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WS 20

DE–659 Sub. Code


11

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017

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) State the rules for resonance. (4)


(b) Discuss the effect of hydrogen bonding on shape and
properties of molecules. (4)
(c) Write note on organic reactions proceeding through
nitrene mechanism. (4)
(d) Explain field effect with suitable example. (4)
(e) Explain any two non-kinetic methods for the
determination of reaction mechanism. (4)

2. (a) What are hard and soft acids and bases? Give an
example for each. (4)
(b) Explain the effect of nucleophile and leaving group
in the SN1 and SN2 reaction. (4)
(c) What are annulens? How would you account for the
aromatic character of annulens? (4)
(d) What is meant by thermodynamically and
kinetically controlled reaction? Explain with
suitable example. (8)
WS 20

3. (a) Write note on partial rate factor. (4)


(b) Give any two possible ester hydrolysis mechanism
with an example. (8)
(c) State and illustrate Saytzell elimination. (4)
(d) Compare aldol condensation with cannizzaro
reaction. (4)

4. (a) How is exhaustive methylation reaction helps in


determinating the structure of alkalodis? (4)
(b) How will you effect the following conversion?
 - pinene to norpinic acid. (4)
(c) Discuss the stereochemistry of hydroxylation
reaction? carry one). (4)
(d) Discuss the orientation of the double bond in
elimination under various condition. (8)

5. (a) Write down the various steps involved in the


synthesis of Indole. (4)
(b) How would you predict the ring size in the
camphor? (4)
(c) Discuss the Grignard addition on ,  -
unsaturated carbonyl compound. (4)
(d) Write the detail mechanism of Wittig reaction. (4)
(e) Discuss the role of lithium dimethylcuprate reagent
in organic reaction (4)

6. (a) Discuss briefly the biosynthesis of Terpene. (8)


(b) Write down the various steps involved in the
synthesis of camphor. (8)
(c) How would you synthesise flavone? (4)

2 DE–659
WS 20

7. (a) Give the mechanism for SN1 and SN2 reaction. (8)
(b) Hydroboration is a regionspecific reaction. Explain
with suitable example. (4)
(c) Write note on pyrolytic cis-elimination. (4)
(d) Explain Zeisel method with suitable example. (2)
(e) Write the structure of the product formed when
morphenol is fused with potassium hydroxide? (2)

8. (a) Write down the any method of end group analysis of


amino group in protein. (6)
(b) Write note on solid phase peptide synthesis. (6)
(c) Describe any two method for determining ring size
of sugar. (8)

———————————

3 DE–659
Ws 11

DE–660 Sub. Code


12

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

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) What is symbiosis? Explain briefly with suitable


examples. (6)
(b) What is lattice energy? How is it calculated by
Born-Lande equation? Explain. (8)
(c) What are the postulates of VSEPR theory? Mention
its defects. (6)

2. (a) Explain the crystal structure of Z nS and fluorite. (8)

(b) What are Schottky and Frenkel defects? Explain


them with suitable examples. (6)
(c) Write a note on F-centres. (6)

3. (a) Explain any two methods of detect and measure


radioactivity. (7)
(b) Discuss in detail the composition and properties of
nuclei. (5)
(c) What are nuclear reactions? Explain any four
nuclear reactions with suitable examples. (8)
Ws 11

4. (a) Discuss briefly the spectral and magnetic properties


of actinides. Compare these properties with
lanthanides. (8)
(b) Discuss the position of lanthanides and actinides in
the periodic table. (8)
(c) How are lanthanides separated by fractional
crystallization method? (4)

5. (a) Discuss in detail the isopoly acids formed by


vanadium and molybdenum. (8)
(b) What are silicates? Explain the structure of
pyroxenes and amphiboles in detail. (8)
(c) Explain the structure of feldspar. (4)

6. (a) Derive Born-Meyer equation for the lattice energy of


an ionic compound. (7)
(b) Write a note on symmetry of molecular orbitals. (5)
(c) State and explain the Pearson’s concept of hard –
soft acids and bases with suitable examples. (8)

7. (a) What is meant by radioactive decay? Explain briefly


the theories of decay processes. (8)
(b) Write a note on liquid drop model and neutron
activation analysis. (8)
(c) State and explain the laws of radioactivity. (4)

8. (a) May trivalent lanthanide ions are coloured. Explain.


