Total No. of Questions : 6] P1949 SEAT No. : [4923]-11 M.Sc. CHEMISTRY CH - 110 : Physical Chemistry - I (2008 Pattern) (Semester - I) [Total No. of Pages : 4 Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answer to the two sections should be written in separate answer books. 2) All questions are compulsory. 3) Figures to the right side indicate full marks. 4) Use of logarithmic table / calculator is allowed. 5) Neat diagrams must be drawn wherever necessary. P.T.O. SECTION - I Q1) Attempt any three of the following: [15] a) Define chemical potential. Derive the expression for the change in gibbs free energy of mixing when two ideal gases are mixed. b) Explain the following terms with examples. i) State function. ii) Path function. iii) Exact differential. iv) Inexact differential. c) Explain the de Broglie wave length of a particle. How does it account for the dual nature of matter? d) Derive the expression for Wmax in the adiabatic expansion of an ideal gas. e) Discuss the inadequancies of first law of thermodynamics giving suitable examples. Q2) Attempt any three of the following: a) [15] Sketch the first four energy levels for a particle in a box with respect to i) wave function ii) probability densities. Write the Schrodinger equation for a particle in a box. b) Write a note on blackbody radiation. What is ultraviolet catastrophe? c) Derive the expression for elevation in boiling point using the concept of chemical potential. d) Explain Einsteins photoelectric effect. e) Explain the zeroth and third law of thermodynamics with their applications. [4923]-11 2 Q3) Attempt any one of the following: [5] a) Calculate the number of photons emitted by a mW bulb emitting 700nm. radiation in one hour. b) Calculate the change in entropy when 21g of nitrogen are mixed with 22g of CO2 and 24g of oxygen at 25ºC. [At. wt. N = 14, O = 16, C = 12]. c) The work function of barium is 2.48eV. If light of 400nm is incident on a barium cathode. What is the maximum velocity of ejected electrons in eV? SECTION - II Q4) Attempt any three of the following: [15] a) Derive Michaelis Menton equation for enzyme catalysed reactions. b) Write a note on experimental methods to study nano-second reactions. c) Assuming following rate law, rate = K[A]h, derive the expression for half life period. d) k For the reaction NO2(g) + CO(g) ⎯⎯ → CO2(g) + NO(g), it is observed that rate of formation of CO2 is second order wrt NO2. Show that following mechanism is consistant with observation. k 2NO2(g) ⎯⎯ → NO3 (+g ) NO(g) (rate determining) 1 k NO3(g) + CO(g) ⎯⎯ → CO2(g) + NO2(g) 2 e) Explain explosive reactions with suitable example. Q5) Attempt any three of the following: [15] a) What is the effect of ionic strength on the reaction rates? b) Define partition function and show that Q T = Q r ⋅ Q v ⋅ Q t ⋅ Q e . c) Derive the expression for rotational partition function. [4923]-11 3 d) Write a note on collision theory of reaction rates assuming kinetic theory of gases. e) Show that unimolecular gas phase reactions are pressure dependant. Q6) Solve any two of the following: [10] a) A first order reaction is 50% completed in 35M. Show that it never goes to 100% completion. b) Calculate the translational partition function of a molecule of oxygen at 1 atm. and 25ºC. c) ⎛ 98.6 ⎞ The Arrhenius equation for a reaction is given by k= 4 × 1013 × e − ⎜ ⎟ ⎝ Rt ⎠ At what temperature reactant concentration its half life be 30 minutes if it follows a first order kinetics? E [4923]-11 E 4 E Total No. of Questions :6] P1950 SEAT No. : [Total No. of Pages :5 [4923]-12 M.Sc. (Part - I) CH-130: INORGANIC CHEMISTRY - I Time : 3 Hours [Max. Marks :80] Instructions to the candidates: 1) All questions are compulsory. 