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Loyola College M.Sc. Chemistry Nov 2008 Organic Reaction Mechanism & Stereochemistry Question Paper PDF Download

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LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

DB 21

M.Sc. DEGREE EXAMINATION – CHEMISTRY

FIRST SEMESTER – November 2008

           CH 1806 – ORGANIC REACTION MECHANISM & STEREOCHEMISTRY

 

 

 

Date : 04-11-08                 Dept. No.                                        Max. : 100 Marks

Time : 1:00 – 4:00

Part-A

                                                     Answer ALL questions.                                      (10 ´ 2 = 20)

  1. R-CN is prepared by treating RCOO– with BrCN. Where the carbon in RCN comes from? How?
  2. How would you effect the following conversion? Explain with mechanism.
  3. What is memory effect in rearrangement? Explain with an example.
  4. What happens when phenyl azide is heated with aniline? Explain the formation of the product.
  5. Explain the mechanism of ozonolysis of alkenes with an example.
  6. What would be the preferred conformer of trans-1,2-dibromocyclohexane? And how its conformation changes with solvent polarity?
  7. Explain why the optically active 2-benzoylpropionic acid undergoes racemization when treated with sodium ethoxide in ethanol?
  8. Define enantiomeric excess. What is its percentage value for active and racemic products?
  9. Solvolysis rate of cis-4-t-butyl cyclohexyl tosylate is greater than that of trans-isomer. Explain.
  10. What is atrolactic acid rule? Give one example.

 

Part-B

                                                     Answer any eight questions.                              (8 ´ 5 = 40)

  1. Explain the mechanism of Arndt-Eistert synthesis. Mention any one evidence for the mechanism.
  2. How do isotopic labeling and stereochemistry help in predicting suitable reaction mechanisms? Give examples.
  3. Explain kinetic and thermodynamic controls of a chemical reaction with a suitable examples.
  4. ‘Diazotisation of aniline follows II order kinetics in nitrous acid’. Explain the mechanism.
  5. How was the mechanism of von-Ritcher rearrangement confirmed? Explain the steps.
  6. How would you effect ring cyclisation reaction in Fischer-Indole synthesis? Explain with mechanism.
  7. What are the conditions to be fulfilled for a resolution process through diastereomers formation?
  8. Why the deamination of (Ph)(Ph’)(OH)C-CH(NH2)CH3 does not follow Curtin-Hammet principle? Explain.
  9. Discuss the steric course of the acetolysis reaction of 2-phenyl-3-pentyl tosylate &
    3-phenyl-2-pentyl tosylate.
  10. Predict the stereochemical change of acetolysis of 3-methoxy-2-bromobutane in the presence of silver acetate in acetic acid.
  11. Discuss the conformation analysis of 1,2 & 1,3-disubstituted cyclohexane.
  12. Predict the Cotton effect for the following compounds
  13. a)                                      b)                                      c)

 

 

Part-C

                                                     Answer any four  questions.                              (4 ´ 10 = 40)

  1. a) How does the kinetic study in chain and parallel reactions help to design the reaction mechanism? Explain with suitable examples.
  2. b) Explain the mechanism of Favorskii rearrangement. How is it useful in ring contraction reactions?
  3. a) Explain the Wagner Meerwein rearrangement reactions. How does neighbouring group help in this rearrangement? How do elimination and substitution reactions compete in the product formation?
  4. b) Explain the mechanism of the following rearrangement reactions. (2 ´ 2½)
  5. a) Beckman rearrangement        b) Baeyer Villiger rearrangement
  6. a) How do amines undergo dehydrogenation? Explain the mechanism.
  7. b) Explain Gomberg-Bachmann Pinacol synthesis with a suitable example.
  8. c) Explain the mechanism of cannizaro reaction.
  9. a) Discuss the optical isomerism of allenes and spiranes.
  10. b) Explain the reaction of erythro-3-bromo-2-butanol with HBr
  11. Explain the following with example
  12. a) Cram’s cyclic model
  13. b) Atropisomerism
  14. c) Chemical method of racemisation by anion intermediate formation
  15. Discuss in detail the stereo selective synthesis of yohimbine.

 

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Loyola College M.Sc. Chemistry April 2009 Thermodynamics & Statistical Mechanics Question Paper PDF Download

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WD 33

     LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

SECOND SEMESTER – April 2009

          CH 2816 / 2810 / 2800 – THERMODYNAMICS AND STATISTICAL MECHANICS

 

 

 

Date & Time: 24/04/2009 / 1:00 – 4:00  Dept. No.                                                   Max. : 100 Marks

 

 

PART A

Answer ALL the questions.                                                          (10 x 2 = 20 Marks)

  1. How does chemical potential vary with pressure?
  2. State any one of the formulations of Konowaloff’s rule.
  3. For the reaction, NH4HS(s) = NH3(g) + H2S(g), the equilibrium pressure at 298 K was found to be 0.67 atm.  Calculate KP of the reaction at 298 K.
  4. The vapour pressures of pure A and B at 250C are 250 mm of Hg and 400 mm of Hg respectively. A solution in which the mole fraction of A is 0.7 has a vapour pressure of 100 mm of Hg at 250 Calculate the activity coefficient (gx) of A in the given solution.
  5. Give the basic postulates of irreversible thermodynamics.
  6. What is Stirling’s approximation? Evaluate ln N! when N = 1040
  7. Calculate the number of ways of distributing 5 particles among 6 energy levels if the particles are a ) electrons b) Bosons
  8. What is the approximate value of ∆So for the reaction,  35Cl35Cl(g) + 37Cl37Cl(g) à  2 35Cl37Cl assuming that any difference in the molar masses, moments of inertia and vibrational energy levels are negligible for the isotopes?
  9. A system consisting of two energy states separated by 2×10-23 J has a ratio of particles in each state of 51/49, what is the temperature of the system?
  10. “Einstein’s introduction of quantisation accounted for the heat capacity of solids at room temperatures.” Explain.