(5)
(b) State and explain Slater’s rules. (5)
(c) Draw and explain the MO diagrams of F2 and HCl
molecules. (10)

————————

2 DE–660
wk7

DE–661 Sub. Code


13

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

PHYSICAL CHEMISTRY — I

(2008 onwards)

Time : Three hours Maximum : 100 marks

Answer any FIVE questions.

Each questions carries 20 marks.


(5 × 20 = 100)

1. (a) State and explain nernst heat theorem. (7)


(b) Derive Gibb’s Duhem equation of chemical
potential. (8)
(c) Define activity and activity co-efficient. (5)

2. (a) What is meant by the term fugacity? Discuss the


determination of fugacity of a real gas. (8)
(b) Give a detailed study of different types of electrodes
with example. (8)
(c) Write note on : transport number. (4)

3. (a) Derive butler volmer equation. (7)


(b) Describe the applications of conductivity
measurements. (8)
(c) Write and explain Debye-Huckel Onsager equation.
(5)
wk7

4. Explain teh following in detail :


(a) Entropy (4)
(b) Reaction isotherm (4)
(c) Eigen value and eigen function (8)
(d) Hydrated electron. (4)

5. (a) Discuss the postulates of quantum mechanics. (10)


(b) Derive and solve schrodinger wave equation for
particle in an one dimensional box. (10)

6. (a) State and explain Heisenberg’s uncertainty


principle. (6)
(b) Discuss the role of mathematical functions in
quantum chemistry. (8)
(c) What are potential energy surfaces? Explain. (6)

7. (a) What are fast reactions? Give and explain any one
method to study fast reaction. (8)
(b) Discuss the applications of ARRT to bimolecular
reactions. (7)
(c) Write note on : Kinetic isotopic effect. (5)

8. (a) Discuss various photo physical processes takes place


in electronically excited molecule. (8)
(b) Give a detailed study of solar energy conversion. (6)
(c) State any two laws of photochemistry. (6)

–––––––––––––––

2 DE–661
WK 6

DE-662 Sub. Code


14

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

INSTRUMENTAL METHODS OF ANALYSIS

(2008 onwards)

Time : Three hours Maximum : 100 marks

Answer any FIVE questions.

Each question carries 20 marks.


(5  20 = 100)

1. (a) What do you mean by fundamental vibrations? How


will you detect the type of hydrogen bonding
involved in particular compound by IR spectra? (8)
(b) Discuss in detail the various factors which influence
the vibrational frequency of a particular group. Give
examples. (6)
(c) How will you determine the formation of charge
transfer complexes using UV spectra? (6)
2. (a) Calculate the absorption maximum for each of the
following compounds using the Woodward Fieser
rule. (8)

(i) (ii)

(iii) (iv)
WK 6

(b) What are the different type of transitions observed


in  ,  -unsaturated carbonyl compounds? How are
absorption maximum and intensity shifted when
carbonyl groups is not conjugated. (7)
(c) Write short notes on Fermi resonance. (5)

3. (a) What is meant by the term chemical shift? What are


the various factors which influence the chemical
shift value? (8)
(b) Explain the following terms in NMR spectroscopy.
(i) Nuclear overhauser effect
(ii) Spin-spin coupling. (6)
(c) Write down the importance of ‘g’ values in ESR
spectroscopy. (6)

4. (a) What do you understand by the terms, double


resonance and spin tickling? How are they helpful
in simplifying the spectra? (8)
(b) Compare ESR and NMR techniques. (8)
(c) Write down the principle of ESR spectra. (4)

5. (a) What do you understand by meta stable ions? How


are these recognised in the mass spectrum? What is
its importance? (8)
(b) Write down the principle involved in paper and thin
layer chromatography. (6)
(c) Explain the different types of ORD curves. (6)

6. (a) State and explain  -halo ketone rule with an


example and give its applications. (8)
(b) Write down
(i) MeLafferty rearrangement and
(ii) Nitrogen rule. (8)
(c) Write short notes on, circular birefringence. (4)

2 DE-662
WK 6

7. (a) What is turbidimetry? How is it related to


calorimetry? (6)
(b) What is meant by thermogram? Explain with an
example. (6)
(c) Discuss the principle and applications of flame
photometry. (8)