2) Answer to the two sections should be written in separate answer books. 3) Neat and labelled diagrams must be drawn wherever necessary. 4) Figures to right side indicate full marks. SECTION - I Q1) Attempt any three of the following: [15] a) Sketch and describe all the symmetry operations in XeF4 and classify it into appropriate point group. b) Classify the following molecules into appropriate point group (any two). Justify. i) BrF3 ii) POCl3 iii) C5H-5 ion c) What are the conditions of a Mathematical group? Explain them considering NF3 molecule. d) Derive character table for the molecule trans H2O2 (planer) using great Orthogonality theorem and all rules. Also label each irreducible representation with approprite Mulliken symbol. e) Give stereographic projection of the following molecule with justification. i) Staggered B2Cl4 ii) Al2Br6 P.T.O. Q2) Answer any three of the following. a) Using Matrix multiplication method, find the product of the following: i) b) c) d) [15] σ (xz) ×σ ii) (xy) C2(x) × σ (yz) Find out the resultant SALC using projection operator of E' irreducible representation which operates on σ1 of the BF3 molecule belonging to point group D3h D3h E 2C3 3C2 σh 2S3 3σV E' 1 1 2 0 2 0 For molecule, PF5 find the reducible representation for which sigma bonds form the basis & find out which orbitals from the central atom will be offered for sigma bonding. Given character table for D3h point group. D3h E 2C3 3C2 σh 2S 3 3σV A'1 1 1 1 1 1 1 A'2 1 1 1 1 1 1 E' 2 1 0 2 1 0 A"1 1 1 1 1 1 1 A"2 1 1 1 1 1 1 Z E" 2 1 0 2 1 0 Rx Ry x2+y2,z2 Rz (x,y) (x2y2,xy) xz,yz Write out the characters of the representation of the following direct product and determine the set of irreducible representations which comprise them for the point group D3h Direct product - E' × A"2 (Character table for D3h point group Question no.2c) e) [4923]-12 Explain slide plane and screw axis with each two examples of each. 2 Q3) Attempt any two of the following. a) By schematic representations give the products of the following symmetry operations in C2H4 molecule. i) b) c) [4923]-12 [10] C2(z) × C2(x) ii) σ (xy) ×σ (xz) On the basis of symmetry, what is the criterion for the molecule to be optically active. Predict the optical activity for the following molecules, Justify your answer. i) 1,3,5,7 tetramethyl cycloocta tetraene ii) Tetrahedral [M L2X2] complex With the help of group multiplication table, given below, group the symmetry operations in to appropriate classes. C4V E C4 C 4 -1 C2 σV1 σV2 σd1 σd2 E E C4 C 4 -1 C2 σV1 σV2 σd1 σd2 C4 C4 C2 E C 4-1 σd1 σd2 σV2 σV1 C 4 -1 C 4 -1 E C2 C4 σd2 σd1 σV1 σV2 C2 C2 C 4-1 C4 E σV2 σV1 σd2 σd1 σV1 σV1 σd2 σd1 σV2 E C2 C 4-1 C4 σV2 σV2 σd1 σd2 σV1 C2 E C4 C 4-1 σd1 σd1 σV1 σV2 σd2 C4 C 4-1 E C2 σd2 σd2 σV2 σV1 σd1 C 4 -1 C4 C2 E 3 SECTION - II Q4) Answer any three of the following. [15] a) Explain with suitable examples, the electron rich and electron deficient hydrides. b) What are the similarities and differences in the structures of layered BN and graphite? c) Discuss the synthesis and structures of xenon fluorides. d) Give the classification of boron hydrides and count the skeleton electrons of B4H10 molecule. e) Give any two synthetic procedures for the preparation of organometallic compounds with suitable examples. Q5) Write short notes (any three): [15] a) Pseudohalides. b) Solution of alkali metal in non - aqueous solvent. c) Phosphonitrilic compound. d) Metal fullerene compounds. e) Types and uses of layered aluminosilicates. Q6) a) [4923]-12 Draw the structures of the following (any five): i) B3N3H6 ii) S4 N 4 iii) [B3O3(OH)4]- iv) P4010 v) Rock salt structure of NaCl vi) 2.2.1 