 

PART – B

Answer ANY EIGHT questions                                            (8 x 5 = 40 Marks)

  1. Draw and explain the phase diagram of a three component system consisting of two solids (B and C) and water with the formation of a salt hydrate (B.nH2O).
  2. A 1:2 salt has a solubility of 1.545 x 10-5 moles lit-1 at 250 Calculate its mean ionic activity coefficient (a) in the absence of any electrolyte and  b) in the presence of 0.01 M BaCl2.
  3. The dissociation of N2O4(g) takes place according to the equation, N2O4(g) Û 2NO2(g). 548 g of N2O4 when heated was found to occupy a volume of 600 ml at 323 K and at a pressure of 850 mm of Hg.  Calculate the value of KP at the above conditions.
  4. Explain the entropy production when current is flowing through a wire.
  5. Show that the phenomenological coefficients must satisfy the following conditions:

L11>0, L22>0 and (L12 + L21)2 < 4 L11 L22

 

  1. Calculate the fugacity of H2 at 1000C and at 300 atm for a van der Waals gas. (a=0.2244 dm6 atm mol-2,

b = 0.0266 dm3 mol-1 and V = 0.119 dm3 mol-1 )

  1. Derive an expression for molecular translational partition function.
  2. Calculate the value of molecular vibrational partition function for N3(g) at 298 K. w1 = 1800 cm-1, w2 = 500 cm-1, g2 = 2 and w3 = 1200 cm-1.
  3. Calculate the rotational contribution to entropy for O2(g) at 250 C( I = 1.937 x 10-46 kg m2)
  4. Compare Debye’s theory of heat capacity of solids with Einstein’s theory.
  5. Calculate the equilibrium constant for the reaction C6H5CH2CH3 ó C6H5CH=CH2 + H2 at 500 K from the following data:  G0-H0/T for         H2 is -27.947 cal K-1 mole-1, for styrene    – 74.44 cal K-1 mole-1 and for ethyl bnzene – 79.64 cal K-1 mole-1.  (∆H0f)0 for Styrene and ethyl benzene are 40.34 and 13.917 k cal/ mol respectively.
  6. Write Sackur-Tetrode equation and deduce the factors affecting Stransl.

PART – C

Answer ANY FOUR questions                                              (4 x 10 = 40 Marks)

  1. a) Derive Gibbs-Duhem equations.                                                                     (6)
  2. b) When a solute is dissolved in 1 Kg of water, the volume V(ml) at 250C and 1 atm is represented as, V = 1000.3 + 20.7 m2 + 2.5 m22. Calculate the partial molal volume of the solute and that of the solvent in 1 molal solution.                                              (5)
  3. a) A gas obeys the equation of state P(V-b)=RT. For this gas b = 0.0391 dm3 mol-1. Calculate the fugacity coefficient at 1000 K and 100 atm pressure.                                      (3)
  4. b) How is Onsager’s reciprocal relationship verified experimentally by thermoelectric method?                                                                                                                      (7)
  5. For the reaction H2S(g)+3/2 O2(g) ó H2O(g) + SO2(g),     DH0298 K = -518.62 kJ mol-1,            DG0298 K = -495.95 kJ mol-1.  Compute the value of KP at 773 K from the CP data in J K-1 mol-1  CP (H2S) = 26.722 + 23.87 x 10-3 T, CP (O2)= 25.51 + 13.62 x 10-3 T, CP (H2O) = 30.21 + 9.93 x 10-3             T and CP (SO2) = 25.72 + 57.92 x 10-3 T
  6. a) Explain the theory of reaction rates using statistical mechanics. (5)
  7. b) Derive an expression for Evib for a harmonic oscillator and show that it reduces to RT at moderate temperatures                                                                                                            (5)
  8. Derive Fermi-Dirac distribution law and show that the Maxwell-Boltzmann distribution law is the classical limit of Fermi-Dirac distribution law             (6+4)
  9. a) Deduce the equation of state for 1 mole of an ideal gas using the definition of partition function and its relation to pressure of the gas                         (6)
  10. b) Explain the properties of liquid helium using the appropriate statistical distribution.(4)

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Loyola College M.Sc. Chemistry April 2009 Quantum Chemistry & Group Theory Question Paper PDF Download

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      LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 27

FIRST SEMESTER – April 2009

CH 1808 – QUANTUM CHEMISTRY & GROUP THEORY

 

 

 

Date & Time: 28/04/2009 / 1:00 – 4:00   Dept. No.                                                    Max. : 100 Marks

 

 

PART-A

 

ANSWER ALL QUESTIONS          (10 ´ 2 = 20)

 

  1. Show that eikx is an eigenfunction of the operator px = -iħδ/δx. What is the eigenvalue?
  2. Give the Laplacian operator in spherical polar coordinates. What are their limits of integration?
  3. What is a node? Draw the ψ2 plot for the first two lowest energy of the particle in a 1-D box and indicate the nodes.
  4. What are the atomic units for length and energy?
  5. What are degenerate states? Find the degeneracy of a state having

E = 26h2/8ma2 in a 3D cubic box of length a.

  1. Explain why an electron in an atom shows a discrete spectrum while a free electron shows a continuous spectrum.
  2. What is a ‘fermion’? Give an example.
  3. Write the Hamiltonian operator for the H2+ molecular ion defining each term involved in it.
  4. Identify the point groups for the following molecules:

(a) C6H6    (b) DCH3         (c) Br2              (d) [Co(NH3)6]3+

  1. Give an example for the point groups Cs. What are its symmetry elements?

PART-B

ANSWER ANY EIGHT QUESTIONS        (8 ´ 5 = 40)

 

  1. Derive the time-independent Schroedinger equation from the time-dependent equation.
  2. What is a hermitian operator? Show that the linear momentum operator is Hermitian.
  3. When do we say two symmetry operations are in the same class? Illustrate with

a suitable example.

  1. The spacing between adjacent rotational lines in the spectrum of HI molecule is 3.924 x 1011s-1.

Calculate the moment of inertia of HI molecule and the  internuclear spacing if the atomic

masses are H = 1 and I = 127.

