)
Atropine
(e)
 -pinene
(a)
(i)
Write a note on solid phase peptide synthesis.
(5)
(ii)
What is meant by ‘End group analysis’? Explain.
(5)
(i)
Write a note on configurations and conformations of disaccharides.
(5)
(ii)
Elucidate the structure of maltose.
(b)
(5 × 4 = 20)
2
(5)
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DISTANCE EDUCATION
M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2011.
INORGANIC CHEMISTRY — I
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
Each question carries 20 marks.
(5  20 = 100)
1. (a)
2.
3.
4.
State and explain Pearson's concept.
(5)
(b)
Discuss in detail valence bond theory developed by Pauling.
(8)
(c)
Explain Hard and Soft Acid and Base concept with suitable examples.
Write the applications of HSAB.
(7)
(a)
Illustrate with examples n-type and p-type semiconductors.
(6)
(b)
Distinguish between Schottky defect and Frenkel defect.
(8)
(c)
How does the structure of Zinc blende differ from that of Wurzite?
(6)
(a)
What are nuclear forces? Explain their origin.
(b)
What is isotopic dilution analysis? Explain the important features and
applications
of
this
analysis.
(10)
(c)
Discuss the theory of alpha decay and beta decay. (4)
(a)
Explain the periodicity in ionization energy and ionic radii on passing
from Lithium to Cesium.
(6)
(b)
How are lanthanides separated by ion exchange method?
(4)
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(6)
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(c)
What are actinides? Why are they so called? Discuss the properties of
actinide elements in respect of the following :
(10)
(i)
Electronic configuration
(ii)
Oxidation reaction
(iii) Ionic radius
(iv)
5.
6.
7.
8.
Magnetic properties.
(a)
Distinguish isopoly anions from heteropoly anions. Discuss the structure
of heteropoly anions.
(8)
(b)
Describe the structure and bonding in each of the following : (i) B4H10 (ii)
Phosphorus cage. (8)
(c)
Explain Anderson structure with examples.
(a)
Determine lattice energy of sodium chloride with help of Born-Haber
cycle.(6)
(b)
Explain the terms with suitable examples :
(i)
Metal excess defect
(ii)
Metal deficiency defect.
(4)
(8)
(c)
What is meant by nuclear fusion? How is the origin of steller energy
explained on the basis? (6)
(a)
Write a brief note on Zeolites.
(b)
Account for the close similarity in the properties of lanthanide elements
and their compounds. (10)
(c)
Explain the term symbiosis with examples.
(a)
Differentiate between a sigma bond and a pi-bond. Explain why a sigma
bond
is
stronger
than
pi
bond.
(6)
(b)
Write notes on semiconductors and transistors.
(8)
(c)
Discuss in detail the structure of Silicates.
(6)
(5)
(5)
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DISTANCE EDUCATION
M.SC. (Chemistry) DEGREE EXAMINATION, MAY 2011.
PHYSICAL CHEMISTRY — I
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(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
All questions carry equal marks.
(5  20 = 100)
1. (a)
State Gibb’s and Helmholtz free energies and its conditions of
equilibrium maxwell relations.
(8)
2.
3.
4.
(b)
Derive and explain Nernst Heat Theorem.
(8)
(c)
Define Fugacity and activity coefficient.
(4)
(a)
Define the terms of entropy of mixing and degradation energy.
(6)
(b)
Derive the chemical potential of Gibb’s-Duhem equation.
(7)
(c)
State second law of thermodynamics and its use in the determination of
entropy. (7)
(a)
Derive and discuss the importance of Butler-Volmer equation and
approximation of the equation.
(10)
(b)
Define the terms of transport number and ionic mobility.
(4)
(c)
Derive Debye-Huckel Onsagar equation.
(a)
Write
(b)
Explain Eigen functions and Eigen values and give their significance.
notes
on
(6)
Heisenberg’s
uncertainty
(4)
principle.
(6)
(c)
Derive equation for particle in schrodinger wave for three dimensional
box.
5.
(10)
(a)
Write notes on degeneracy.
(4)
(b)
Explain wave particle dualism and write in mathematical preparation for
quantum chemistry.