crypt 4 [5] b) Complete the following reactions (any five): i) 4LiAlH4 + SiCl4 ⎯⎯ → _________ + SiH4 + 4LiCl ii) → ___________ CH3Cl + [IrL2Cl(CO)] ⎯⎯ iii) Δ ,C H Cl 3NH4Cl + BCl3 ⎯⎯⎯⎯ → iv) → _______ PCl5 + PhNH2 ⎯⎯ v) S8 + AsF5 ⎯⎯ → __________ vi) XeF6(s) + H2O 6 (l) ⎯⎯ → ___________ + HF(g) O [4923]-12 5 O 5 O [5] Total No. of Questions : 6] SEAT No. : P1951 [Total No. of Pages : 5 [4923] - 13 M.Sc. (Part - I) ORGANIC CHEMISTRY CH - 150 : Organic Reaction Mechanism and Stereochemistry (2008 Pattern) (Semester - I) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All Questions are compulsory. 2) Figures to the right indicate full marks. 3) Answers to the two sections should be written in separate answer books. SECTION - I Q1) Attempt any four of the following: a) Explain nucleophilicity and basicity with suitable examples. b) Which of the following is optically active? Justify your answer. c) Which of the following is more acidic? Why? d) Cyclo-octatetraene is not automatic. Explain. e) Explain IPSO substitution with suitable example. [4923] - 13 1 [16] P.T.O. Q2) Attempt any three of the following: [12] a) Explain stereospecific and stereoselective reactions with suitable examples. b) Assign E/Z configuration to the following. Justify. i) c) ii) Assign R/S configuration to the following. Justify. i) d) ii) Convert Fischer Projection to Newman or Sawhorse projection as shown below. ii) i) Q3) Attempt any four of the following: a) [12] Explain the pKa values. (i) [4923] - 13 (ii) 2 (iii) b) Assign Re & Si & Justify. c) Explain SNi reaction with suitable example. d) Write short note on Ambident Nucleophiles. e) Differentiate between protic & Aprotic solvents. SECTION - II Q4) Give mechanism of any four: [16] a) b) c) d) e) [4923] - 13 3 Q5) Predict the products-(any six) [12] a) b) c) d) e) f) g) h) [4923] - 13 4 Q6) Attempt any four from the following: [12] a) Nitration of aniline with nitrating mixture always gives m-nitroaniline. Explain. b) Naphthalene on sulphonation with sulphuric acid at lower temperature gives Naphthalene-1-sulphonic acid while at higher temperature, naphthalene 2-sulphonic acid is formed. Explain. c) Propene on reaction with HBr gives Isopropylbromide but gives 1bromopropane in presence of HBr/H2O2. Explain. d) Write a note on Hoffman elimination. e) Explain Michael Reaction with suitable examples. f) Write note on Friedal Crafts Acylation. l [4923] - 13 l 5 l Total No. of Questions : 6] P1952 SEAT No. : [Total No. of Pages : 4 [4923] - 21 M.Sc. CH - 210 : PHYSICAL CHEMISTRY - II (Old) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE answer books. 2) All questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table/calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION - I Q1) Attempt any three of the following: [15] a) What is the energy range of IR radiation? Write a note on signal to noise ratio. b) Discuss advantages of FTIR spectroscopy. c) Show that for a rigid diatomic rotator the moment of inertia I = μr2, where μ is reduced mass and r is the bond length. d) How does isotopic substitution reveal the exact isotopic mass and relative isotopic abundance in microwave studies? e) spectra. Explain the applications of Mossbauer Q2) Attempt any three of the following: [15] a) Explain the classical theory of Raman effect. b) Sketch and explain the polarizability ellipsoids for the various vibration modes of H2O molecule, which of these are Raman active? c) Write a note on Fortrat Parabola. d) Explain the applications of ESR spectroscopy. e) Explain the structure of nitrous oxide molecule in the light of XPES. Q3) Solve any two of the following: [10] a) Predict the position of rotational Raman