  1. Explain quantum mechanical tunneling with a suitable example.
  2. (a) Show that [d/dx, x] = 1

(b) What are the values of [x, px] and [L2, Lx]? What is their physical significance?

(2+2+1)

  1. State the Variation Theorem and prove it with a suitable example. (2+3)
  2. Prove that y0 = (b/p)1/4exp(-bx2/2) is a normalized wave function. [You may make use of the standard integral 0ò¥ exp(-bx2) dx = (1/2)(p/b)1/2.]
  3. Define or explain the three parts that make an atomic term symbol and

formulate the term symbols for the ground state configuration of F atom.

  1. In solving the H2+ problem using the LCAO method, the lowest energy obtained is given by

E+ = (HAA + HAB) / (1+SAB) where A and B refer to the two  hydrogen nuclei. Explain each of

the integrals in the above equation and their significance.

 

  1. The wave function of 1s orbital of Li2+ is Ψ1s = (1/√π) (Z/a0)3/2 exp(-Zr/a0),

where a0  is the most probable distance of the electron from the nucleus. Show

that the average distance is a0/2. [Help:  0ò¥ xne-qx =  n!/qn+1]

 

 

 

 

 

 

  1. Applying group theory, find out the nature of the three C-H bonds in CH3Cl

which belongs to C3V point group.

 

C3V   E          2C3      3σv

 

A1    1          1         1              z                   x2 +y2, z2

A2    1          1         -1             Rz

E      2          -1         0         (x,y) (Rx,Ry)    (x2-y2,xy) (xz,yz)

 

PART-C

ANSWER ANY FOUR  QUESTIONS                    (4 ´ 10 = 40)

 

  1. a) Set up the Schroedinger equation for a particle in 1-D box and solve it for its energy and

wave function.

  1. b) An aliphatic conjugated diene (linear) has an end to end distance of 8.67 Ǻ and it absorbs at

3540Ǻ.

  1. Determine the number of double bonds and hence predict the structure of the molecule.
  2. If the bond length of C-C is 1.48 Ǻ and C=C is 1.34 Ǻ, calculate the penetration effect.                                     (7+3)

 

  1. Discuss the Pauli Exclusion Principle in quantum mechanics applied to He atom in its ground state.                                    (10)
  2. Discuss the Molecular Orbital treatment of H2 molecule and explain the contribution made by Heitler-London and its significance.                                          (10)
  3. a) What are the three important approximations that distinguish the HMO method from other

LCAO methods.

  1. b) Write down the secular determinant obtained on applying Huckel’s method to allyl cation.

Obtain expressions for the energy levels and the wave functions.              (3+7)

  1. a) Explain Bohr Correspondence Principle with respect to particle in 1-D box model
  2. b) Explain the Born-Oppenheimer approximation with an example. (6+4)

 

  1. Find the number, symmetry species of the infrared and Raman active vibrations of CCl4, which

belongs to Td point group. State how many of them  are coincident.

(You may, if you wish, use the table of f(R) given below for solving this).

Operation:       E     σ       i       C2      C3     C4     C5         C6     S3       S4      S5       S6            S8

              f(R):       3       1    -3      -1       0       1     1.618      2      -2      -1     0.382     0         0.414

For any Cn, f(R) = 1 + 2cos(2π/n),            For any Sn, f(R) = -1 + 2cos(2π/n)

 

 

Td         E          8C3      3C2      6S4       6σd

A1        1          1          1          1          1                             x2+y2+z2

A2        1          1          1          -1        -1

E          2          -1         2          0          0                             (2z2-x2-y2, x2-y2)

T1         3          0          -1         1         -1      (Rx,Ry,Rz)

T2         3          0          -1         -1         1          (x,y,z)        (xy,xz,yz)

 

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Loyola College M.Sc. Chemistry April 2009 Photochemistry & Organic Synthesis Question Paper PDF Download

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   LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 39

THIRD SEMESTER – April 2009

CH 3808 – PHOTOCHEMISTRY AND ORGANIC SYNTHESIS

 

 

 

Date & Time: 16/04/2009 / 1:00 – 4:00         Dept. No.                                                       Max. : 100 Marks

 

 

PART-A

Answer ALL questions.                                                                                 (10 ´ 2 = 20)

  1. What are the advantages of using phosphoryl esters instead of phosphanes in Wittig reactions?
  2. 25 g of benzaldehyde after various reactions forms 20 g of benzamide. What is the percentage yield of reaction?

03     What is FGI? Give an example.

04     Differentiate homogeneous and heterogeneous catalytic reductions.

05     What are the advantages of electro organic synthesis?

06     Write the Woodward Hoffmann rules for cycloaddition reactions.

07     How will you effect the following conversion?

08     What is Alder’s endo rule? What is its effect on the stability of the products?

  1. Represent various photophysical processes using Jablonskii diagram.
  2. What is Norrish type II reaction? Give an example.

 

 

PART-B

Answer any EIGHT questions.                                                                      (8 ´ 5 = 40)

  1. Write the mechanism of Simmon-Smith reaction.
  2. Carbonyl compounds have a key position in organic synthesis. Justify this statement.
  3. How the following compounds can be disconnected to get suitable synthons?
  4. a) b)

 

 

  1. Perform retrosynthesis and subsequently synthesize the given compound.
  2. Explain the effect of substituents on Birch reduction.
  3. Compare in detail the Clemmensen and Birch reductions with examples.
  4. How is electro organic oxidation performed? Explain with any two examples.
  5. Explain the mechanism of following reactions.
  6. a) Reformatsky reaction
  7. b) Hydroboration reaction

 

 

 

  1. How is degenerate sigmatropic rearrangement explained in the following compound?
  2. Draw correlation diagram for the electrocyclization of 1,3-butadiene by con rotation. Predict whether the reaction is thermally or photochemically allowed.
  3. What is Barton reaction? Predict the product in the following compound.
  4. Explain the photochemistry of a,b-unsaturated compounds with atleast two examples.