(8)
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(c)
Discuss the simple collision theory and its thermodynamic and statistical
treatment.
6.
(a)
(8)
Derive the rate constant from ARRT theory for a chemical reaction.
(10)
(b)
Write the qualitative approach for kinetic isotopic effect.
(5)
(c)
Write
notes
on
consecutive
and
reversible
reactions.
(5)
7.
(a)
Discuss and explain the Lindemann and Hinshelwood hypothesis for a
unimolecular reaction.
(10)
(b)
Explain the photophysical processes.
(4)
(c)
Draw and compare the fluorescence and phosphorescence processes.
(6)
8.
(a)
Write the energy transfer mechanisms.
(5)
(b)
Write notes on solar energy conversion and its applications.
(6)
(c)
Write notes on :
(i)
Chemiluminescence.
(3)
(ii)
Radiolysis of water
(3)
(iii) Flash photolysis.
(3)
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DISTANCE EDUCATION
M.Sc.(Chemistry) DEGREE EXAMINATION, MAY 2011.
INSTRUMENTAL METHODS OF ANALYSIS
(2008 onwards)
Time : Three hours
Maximum : 100 marks
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Answer any FIVE questions.
Each questions carries 20 marks.
(5  20 = 100)
1. (a)
(8)
(b)
Discuss briefly the solvent effects in electronic excitations.
Write a short note on
(i)
Bending vibrations
(ii)
Overtone and combination bands
(3  4 = 12)
(iii) Fermi resonance
2.
Discuss the basic principles, instrumentation and applications of IR
spectroscopy.
(20)
3.
(a)
Explain briefly the various factors affecting the chemical shift in proton
NMR spectroscopy.
(8)
(b)
How will you determine the first order and non-first order spectra in
'HNMR' spectra? (8)
(c)
Write any two important applications of
(4)
(a)
Distinguish between NMR and ESR spectra.
(b)
What is 'Nitrogen rule'? Briefly explain this rule with suitable examples.
(6)
(c)
Explain in details the importance of fragmentation in mass spectroscopy.
(6)
(d)
What is cotton effect? Explain the various types of cotton effect.
(4)
(a)
What is meant by octant rule? Discuss any four applications based on
octant- rule.
(10)
(b)
What are meta stable ions? How are they identified? Write their
significant characteristics.
(6)
(c)
Discuss the basic principle of chromatography.
(a)
Discuss briefly the various applications of HPLC. Give its principle.
Write
the
disadvantage
of
HPLC.
(10)
(b)
Explain how TLC is useful for identifying the extent of reaction that has
gone. How are TLC plates prepared? Explain how TLC analysis is carried
out.
(10)
4.
5.
6.
7
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C  NMR spectroscopy.
(4)
(4)
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7.
8.
Explain the following:
(a)
Differential thermal analysis
(b)
Thermometric titrations
(c)
Nephelometry
(a)
Discuss the basic principle and instrumentation of cyclic voltammetry.
(7)
(b)
Give the important applications of cyclic voltammetry to organic and
inorganic compounds. (5)
(c)
Explain the Q – test and F-test with suitable examples in error analysis.
(8)
(6 + 7+ 7)
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DISTANCE EDUCATION
M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2011.
ORGANIC CHEMISTRY — II
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
Each question carries 20 marks.
(5  20 = 100)
1. (a)
How would you decide
intramolecular or intermolecular? (4)
whether
a
rearrangement
process
is
(b)
Predict the product and explain the mechanism. (4)
(c)
Explain the schematic analysis of the total synthesis of trans-9-methyl-1decalone. (4)
(d)
Identify the product and explain the mechanism of the following
transformation. (4)
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2.
3.
4.
(e)
Bring out the significance of blocking groups with suitable examples.
(4)
(a)
What are enantiotopic and diastereotopic atoms? Explain with suitable
example. (5)
(b)
Discuss the optical activity of biphenyl and spirane compounds.
(5)
(c)
Explain any two methods of determination of geometrical isomers.
(5)
(d)
Discuss the cis-trans isomerism of 1, 2– and 1, 4-dimethyl cyclohexane
molecules. (5)
(a)
Discuss the conformations and stability of isomeric cyclohexane diols.