spectral lines for [B = 1.99cm1, excitation frequency = 891 THz]. b) The anharmonicity constant for a diatomic molecule is 0.0061. Evaluate the vibrational quantum number that would lead to dissociation of molecule. [4923] - 21 2 14 N 2. c) The first rotational absorption of 12C 16O occurs at 3.84235cm1, while that of 13C 16O occurs at 3.67337cm1. Evaluate the exact atomic weight of 13C [mass of oxygen = 15.9994]. SECTION - II Q4) Attempt ANY THREE of the following: [15] a) Explain the constraction and working of G.M. counter. b) Discuss in detail, the mechanism of radiolysis of water. c) Explain the different units for measuring absorption of radiations. d) What are the various modes of interaction of γ- rays with matter? Discuss any one of them in detail. e) Explain isotope separation method for plutonium. Q5) Attempt ANY THREE of the following: [15] a) What is the breeder reactor? Explain the principle of breeding with an example. b) What is design parameter? Classify the reactors on the basis of fuel and moderator. c) Explain in detail critical size of thermal reactor. d) What is isotope dilution analysis (IDA)? Explain its principle. Give the applications of isotope dilution analysis. e) Describe the use of radio isotope in the measurement of thickness of moving sheet. [4923] - 21 3 Q6) Solve ANY TWO of the following: [10] a) The half life period of 226Ra is 1600 years. How many gram of it will be left undisintegrated from 1.0 gm of the isotope after 4750 years. b) Calculate the linear absorption coefficient of methanol. (Given, eμ = 0.211 barn/electron density of methanol is 0.713 gm cm3. Z of C = 6, H = 1, O = 8 A of C = 12, H = 1 , O = 16) c) 0.1g of Mn sample was irradiated in a neutron flux of 107 n. cm2s1, for 30 minutes. What will be its activity at the end of the irradiation. (γ = 100%, σ = 13.3 b, t 12 of 56Mn = 2.58h). l [4923] - 21 l 4 l Total No. of Questions : 6] P1953 SEAT No. : [Total No. of Pages : 6 [4923] - 22 M.Sc. I INORGANIC CHEMISTRY CH - 230 : Inorganic Chemistry - II (2008 Pattern) (Semester - II) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All Questions are compulsory. 2) Answers to the two sections should be written in separate Answer books. 3) Neat and labelled diagrams must be drawn wherever necessary. 4) Figures to the right indicate full marks. 5) Use of logtables and calculator is allowed. 6) Given Atomic Numbers Cr = 24 V = 23 Ni = 28 Sm = 62 Gd = 64. SECTION - I Q1) Attempt any three of the following: [15] a) Prepare a table of microstates and hence derive the allowed R.S. terms for the (n1) pnp configuration. b) Give the appropriate term symbols for the states with following values of L and S. Also work out possible values of J. 3 2 i) L = 3 and S = ii) L = 2 and S = 3. c) Give the splitting of 3F term in weak cubic field using character table for pure rotational point group O. d) Predict the expected electronic transitions in the following complexes. -3 i) ⎡⎣Cr (OX)3 ⎤⎦ ii) ⎡⎣ V (H 2O )6 ⎤⎦ +3 P.T.O. Q2) Attempt any three of the following: [15] a) Explain non crossing rule with the help of suitable example. b) How would you account for the magnetic moment of the following complexes. c) i) ⎡⎣ Ni ( NH 3 )6 ⎤⎦ SO 4 μ = 2.84 BM ii) K 2 ⎡⎣ Ni (CN )4 ⎤⎦ A single absorption peak is observed at 9000 cm1 in the electronic spectrum of Vcl4. What will be the value of Δ if the molecule is tetrahedral? Estimate the value of Δ of vanadium (IV) complex in an octahedral evironment. d) Determine the ground state terms for the following ions. i) V+2 ii) Cr+2 iv) Sm+2 v) Gd +3 iii) Ni+2 Q3) Answer any two of the following: a) Redox spectra. b) Quenching of orbital angular momentum in complexes. c) Racah