 

PART-C

Answer any FOUR questions.                                                                       (4 ´ 10 = 40)

  1. a) How Wittig Horner method is used to synthesize unsaturated compounds? Give suitable examples.
  2. b) How protecting groups help suitably during FGI? Explain with an example.
  3. a) How 1,2- and 1,3-difunctionalised compounds synthesized? Give one example for each.
  4. b) Explain the retrosynthesis of the following compound.
  5. a) How is cubane synthesized?
  6. b) Explain the mechanism of mercuric acetate oxidation.
  7. a) How NaBH4 reduction is performed? Write the mechanism of reaction.
  8. b) How active methylene compounds play significant role in organic synthesis? Explain the mechanism of Knoevenagal reaction.
  9. a) Discuss the FMO interaction of following pericyclic reactions.
  10. i) 1,5-sigmatropic rearrangement reaction
  11. ii) thermal-6 electron-electrocyclization reaction
  12. b) How cycloaddition is regioselective? Explain with any two examples.
  13. a) What is photoisomerisation? How does it vary with respect to various photosensitizers used?
  14. b) Derive Stern-Volmer expression.

 

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Loyola College M.Sc. Chemistry April 2009 Organic Substitution,Addition & Elimination Rxns Question Paper PDF Download

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      LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

WD 31

M.Sc. DEGREE EXAMINATION – CHEMISTRY

SECOND SEMESTER – April 2009

                    CH 2814 / 2808 – ORGANIC SUBSTITUTION, ADDITION & ELIMINATION RXNS

 

 

Date & Time: 20/04/2009 / 1:00 – 4:00  Dept. No.                                                       Max. : 100 Marks

 

 

PART – A

Answer ALL questions             (10 ´ 2 = 20 marks)

  1. ‘2-Bromo-2-methylbutane with ethoxide ion gives 2-methyl-2-butene but with t-butoxide gives 2-methyl-1-butene as major products’. Explain.
  2. How many stereoisomers are possible for 1,2,3,4,5,6-hexachlorocyclohexane? Which one will undergo slowest dehydrochlorination?  Why?
  3. What happens when 2-methyl-1-propanol is treated successively with CS2/NaOH, CH3I and heated to 200°C? Explain.
  4. Explain Sommelet-Hauser rearrangement with mechanism.
  5. What are extrusion reactions? Give an example.
  6. Define the following
  7. a) Partial rate factor           b) Hammett equation
  8. How does HNO2 react with 1° and 2° amines?
  9. Between CH3CH=CHCH2HgBr and CH3CH2CH2CH2HgBr which is more reactive with hydrochloric acid and why?
  10. What are possible termination steps in the free radical substitution in aromatic substrates?
  11. Arrange the following –HgR group in their decreasing order of leaving ability in the SE1 & SE2 reactions.

-HgMe,   -Hg is-Pr,   -HgEt,   -Hg-t-Bu

 

PART – B

Answer ANY EIGHT questions            (8 ´ 5 = 40 marks)

  1. ‘Acetolysis of both 4-methoxy-1-pentylbrosylate and 5-methoxy-2-pentylbrosylate gave the same mixture of products’. Explain.
  2. ‘Triphenyl methyl chloride reacts more rapidly with p-nitrobenzyl alcohol in benzene than with p-methylbenzyl alcohol’. Explain.
  3. ‘p-methoxybenzhydryl hydrogen phthalate on solvolysis in methanol results a     racemic ether’. Justify your answer.
  4. ‘Treatment of substituted anisoles with HI yields CH3I and a substituted phenol, rather than methanol and a substituted iodobenzene’.  Explain
  5. How does selenoxide undergo thermal syn elimination at room temperature? Explain with an example.
  6. Is the nucleophilic substitution at a vinyl carbon easy? Justify your answer with a suitable example.
  7. Give the mechanism of nitration of benzene. What are the various nitrating agents? Give evidences for the mechanism.
  8. Explain the following with suitable example.
  9. a) isoracemisation                        b) isoinversion
  10. Explain why in the abstraction step of photochemical chlorination of ethane, ethyl radical is formed and not the hydride radical.
  11. Give the mechanism of oxymercuration reaction. Also give the evidences for the free
    radical mechanism for the cleavage of Hg.
  12. Give the evidences for the syn, anti, and non stereoselective electrophilic addition of olefins.
  13. Arrange the following alkenes in their decreasing order of stereoselectivity of anti addition of Br2 and explain your answer.

MeCH=CHMe,      PhCH=CHMe,      PhC(Me)=CHMe

 

PART – C

Answer ANY FOUR questions                        (4 ´ 10 = 40 marks)

  1. a) Elimination of HBr from 2-bromobutane and elimination of trimethylamine from
    2-(N,N-dimethylamino)butane give different products in major amounts. Why?
  2. b) The dehydrochlorination in cis and trans 2-chloromaleic acid , the trans isomer reacts about 50 times faster than the cis compound.
  3. a) ‘The rates of hydrolysis of 0.1M alkyl bromides in 0.01M NaOH are in the order:
    t-BuBr > MeBr > EtBr > i-PrBr’.  Explain.
  4. b) ‘Solvolysis of L-threo-3-phenyl-2-butyl tosylate in acetic acid gives threo product as the major’.
  5. a) ‘For SN1 mechanism, a branching increases the rate of the reaction’. Justify this statement with suitable examples.
  6. b) ‘When the threo isomer of Ph-CO-CHBr-CHPh-COOH is treated with pyridine, it undergoes decarboxylative debromination, but erythro isomer under the same conditions undergoes dehydrobromination’.
  7. a) Give the mechanism of the following:
  8. i) Wohl-Ziegler bromination          ii) Eglinton reaction
  9. b) Explain neighboring group assistance in free radical bromination reaction and discuss the steric course of the reaction.
  10. a) Give the mechanism of free radical substitution at an aromatic substrate. Substantiate it with suitable evidences.
    b) Chlorination of 2, 3-dimethylbutane gives different ratio of products in aliphatic and aromatic solvents. Why?
  11. Predict A, B, C, D, and E for the following reactions.