(8)
(b)
Write briefly on Eliel-Rao equation.
(c)
Write notes on :
(a)
(i)
Barton reaction
(ii)
Ullmann reaction.
(4)
(4 + 4)
Complete the following reactions :
(i)
(ii)
5.
6.
(2 + 2)
(b)
Discuss [2 + 2] and [4 + 2] cycloaddition reactions.(8)
(c)
Write notes on :
(i)
Paterno-Buchi reaction.
(ii)
Photo sensitization.
(2 + 2)
(d)
Irradiation of 1, 3-butadiene with and without benzophenone gives
different products. Explain.
(4)
(a)
What is convergent synthesis? Explain it with an example.
(4)
(b)
Give the structure of vitamin D. What happens when it is heated?
(4)
(c)
Give an account on bile acids. Indicate how cholesterol is converted into
cholanic acid.
(8)
(d)
Explain the chemical evidences for the position of angular methyl groups
in cholesterol.
(4)
(a)
Explain Umploung reaction with an example.
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7.
(b)
What is meant by retrosynthetic analysis? Explain the retrosynthetic
analysis of any two simple organic compounds.
(6)
(c)
Elucidate the structure of Oestrone.
(a)
Discuss the any two oxidation reactions of the following reagents :
(4  2 = 8)
(i)
Chromic acid
(ii)
DMSO-DCC
(10)
(iii) MnO2
(iv)
(b)
Lead tetraacetate.
Discuss the following :
(i)
Pschorr reaction
(ii)
Hunsdiecker reaction
(iii) Chemotropic reaction
(iv)
8.
Sigmatropic rearrangement.
(4  3 = 12)
(a)
Discuss the Woodward-Hoffmann rules with examples.
(4)
(b)
Write notes on :
(c)
(i)
Wolff rearrangement
(ii)
Stern rearrangement.
(4 + 4)
Explain the following with suitable examples.
(i)
Photo-oxidation
(ii)
Photo reduction.
(4 + 4)
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DISTANCE EDUCATION
M.Sc.(Chemistry) DEGREE EXAMINATION, MAY 2011.
INORGANIC CHEMISTRY – II
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
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Each question carries 20 marks.
(5  20 = 100)
1. (a)
Explain the various factors influencing the magnitude of crystal filed
splitting. (7)
(b)
Ni and Pt belongs to the same family but the complexes [NiCl4]2– and
[PtCl4]2– differ in geometry – Explain.
(7)
(c)
Discuss the geometrical isomerism exhibited by square planar complexes.
(6)
2.
(a)
Discuss the mechanism of acid hydrolysis of CO (III) complexes.
(6)
(b)
Describe the salient features of an outer - electron transfer reaction with
an example.
(c)
(6)
Describe the polarographic method for the determination of stability
constant of a complex species.
(8)
3.
(a)
With suitable example explain the effect of distortion and spin-orbit
coupling on the electronic spectra of metal complexes.
(b)
Give the Tanabe – Sugano diagram for [Ni(H2O)6]2+ and explain the
electronic spectrum.
(c)
(6)
(8)
Account for the fact that the magnetic moments of octahedral Ni(II)
complexes are less than those for tetrahedral Ni(II) complexes.
4.
5.
(6)
(a)
Discuss the mechanism of hydrogenation using Wilkinson's catalyst.
(8)
(b)
Discuss the structure of Zeise's salt.
(c)
Describe briefly about the preparation and reactions of metal alkyls and
aryl. (6)
(a)
Describe the structure and biological functions of cytochromes.
(5)
(b)
How is Vitamin B12 coenzyme biologically produced? Write the special
features of corrin ring in the place of porphyrin in Vitamin B12 system.
(10)
(c)
Describe invivo and invitro nitrogen fixation with examples.
(5)
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6.
7.
8.
(a)
Draw Mo energy level diagrams of [CO(NH3)6]3+ and [COF6]3– and discuss
the significance of  0 values of the complexes.
(12)
(b)
What is Jahn-Teller effect? Illustrate with an example.
(8)
(a)
Give a brief account of essential and trace elements in biological system.
(6)
(b)
Discuss the structure of hemoglobin and explain how is it used in the
vital process of human system.