parameters. [10] SECTION - II Q4) Answer any three of the following: [15] a) Explain the process of detoxification of mercury. b) Explain the mechanism of cis-platin as anti-cancer drug. c) What are the different binding sites present in amino acids for binding metals? d) Explain the role of calcium binding calmoduline. [4923] - 22 2 Q5) Write short notes (any three): [15] a) Metal junctions in metalloproteins. b) Chelate effect and Irving - Williams series. c) Model compounds and spontaneous self-assembly. d) Uptake of chromate ion. Q6) Draw the structures (any five) of the following: a) Enterobactin. b) Fe4S4. c) Cardiolyte. d) Cytosine. e) Glycine. f) Hemoglobin. [4923] - 22 3 [10] [4923] - 22 4 [4923] - 22 5 l [4923] - 22 l 6 l Total No. of Questions : 6] SEAT No. : P1954 [Total No. of Pages : 4 [4923] - 23 M.Sc. I ORGANIC CHEMISTRY CH - 250 : Synthetic Organic Chemistry and Spectroscopy (2008 Pattern) (Semester - II) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All Questions are compulsory. 2) Figures to the right indicates full marks. 3) Answers to the two sections should be written in separate Answer book. SECTION - I Q1) Explain any four of the following: [16] a) Cis - 2 - butene on reaction with I2, AgOAc in aqueous condition gives meso diol. b) Explain any four methods for synthesis of epoxide. c) β-hydroxy esters are prepared by organozine reagents and not organo magnesium reagent. d) Use of aluminium isopropoxide in organic synthesis. e) Wolff Rearrangement is used to prepare higher homologue of starting acid. Q2) Write short note on any three of the following: a) Claisen rearrangement. b) Favorskii rearrangement. c) Birch reduction. c) Simmons-Smith reaction. [12] P.T.O. Q3) Predict the product and suggest the mechanism for any four of the following:[12] SECTION - II Q4) Suggest Mechanism for any four of the following: [4923] - 23 2 [12] Q5) Attempt Any Four of the following: [16] a) Carbonyl stretching frequency increases in the following order. Explain. b) Write a note on factors affecting on chemical shift. c) Calculate λmax for the following compounds. Clearly show your calculations. d) How will you monitor the following reaction sequence by IR. e) Explain the chemical shift of underlined protons. Q6) Deduce the structure of any three of the following compounds using spectral data and justify your answer. [12] a) MF : C5H8O2 IR : PMR 1695, 1620, 990 and 910 cm1 δ 1.6(t,J = 6Hz,3H), 4.3 (q, J = 6Hz,2H) 5.8 (dd, J = 4 Hz and 10Hz, 1H) 6.11(dd, J = 10Hz and 16Hz, 1H) 6.4(dd, J = 4Hz and 16 Hz, 1H) [4923] - 23 3 b) MF : C4H7BrO2 IR : 3300 - 2700, 1720 cm1 PMR δ 1.08 (t, J = 7Hz, 3H), 2.07 (m, 2H) 4.23(t, J = 7Hz, 1H) 10.97 (S,1H, Exchangable with D2O). c) MF : C8H8O2 IR : 1735cm1, 1600, 1500 cm1 PMR : δ 4.0 (s, 3H) 7.3 (s, 5H). d) MF : C10H11NO4 IR : 1735, 1530, 1350 cm1 PMR : δ 1.3 (t, 7Hz, 12mm) 2.6(s, 12mm) 4.25(q, 7Hz, 8mm) 7.4 (d, 8Hz, 4mm) 7.9 (dd, 8 and 2Hz, 4mm) 8.3 (d, 2Hz, 4mm). l [4923] - 23 l 4 l Total No. of Questions : 5] SEAT No. : P1955 [Total No. of Pages : 4 [4923] - 31 M.Sc. II PHYSICAL CHEMISTRY CH - 310 : Quantum Chemistry and Solid State Chemistry (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the two sections should be written in separate Answer books. 2) All Questions are compulsory. 3) Figures to the right side indicate full marks. 4) Use of logarithmic table calculator is allowed. 