 

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Loyola College M.Sc. Chemistry April 2009 Organic Reaction Mechanism & Stereochemistry Question Paper PDF Download

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         LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 49

FOURTH SEMESTER – April 2009

CH 4955 – ORGANIC CHEMICAL TECHNOLOGY

 

 

 

Date & Time: 28/04/2009 / 9:00 – 12:00  Dept. No.                                                 Max. : 100 Marks

 

 

PART-A

Answer ALL questions.                                                                       (10 ´ 2 = 20 marks)

 

  1. Define back mixing. What are its advantages and disadvantages?
  2. Why sulphonated products are very much useful industrially? Give reasons with example.
  3. What are the types of hydrogenating agents?
  4. Compare batch and parallel reactors.
  5. Narrate the preparation of titanium dioxide.
  6. A simple U-tube manometer is filled with mercury (specific gravity = 13.6) and the liquid above the mercury level is carbon tetrachloride (specific gravity = 1.6). The manometer reads 8.30 in. What is the pressure difference over the manometer in inches of water?
  7. What is Reynolds number? Give its significances.
  8. What is velocity gradient in a laminar flow?
  9. Define Couette flow.
  10. What is theoretical or equilibrium diagram?

 

 

PART-B

Answer any EIGHT questions.                                                           (8 ´ 5 = 40 marks)

 

  1. What are the physical factors that affect chemical process kinetics of chemical reactions? Write a short note on each.
  2. How is nitration of 2-methylpentane carried out? What are the products formed? Write the mechanism of the reaction.
  3. Explain in detail the workup procedure for sulphonation reaction and its products.
  4. How are various types of chlorination reactions performed industrially?
  5. What is the need for a research and development unit in industry? Discuss in detail.
  6. With the flow diagram explain the manufacture of paint.
  7. Describe the pump work in Bernoulli equation.

 

  1. Write short notes on impellers.
  2. Explain the working principle of bubble cap column with diagram.

 

 

 

  1. Explain the following
  2. a) energy balance over a flow system
  3. b) effect of temperature upon heat of the reaction
  4. Describe the various components involved in the fractionating column.
  5. What is differential distillation and give its applications?

 

PART-C

Answer any FOUR questions.                                                            (4 ´ 10 = 40 marks)

 

  1. a) Explain the effect of back-mixing on the product distribution and holding time in parallel and series reactions.
  2. b) How are temperature controlled reactions performed industrially?
  3. c) How is spent acid from nitration reaction recycled?
  4. a) Explain the method of nitration of hydrocarbons using Schmid nitrator.
  5. b) How is phenol manufactured industrially from cumene? Explain in detail.
  6. a) Explain the industrial preparation of hydrogenation of vegetable oil.
  7. b) What are the functions of quality control unit?
  8. a) Derive Barometric equation.
  9. b) Give the working principle of continuous gravity decanter.
  10. a) Explain the terms Newtonian and non-Newtonian flow.
  11. b) Write note on the mechanical energy balance in potential flow.
  12. How will you calculate the vapour composition of a mixture using Raoult’s law?

 

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Loyola College M.Sc. Chemistry April 2009 Organic Chemical Technology Question Paper PDF Download

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         LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 49

FOURTH SEMESTER – April 2009

CH 4955 – ORGANIC CHEMICAL TECHNOLOGY

 

 

 

Date & Time: 28/04/2009 / 9:00 – 12:00  Dept. No.                                                 Max. : 100 Marks

 

 

PART-A

Answer ALL questions.                                                                       (10 ´ 2 = 20 marks)

 

  1. Define back mixing. What are its advantages and disadvantages?
  2. Why sulphonated products are very much useful industrially? Give reasons with example.
  3. What are the types of hydrogenating agents?
  4. Compare batch and parallel reactors.
  5. Narrate the preparation of titanium dioxide.
  6. A simple U-tube manometer is filled with mercury (specific gravity = 13.6) and the liquid above the mercury level is carbon tetrachloride (specific gravity = 1.6). The manometer reads 8.30 in. What is the pressure difference over the manometer in inches of water?
  7. What is Reynolds number? Give its significances.
  8. What is velocity gradient in a laminar flow?
  9. Define Couette flow.
  10. What is theoretical or equilibrium diagram?

 

 

PART-B

Answer any EIGHT questions.                                                           (8 ´ 5 = 40 marks)

 

  1. What are the physical factors that affect chemical process kinetics of chemical reactions? Write a short note on each.
  2. How is nitration of 2-methylpentane carried out? What are the products formed? Write the mechanism of the reaction.
  3. Explain in detail the workup procedure for sulphonation reaction and its products.
  4. How are various types of chlorination reactions performed industrially?
  5. What is the need for a research and development unit in industry? Discuss in detail.
  6. With the flow diagram explain the manufacture of paint.
  7. Describe the pump work in Bernoulli equation.

 

  1. Write short notes on impellers.
  2. Explain the working principle of bubble cap column with diagram.

 

 

 

  1. Explain the following
  2. a) energy balance over a flow system
  3. b) effect of temperature upon heat of the reaction
  4. Describe the various components involved in the fractionating column.
  5. What is differential distillation and give its applications?

 

PART-C

Answer any FOUR questions.                                                            (4 ´ 10 = 40 marks)

 

  1. a) Explain the effect of back-mixing on the product distribution and holding time in parallel and series reactions.
  2. b) How are temperature controlled reactions performed industrially?
  3. c) How is spent acid from nitration reaction recycled?
  4. a) Explain the method of nitration of hydrocarbons using Schmid nitrator.
  5. b) How is phenol manufactured industrially from cumene? Explain in detail.
  6. a) Explain the industrial preparation of hydrogenation of vegetable oil.
  7. b) What are the functions of quality control unit?
  8. a) Derive Barometric equation.
  9. b) Give the working principle of continuous gravity decanter.
  10. a) Explain the terms Newtonian and non-Newtonian flow.
  11. b) Write note on the mechanical energy balance in potential flow.
  12. How will you calculate the vapour composition of a mixture using Raoult’s law?