8. (a) Write down the principle and applications of cyclic


voltammetry. (8)
(b) Give the principle of coulometric analysis. Discuss
some important coulometers used in this analysis.
(6)
(c) What are ion selective electrodes? Write their
advantages. (6)

————————

3 DE-662
wk12

DE–663 Sub. Code


21

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

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) Write the mechanisms of Wagner-Meerwein and


Baeyer-Villiger rearrangements. (12)
(b) Discuss the mechanism of Wolff-Kishner reduction.
(4)
(c) Illustrate Robinson annulation reaction with
example. (4)

2. (a) Give an account of Cram’s and Prelog’s rules. (6)


(b) Elucidate the optical activity of allenes and
biphenyls. (6)
(c) How would you determine the configuration of
geometrical isomers by physical methods? (8)

3. (a) Give an account of conformation and reactivity of


cyclohexanones. (10)
(b) Describe the mechanism of E2 elimination reaction
with suitable example. (6)
(c) Explain briefly the Barton and Gomberg
rearrangements. (4)
wk12

4. (a) Explain briefly Norrish I and II type reactions with


suitable examples. (10)
(b) Explain Frontier molecular orbital method for 4+2
cycloaddition of 1,3-butadiene and ethylene. (10)

5. (a) Give the synthesis of progesterone and


androsterone. (10)
(b) Describe the physiological significance of vitamins.
(5)
(c) Elucidate the structure of vitamin B2. (5)

6. (a) What are blocking groups? Explain with example. (5)


(b) Illustrate the Clemmensen reduction with suitable
example. (7)
(c) Discuss in detail the optical isomerism of
compounds containing one asymmetric carbon. (8)

7. (a) Explain the following reactions with examples :


(3  3 = 9)
(i) Ullmann
(ii) Pschorr
(iii) Hunsdiecker.
(b) Discuss the stability and reactions of free radicals.
(8)
(c) Give an account of polymerization reaction. (3)

8. (a) Give the biosynthesis of cholesterol. (8)


(b) Illustrate the structural elucidation of oestrone. (7)
(c) Write a short note on Oppenauer oxidation. (5)

———————

2 DE–663
wk10

DE–664 Sub. Code


22

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

INORGANIC CHEMISTRY – II

(2008 onwards)

Time : Three hours Maximum : 100 marks

Answer any FIVE questions.

Each question carries 20 marks.


(5  20 = 100)

1. (a) Give the IUPAC names of the following compounds:

(i) K 4 FeCN 6 

(ii) CrNH3 6  CoCN 6 

(iii) CoNH3 4 Cl 2 

(iv) Pt Cl 4 2 . (4  1 = 4)

(b) Discuss the isomerism in square-planar complexes.


(6)

(c) State and explain the Jahn-Teller theorem. What


are its consequences? (10)

2. (a) How do the stabilities of chelates differ with

(i) size of the Chelate rings and

(ii) number of Chelate rings? 2 12  2 12  5


wk10

(b) Describe the behaviour of a complex which is both


thermodynamically stable and kinetically labile. (5)
(c) What are step wise and overall formation
constants? How are they related? Explain how the
stability constant of complex is determined by
polarographic and spectro photometric methods. (10)

3. (a) What are Tanabe-Sugano diagrams? Explain its


importance with one example. (8)
(b) List out the significance of Racah parameter.
Explain how 10 Dq can be determined for Ni (II)
octahedral complexes. (8)

Predict the d-d absorption spectrum of NiCl 4  . (4)


2
(c)

4. (a) Write a note on acetylene complexes. (6)


(b) Explain the oxidative addition and reductive
elimination with suitable examples. (7)
(c) What are metallocenes? Explain the structure and
bonding in ferrocence. (7)

5. (a) What are the factors affecting 10 Dq values? (6)


(b) What are complementary and non-complementary
reactions? Explain with suitable examples. (5)
(c) What are inner sphere and outer sphere complexes?
Explain the mechanisms for the formation of these
complexes with suitable examples. (9)

6. (a) Explain the functions of hemoglobin and myoglobin


with structure. Discuss briefly the Perutz
mechanism to explain the function of hemoglobin
and myoglobin. (7)
(b) Discuss the structure and function of
carboxypeptidase A. (7)
(c) Write a note on sodium ion pump. (6)

2 DE–664
wk10

7. (a) What is meant by chelating agent? Explain the


importance of any three chelating agents in
medicine. (7)
(b) Sketch the structure and discuss the biological
activity of vitamin B12. (8)
(c) Discuss in detail on Vaska's compound. (5)

8. (a) Sketch the possible geometrical isomers for


CrNH3 2 Cl 4  . Which of these isomers will exhibit
optical isomerism? (6)
(b) List out the postulates and limitations of CFT. (8)
(c) Discuss the site preferences in Spinnels. (6)

——————————

3 DE–664
wk4

DE–665 Sub. Code


23

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

PHYSICAL CHEMISTRY — II

(2008 onwards)

Time : Three hours Maximum : 100 marks

Answer any FIVE questions.