(8)
(c)
Explain the structure of Ferredoxins and Rubredoxins.
(6)
Explain briefly the following:
(a)
Template effect and Macrocyclic ligands.
(8)
(b)
Complementary and Non-complementary reactions.
(6)
(c)
Anation reactions.
(6)
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DISTANCE EDUCATION
M.Sc.(Chemistry) DEGREE EXAMINATION, MAY 2011.
PHYSICAL CHEMISTRY – II
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
(5  20 = 100)
Each questions carries 20 marks.
1. (a)
Derive an expression for the molecular vibrational partition function.
(12)
2.
(b)
Discuss the salient features of the Einstein theory of the heat capacity of
mono – atomic crystals. (8)
(a)
Set up the schrodinger wave equation for a simple harmonic oscillator
model and obtain its solution.
(14)
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3.
(b)
Write a note on Slater determinant.
(6)
(a)
Construct the character table for C3v point group using the postulates of
great orthogonality theorem.
(10)
(b)
Find out the symmetry of normal modes of vibration of water molecule.
predict the IR and Raman active fundamental vibrations of water
molecule.
Character table of C2v point group.
4.
5.
6.
7.
8.
(10)
C2v
E
C2
 V ( XZ )
 V (YZ )
A1
1
1
1
1
Z
X 2 , Y 2 , Z2
A2
1
1
–1
–1
Rz
XY
B1
1
–1
1
–1
X, Ry
XZ
B2
1
–1
1
1
Y, Rz
YZ
(a)
Derive Bronsted-Bjerrum equation and discuss the applications of this
equation. (10)
(b)
Discuss the application of Hammett and Taft equations in the study of
effect of substituents on the rates of chemical reactions.
(10)
(a)
Bring out the differences between physisorption and chemisorption.
(8)
(b)
Derive Langmuir adsorption isotherm and explain its merits and
demerits.
(12)
(a)
Write notes on Onsager reciprocal relations.
(6)
(b)
Write a note on pauli exclusion principle.
(6)
(c)
Give the matrix representations of E, Cn, i and  XY .
(8)
(a)
Derive the expression for Bose – Einstein statistics.
(6)
(b)
Discuss the application of variation principle in solving hydrogen atom
problem. (6)
(c)
Write note on Hammett acidity function.
(a)
Predict the Point groups of the following molecules.
(b)
(i)
CHCl3
(ii)
BF3
(8)
(4)
Give the general protolytic and prototropic schemes of acid-base catalytic
reactions. (4)
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(c)
Discuss the applications of the adsorption phenomenon.
(12)
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DISTANCE EDUCATION
M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2011.
APPLIED CHEMISTRY
(2008 onwards)
Time : Three hours
Maximum : 100 marks
Answer any FIVE questions.
(5  20 = 100)
1. (a)
(8)
2.
3.
4.
5.
List out the hazardous materials with their ill effect.
(b)
Discuss the biological effects of radiation and the various methods of
preventing radioactive pollution.
(12)
(a)
Write notes on corrosion inhibitors.
(b)
Discuss the principle of anodizing and types of anodizing both.
(12)
(a)
Give the mechanism of free radical, anionic and cationic polymerization.
(12)
(b)
Write notes on
(i)
Conducting polymers
(ii)
Bio-degradable polymers.
(8)
(8)
(a)
Write briefly on the synthesis of nanomaterials by physical methods.
(10)
(b)
Discuss the important aspects of the following microscopic
characterization techniques of nanomaterials : SEM and TEM.
(10)
(a)
Give an account of various internet service providers.
(12)
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6.
7.
8.
(b)
With special reference to chemistry journals point out the utility value of
chemistry data bases. (8)
(a)
Write notes on depletion of ozone layer and green house effect.
(10)
(b)
Discuss the principle, mechanism and applications of composite coating.
(10)
(a)
Discuss the following methods of polymerization. (8)
(i)
Emulsion polymerization
(ii)
Suspension polymerization.
(b)
Give a brief account of physical characterisation techniques like FT-IR
and Laser Raman spectroscopy.
(12)
(a)
Explain the importance of special terms used in internet with details.
(12)
(b)
Write a note on the electrochemical methods of protection against
corrosion. (8)
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