 

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Loyola College M.Sc. Chemistry April 2009 Nuclear & Radio Chemistry Question Paper PDF Download

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    LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 36

SECOND SEMESTER – April 2009

CH 2954 / 2952 – NUCLEAR AND RADIO CHEMISTRY

 

 

 

Date & Time: 27/04/2009 / 1:00 – 4:00       Dept. No.                                                       Max. : 100 Marks

 

 

PART A

Answer the following:                                                                     10 x 2 = 20 marks

 

  1. How are basic particles different from sub-atomic particles?
  2. Why do nuclei show quadrupole moment?
  3. Explain nuclear isomerism?
  4. When does a nucleus emit α-particle?
  5. What is a compound nucleus? Cite an example.
  6. What is the source of neutrons in a fission reactor?
  7. What is the range of α particles less than that of β?
  8. What is meant by ‘Linear Energy Transfer’?
  9. What is the application of positron-annihilation technique
  10. What is the principle of carbon-dating?

PART B

 Answer any EIGHT of the following:                                           8 x 5 = 40 marks

 

  1. Compare properties of mesons and electrons.
  2. Explain any two reasons to expect nucleons inside the nucleii are independent of each other.
  3. Using Shell Model of nucleus explain magic numbers.
  4. Explain the principle of Mossbauer spectroscopy.
  5. A radioactive isotope (mass number=200) emits one α particle with a half life of 30min. If 20g of this isotope was allowed to stand in a sealed vessel for 40min, what shall be the volume (at STP) of helium present in the container?
  6. Give an account of counters employed to measure intensity of radiation.

 

 

 

 

 

  1. Explain nuclear fusion reaction and its applications.
  2. Explain principle and working of cyclotron.
  3. Write a note on chemical dosimeters.
  4. Discuss the preparation and properties of solvated electrons.
  5. How are radioactive isotopes useful in understanding chemical reaction mechanisms?
  6. What are the advantages, disadvantages and threats of tapping nuclear energy?

 

PART C

 Answer any FOUR of the following:                                                4 x 10 = 40 marks

 

  1. Using concepts of liquid drop model derive an expression for binding energy of a nucleus.
  2. Discuss various spontaneous and induced nuclear processes.
  3. Explain the use of fission reaction to produce energy and principle involved in it.
  4. Explain proposed mechanisms for radiolysis of water.
  5. Explain the principle and uses of isotope dilution analysis.
  6. Write short notes on
    • Szillard Charmer’s Process.
    • Aufbau Order for filling of nucleons in shells.

 

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Loyola College M.Sc. Chemistry April 2009 Molecular Spectroscopy Question Paper PDF Download

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        LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 42

THIRD SEMESTER – April 2009

CH 3810 – MOLECULAR SPECTROSCOPY

 

 

 

Date & Time: 04/05/2009 / 9:00 – 12:00  Dept. No.                                                   Max. : 100 Marks

 

 

PART A

Answer ALL the questions.                                                 (10 x 2 = 20 Marks)

  1. What is S/N ratio? How can it be enhanced?
  2. The rotational constant of a rigid diatomic molecule is 1.566 cm-1. Determine the transition which gives the most intense line at 300 K.
  3. Differentiate between hot band and overtone in the nature of their transitions.
  4. From the relative abundance of the (M+2)+ peaks in the mass spectra, can you distinguish Chloro compounds from Bromo compounds.
  5. What is the basic principle of Mossbauer Spectroscopy?
  6. Calculate the Larmor precessional frequency of a proton when placed in a magnetic field strength of 1.5 T ( gN = 5.585)
  7. What are diagonal and off-diagonal peaks in 2DNMR.
  8. Sketch the EPR spectrum of HCl radical.
  9. What are the conditions to observe NQR transitions.
  10. Mention the importance of a saturable absorber dye.

PART – B

Answer ANY EIGHT questions                                          (8 x 5 = 40 Marks)

  1. Explain the factors that affect the intensity of spectral lines.
  2. The rotational spectrum of 12C16O shows a series of equidistant lines spaced 3.8424 cm-1 Calculate the rotational constant and the C-O bond length in this molecule.
  3. Explain the pure rotational Raman spectrum of a symmetric top molecule.
  4. A molecule AB2 has the following IR and Raman spectra. Discuss the molecular structure and assign the observed lines to molecular vibrations.
Frequency (cm-1 )              IR                    Raman

3750                    very strong                  –

3650                    strong                      strong, polarized

1595                    very strong                  –

 

  1. Calculate the recoil velocity of the free Mossbauer nucleus 119Sn when emitting a γ- ray of frequency 5.76 x 1018 What is the Doppler shift of the γ- ray frequency to an outside observer?
  2. The mass spectrum of a compound having the empirical formula C5H8O2, shows the following peaks at m/e : 28, 43 (Base peak), 85, 100 (Molecular Peak). Identify the compound and account for the fragments.
  3. What is the effect of shielding and deshielding on precessional frequency?
  4. Odd number of bonds give positive J vale while even number of bonds give negative J values – explain.
  5. Discuss the EPR spectrum of a triplet state radical.

 

 

  1. Calculate the NQR frequency of a compound that has a C3 axis of symmetry. Given that e = 4.8 x 10-10 esu, Q = 0.08 x 10-24 cm2 and q = 2 x 1025
  2. How is pulse operation achieved in Q-switching?
  3. Explain the mechanism of mode locking method of producing laser pulses.