5) Neat diagrams must be drawn wherever necessary. P.T.O. SECTION - I Q1) Attempt any four of the following: a) [20] Show that the function U(x) = eax2 is an eigen function of operator ⎛ ∂2 2⎞ ⎜ 2 − x ⎟ for a = 0.5. ⎝ ∂x ⎠ b) c) Classify the operators as linear or nonlinear. i) ∫ dx ii) exp iii) ∑ iv) ( )2 v) d2 2x dx 2 2 Find the term symbols for the following configuration. i) 2S1 2P1 and ii) d) Explain the properties of Ladder operators in brief. e) Compare the variation method with the perturbation method. f) Show that Hermitian operators have real eigenvalues. Q2) Attempt any four of the following: [20] a) energies for cyclobutadiene, why is the molecule not Deduce the Huckels stable? b) State Huckels (4m+2) rule and explain how it accounts for the stability of cyclooctatetraene dianion. c) Sketch the MO for butadiene on the basis of HMO theory. Deduce the energies of these orbitals on the basis of secular determinant. [4923] - 31 2 d) Explain the mnemonic Model of Frost and Musulin used to deduce HMO energies for annulenes. e) Comment, giving examples on the positive or negative nature of REPE Value for a molecule. f) Derive the equation for first order perturbation energy for nondegenerate systems in a generalized situation. SECTION - II Q3) Attempt any three of the following: a) What are the differences between Schottky and Frenkel defects? b) Explain the photo conductivity in ionic crystals. c) Discuss Einsteins specific heat theory of metals. d) Explain the formation of F and V colour centres in crystals. e) Write a note on Kirkendall effect. Q4) Attempt any three of the following: [15] [15] a) What are the different methods to grow crystals from their melts? Describe the merits and demerits of any two such methods? b) How is the parabolicrate law useful in explaining the mechanism of a gas-solid reaction? c) Write a note on transistors. d) What are the main types in which materials can be divided on the basis of their response to magnetic filed? Discuss briefly. e) Explain the various mechanism of diffusion insulator. [4923] - 31 3 Q5) Solve any two of the following: [10] a) How long would it take for Li to penetrate in Se at 550 oC to a 0.65 mm depth? [D = 106 cm2/sec]. b) Calculate the relaxation time for Cu having density 8.92 g/cc. [Given At. Wt. of Cu - 63.5]. c) The number of free electrons in a monovalent crystal is 9.8 × 1018 per cm3 at 350 K. Evaluate Eo in eV. l [4923] - 31 l 4 l Total No. of Questions : 6] P1956 SEAT No. : [Total No. of Pages : 4 [4923] - 32 M.Sc. PHYSICAL CHEMISTRY CH - 311 : Nuclear and Radiation Chemistry (2008 Pattern) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE Answer books. 2) All Questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table/calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION - I Q1) Attempt any three of the following: [15] a) Discuss Bhor-wheeler theory of Nuclear fission. b) Write a note on Breeder Reactor. c) Give salient features of liquid drop model. d) Write down four factor formula and describe each term in it. e) Discuss the principle of Pix technique. Q2) Attempt any three of the following: [15] a) Write a note on conservation of nuclear reactions. b) Write a note on Cockroft-Walton accelerator. c) Discuss the working of Fricke-dosimetry. d) Discuss the various stages of interaction of radiation with biological cells. e) What are the after effects of charnobyl accident? Q3) Solve any two of the following: a) [10] What is the excitation energy of the compound nucleus resulting in the bombardment of 27Al by α-particles of energy 6MeV? [Given : m27A1 = 26.981535, Mα = 4.002604, M 31P = 30.973763 amu) b) Find out the dose due to 400 μci 60Co source at a distance of 4 meters. Given = 1170 and 1330 kev. c) Compute the number of uranium atoms that must fission per second such a that the power generated equals 100 MW. [Given : energy released per uranium fission is 200 MeV]. [4923] - 32 2 SECTION - II Q4) Attempt any three of the following: [15] a) Distinguish