Each question carries 20 marks.

(5  20 = 100)

1. (a) Estimate the rotational partition function of HCl at


25C and 250C. (10)
(b) Use concepts of statistical thermodynamics to
describe the molecular features that lead to the
equations of state of perfect and real gas. (10)

2. (a) Illustrate the wave mechanical treatment of a


particle in a one-dimensional box. (13)
(b) Write note on Slater determinant. (7)

3. (a) Describe the great Orthogonality theorem. (8)


(b) What are the symmetry operations in the point
group C2v? Identify a molecule that belongs to the
group. By examining the effect of sequential
application of the various symmetry operations in
the group, construct the group multiplication table.
(12)
wk4

4. (a) Derive an equation for the variation of rate constant


with ionic strength. (12)
(b) Discuss the Hammet and Taft equation for various
substituents. (8)

5. (a) Show that the BET equation reduces to the


Langmuir isotherm when p0  p . (6)
(b) Prove that the bimolecular surface reaction order
+1 for one molecule and –l for another molecule. (7)
(c) Prove that the bimolecular surface reactions order
increases from 1 to 2. (7)

6. (a) Consider an electron moving in one dimensional box


of 3 Aº width. Calculate the transition in energy
when electron jumps from second orbit to first orbit.
Also calculate the wavelength of the emitted
radiation. (10)
(b) Discuss the features, advantages and limitations of
the Michaelis-Menten mechanism of enzyme action.
(10)

7. (a) State and derive the mathematical statement of


Boltzmann distribution law. (12)
(b) Write note on Temkin isotherm. (4)
(c) How does HMO method apply to butadiene
molecule? (4)

8. Write notes on :
(a) Assembly and ensemble
(b) Negative absolute temperature
(c) Micro and macro state
(d) Fermi statistics. (4  5 = 20)

————————

2 DE–665
SER

DE-666 Sub. Code


24

DISTANCE EDUCATION

M.Sc. (Chemistry) DEGREE EXAMINATION, MAY 2017.

APPLIED CHEMISTRY

(2008 onwards)

Time : Three hours Maximum : 100 marks

Answer any FIVE questions.

Each question carries 20 marks.


(5  20 = 100)

1. (a) Explain the term green house effect? (5)


(b) Describe in detail the methods of waste water
treatment. (10)
(c) How are the environment polluted by pesticides? (5)

2. (a) What is meant by corrosion of metals? Describe the


methods to control the corrosion? (10)
(b) Discuss the principles, advantages and limitations
of electroless plating. (10)

3. (a) Discuss the emulsion and Pearls polymerization


techniques. (10)
(b) Write note on fire retardant. (5)
(c) What is initiator? Explain the different types of
initiator. (5)

4. (a) Explain the synthesis of nanomaterials by chemical


vapour deposition technique. (7)
(b) Illustrate the characterization of nanoparticles by
XRD, XPS and SEM. (13)
SER

5. (a) What is journal? What are the various sources?


How are the abstracts collected using internet? (10)
(b) Using computer how does calculate the standard
deviation and correlation coefficient? (10)

6. (a) What is TG/DTA analysis? How does it useful to


characterize the nanoparticles? (10)
(b) Write note on biodegradable polymers. (5)
(c) Sketch and explain the pourbaix diagram of water
system. (5)

7. (a) What is electroforming? Discuss the principles and


application of electroforming. (10)
(b) What is anodizing? Discuss elaborately principles
and various types of anodizing with suitable
examples. (10)

8. (a) Discuss the various sources and effects of water


pollution. (10)
(b) Compare the nanoparticles size determination
results using SEM, AFM and XRD and
mention which method is more reliable. (10)

_________________

2 DE-666

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