PART – C

Answer ANY FOUR questions                                            (4 x 10 = 40 Marks)

  1. a) The fundamental and first overtone transitions of  1H35Cl are centered at 2886 cm-1 and 5668 cm-1  Evaluate the equilibrium vibration frequency, the anhormonicity constant, and the force constant of the molecule.                                                  (6)
  2. b) Give any four basic differences between IR and Raman spectra                                    (4)
  3. a) The fundamental band of 14N16O is centred at 1904 cm-1 and its bond length is 0.1151 nm. Calculate the rotational constant B and the first two lines of the P and R branches of the vibration-rotational spectrum of NO.                                                                   (6)
  4. b) Explain briefly Quadrupole Mass analyzer.                                                         (4)
  5. a) Discuss any two applications of Mossbauer spectroscopy.                                  (6)
  6. b) The Raman line associated with a vibrational mode which is both Raman and IR active is found at 460 nm when excited by light of wavelength 435.8 nm. Calculate the wavelength of the corresponding infrared band.                         (4)
  7. (a) How will you interpret the Hetero nuclear correlation spectrum of a compound?(6)

(b) NMR of benzene is observed at a lower field while acetylene is at a higher field – explain                                                                                                             (4)

  1. (a) Explain the importance of the following (i) Electric field gradient (ii) asymmetry parameter                                                                                                           (6)

(b)  The benzene radical anion has a g value of 2.0025.  At what field would you search for resonance in 9.525 GHz instrument.                                                                 (4)

  1. (a) How will you characterize the delocalization of an unpaired electron in a transition

metal complex?                                                                                                     (5)

(b) How will you account for the variation in intensity of electronic transitions?     (5)

 

 

 

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Loyola College M.Sc. Chemistry April 2009 Instrumental Analysis Question Paper PDF Download

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        LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – PHYSICS

WD 44

THIRD SEMESTER – April 2009

CH 3900 – INSTRUMENTAL ANALYSIS (FOR PHYSICS)

 

 

 

Date & Time: 29/04/2009 / 9:00 – 12:00  Dept. No.                                                 Max. : 100 Marks

 

 

 

PART-A

Answer ALL the questions:                                     (10 x 2 = 20marks)

 

  1. Calculate the molarity of a solution which contains 6 g of NaOH (M.W.= 58.44) in

200mL of  solution?

  1. What are the conditions involved in good fractionation?
  2. What is the effect of temperature on HPLC?
  3. Write the types of ion exchange resins with an example?
  4. Define solubility product?
  5. Calculate the pH and pOH of a 0.01 M solution of NaOH at 25 °C?
  6. Calculate the frequency of C-H stretching vibration from the following data.

k = 5×105 dyne cm-1   and     m = 1.532×10-24g.

  1. Distinguish between AAS and FES.
  2. What is the principle DSC. Mention the reference material used in it.
  3. Compare DTA and TGA.

 

PART-B

Answer any EIGHT  questions:                                          (8 x 5 = 40marks)

 

11.a) What are primary and secondary standard solutions?

  1. b) Mention the prerequisites for secondary standard.
  2. Explain the method of purifying the mixture of solvents by steam distillation.
  3. How can a mixture of ethanol and water be separated by azeotropic distillation?
  4. How TLC is superior to other chromatographic techniques?
  5. Explain the difference between adsorption and partition chromatography?
  6. How is solubility determined using potentiometer?
  7. A buffer solution contains0.20 mole of NH4OH and 0.5 mole of NH4Cl per litre.

Calculate the pH of the solution (Kb of NH4OH at 25 °C is 1.81 X 10-5)

  1. Discuss the principle involved in flame photometry.
  2. Write a short note on finger print region.
  3. Describe the main parts of double beam spectrophotometer and give the function of

each component.

  1. Explain the factors which affect DTA curves.
  2. Discuss the applications of TGA.

 

PART-C

Answer any FOUR questions:                                             (4 x 10 = 40marks)

 

23.. a) Explain the principles involved in the following.(5)

(i) Column chromatography  (ii) Paper chromatography

  1. b) Define Rf What are the factors affecting it? (5)
  2. a) How can a mixture of aminoacid be separated by paper chromatography? (5)
  3. b) Explain the detectors used in ion exchange chromatography? (5)
  4. a) Derive Henderson equation to determine the pH of a buffer solution.(6)
  5. b) Write the principle of thermometric titrations.How is it applied for the titratiuon between a strong acid and strong base.(4)
  6. Draw and explain the thermograms expected for the following.(5+5)

(i) CuSO4.5H2O   (ii) CaC2O4.H2O

  1. a) Briefly describe the two basic types of vibrational modes of triatomic molecule. (7)
  2. b) How does lead in petrol determined using AAS?
  3. Derive Beer-Lasmbert’s law. How can it be verified?

 

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Loyola College M.Sc. Chemistry April 2009 Electrochemistry Question Paper PDF Download

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        LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 47

FOURTH SEMESTER – April 2009

CH 4808 / 4805 / 4803 – ELECTROCHEMISTRY

 

 

 

Date & Time: 21/04/2009 / 9:00 – 12:00  Dept. No.                                                     Max. : 100 Marks

 

 

Part–A (20 Marks)

Answer ALL questions (10 x 2 = 20)

  1. Calculate the ionic strength of a solution obtained by mixing 50 ml of 0.02 M
    Na2SO4 and 50 ml of 0.02 M cerium (III) sulphate solutions.
  2. Mention the factors affecting the thickness of the ionic atmosphere of an electrolytic solution.
  3. E°red of Au+/Au is 1.68 V, E°red Au3+/Au is 1.50 V. Calculate E°oxi  of Au+/Au3+
    at 25°
  4. Calculate the zeta potential of a colloidal particle in aqueous solution that has an
    electrophoretic mobility of 1.1   10-8 m2 s-1 V-1.  The coefficient of viscosity of water  is 8.91 x 10-4 kg m-1 s-1 and  Î = 78.3.
  5. What is ‘Dorn Effect’?
  6. Draw the general pattern of the plot of current density vs overvoltage for an electrode having symmetry factor 0.75.
  7. What do you mean by the high field approximation of the Butler-Volmer equation.
  8. The diffusion current of a certain metal ion at  3 × 10-2 mM is 3.3µA calculate its diffusion current at 6.9 × 10-2 mM concentration.
  9. Bring out the difference between voltammetry and polarography.
  10. Differentiate between half wave and standard reduction potentials.

Part-B (40 Marks)

Answer ANY EIGHT questions (8 x 5 = 40)

  1. Deduce Lippmann’s equation and mention its significance.
  2. Explain the influence of electrolytes on electrokinetic effects.
  3. The thermodynamic dissociation constant of a weak acid (HA) at 25°C is 2 10-5.
    What is the degree of dissociation of 0.1 M acid in 0.01 M KNO3 (aq) solution?
  4. Calculate Kh for NH4Cl if the EMF of the cell.

Pt½H2(1 atm)½NH4Cl(0.2M) ½½ KCl(1M)½Hg2Cl2½Hg

at 25° C is 0.574 V and E°red of calomel electrode is 0.28 V.

  1. Determine the potential due to ionic atmosphere around cation at 25° C for
    10-3M CaCl2(aq)  if Î0 = 8.854  ´ 10-12 C2J-1m-1 and dielectric constant of water is
    3.
  2. Explain Wien’s effect and its importance in the study of strong electrolytes.
  3. Electrolysis of a solution of Cu2+ produces 16 mg of Cu in 2 minutes. Calculate the rate of the reaction.

 

  1. What do you mean by non polarisable electrode? How is it related to its current density?
  2. Calculate the current density across an electrode (β = 0.45) at an applied potential of 0.23V if its equilibrium potential is 0.09V
  3. Explain migration and diffusion currents. Which current is significant in poloragraphy? How is it achieved?
  4. The dissolution of iron follows the following mechanism:

Fe  +  H2O         FeOH      +  H+ +   e–  ;  Eq Const K1……….……1

FeOH                  FeOH+    +   e–                ;   Eq Const K2……….…….2

FeOH+   + H+       Fe2+  + H2O              ;  Eq Const K3 …………….3

Determine its transfer coefficients if step-2 is the rate determining step.

  1. Explain the electrochemical reduction of a typical aromatic ketone.

Part-C (40 Marks)

Answer ANY FOUR questions (4 x 10 = 40)

  1. What is the need for a model on electrical double layer? Explain Helmohlltz-Perrin model and mention its defects.                                         (3 + 5 + 2)
  2. (a) Mention the assumptions of Debye-Huckel theory and explain any one
    application of Debye-Huckel limiting law equation.                  (3 + 4)

(b) What is the need to modify the limiting law equation.            (3)

  1. Explain any two of the following:
  • Relaxation effect
  • Electroosmosis
  • Gouy-Chap mann model of electrical double layer
  • van’t Hoff factor.
  1. Derive the relation between current density and applied potential for an electrode undergoing multistep multi electron reaction
  2. Define limiting current. Derive an expression for it relating to concentration on the basis of the concept of concentration polarization.
  3. Explain the following with suitable examples and figures.
  • Amperometric titrations
  • Electrodes as anodic rectifiers
  • Three electrode system.

 

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Loyola College M.Sc. Chemistry April 2009 Coordination Chemistry Question Paper PDF Download

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         LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 40

THIRD SEMESTER – April 2009

CH 3809 – COORDINATION CHEMISTRY

 

 

 

Date & Time: 06/05/2009 / 1:00 – 4:00  Dept. No.                                                   Max. : 100 Marks

 

 

PART – A

Answer all the questions                                                            (10 x 2 = 20)

  1. Calculate CFSE for high and low spin d5 metal complexes.
  2. What is spectrochemical series? Mention any two applications.
  3. Derive the ground term configuration of d6.
  4. The magnetic moment of mobs of [FeF6]3- is not equal to the magnetic moment value of mcal (spin only value), while in  [Fe(CN)6]3-, mobs is equal to mcal.  Explain.
  5. Explain why large numbers of sharp bands of low intensity are observed for d5 configuration?
  6. Why do electronic spectra of [V(H2O)6]3+ show only two absorption bands against three predicted for the system?
  7. What are the factors that favour charge transfer transition in metal complexes.
  8. What are supramolecules?
  9. What is Wilkinson catalyst? What type of chemical reaction can be effected by using this catalyst?
  10. Mention two biologically important coordination compounds and their applications.

PART – B

Answer any EIGHT questions                                                      (8 x 5 = 40)

  1. Discuss any two evidences of crystal field theory.
  2. Calculate OSSE and state whether the following oxides are spinel or inverse spinel : Mn3O4, Fe3O4, CuFe2O4.
  3. Differentiate labile and inert complexes using crystal field theory.
  4. What is linkage isomerism? How are these isomers differentiated by IR spectral analysis?
  5. Explain the bonding present in ferrocene using MO theory.
  6. State and explain Jahn-Teller effect.
  7. What is trans effect? Explain the theories of trans effect in explaining the mechanism of substitution reaction of square planar complexes.
  8. Discuss the expected esr spectrum of  [Cu(salicylaldimine)2]2+ ion.
  9. Explain the nature and types of interactions of supramolecule.
  10. Discuss the structure and functions of the enzyme, carboxypeptidases.
  11. Explain the types of photochemical reactions with examples.
  12. Write notes on i) the Wackers process ii) hydroformylation reaction

PART C

Answer any FOUR questions                                                (4 x 10 = 40)

 

  1. How do the d-orbitals split in square planar and tetrahedral crystal field of ligands?
  2. Explain how ORD and CD studies help in determining the absolute configurations of chiral complexes.
  3. Explain with the help of MO theory why Cl– acts as a weak ligand where as CN–acts as a strong ligand in octahedral transition metal complexes.
  4. Explain the features of Tanabe-Sugano and Orgel diagram. Construct orgel diagram for d2, d7 octahedral and d8, d3 tetrahedral of metal ion and explain the possible electronic transitions.
  5. Explain the mechanism and factors affecting the innersphere and outersphere electron transfer reaction of metal complexes.
  6. Explain the structural aspects of haemoglobin in the oxygen transport.

 

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