between intrinsic and extrinsic semiconductor. What are requirements of semi conductor to be good radiation detector. b) Give an account of szilard-chalmers reaction. c) Discuss the working of Li-drifted detector. d) Describe the mechanism of radiation annealing. e) Explain the terms, scavanger, G-value, LET and prp. Q5) Attempt any three of the following: [15] a) Discuss the ICRP recommendation for maximum permisible dose. b) Write a note on radioactive waste management. c) What precautions are to be taken while handling radioactivity? d) Discuss how external radiation hazards can be controlled with the help of time, distance and shielding. e) Write down the various stages of interaction of radiations with biological cells. [4923] - 32 3 Q6) Solve any two of the following: [10] a) If the linear mass absorption coefficient of pb is 0.57 cm1. What thickness of lead required to reduced the activity from 10,000 cpm to 6,000 cpm. b) When chloroform is exposed to Gamma radiation what is the absorbed in 6 hours. Given (Z A ) of frick solution is 0.553 and the dose absorbed by Frick solution at the same position is 4.06 Gy/min. c) The recoil energy of Mossbauer nuclei is 1950KeV. Find the energy of a gamma photon emitted by the nucleus. l [4923] - 32 l 4 l Total No. of Questions : 6] SEAT No. : P1957 [Total No. of Pages : 4 [4923] - 33 M.Sc. PHYSICAL CHEMISTRY CH - 312 : Advanced Instrumental Methods of Analysis (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the two sections should be written in separate Answer books. 2) All Questions are compulsory. 3) Figures to the right side indicate full marks. 4) Use of logarithmic table calculator is allowed. 5) Neat diagrams must be drawn wherever necessary. P.T.O. SECTION - I Q1) Attempt any three of the following: [15] a) Draw and explain block diagram for apparatus used for x-ray absorption. b) What is wavelength dispersive and energy dispersive device on x-ray analysis? Draw flow - sheet diagram for them. c) Discuss the spherical electrostatic field analyzer used in ESCA. d) Enlist the various steps involved in radioactivation analysis. Explain briefly post - irradiation treatment in NAA. e) Explain the terms i) Target ii) Matrix iii) Cross section iv) Isotope abundance. Q2) Attempt any three of the following: [15] a) With a neat labelled diagram explain the time of flight analyzer used in mass spectrometry. b) Discuss the applications of NAA. c) State the function of ionic source and describe briefly electron bombardment ionization method used in mass spectrometry. d) Explain the terms spectral splitting and chemical shift used in ESCA. e) Explain the termsi) binding energy ii) work function and kinetic energy of electron with suitable energy level diagram. [4923] - 33 2 Q3) Solve any two of the following: a) [10] What mass difference can just be resolved at M values of 100, 500, 1500, 3000 and 5000 if the mass spectrometer has resolution of i) 500 ii) 1000. b) The mass absorption coefficient for Ni measured with Cu Kα line is 49.2 cm2/g. Calculate the thickness of a nickel foil that was found to transmit 47.8% of the incident power of a beam of CuKα radiation. The density of Ni is 8.90 g/cm2. c) What weight of the alloy should be taken which contain 2% gold, if the irradiation period is 2 days in a neutron flux of 1.8 × 107 n cm2s1 and desired activity after a cooling period of 1 day is 500 cpm. Given : γ = 100%, σ = 98.8 b, half life of 198Au = 2.7 days. SECTION - II Q4) Attempt any three of the following: [15] a) What is plasma? Explain briefly the principle underlying inductively coupled plasma atomic emission spectroscopy. b) Write a note on applications of ICP emission spectroscopy. c) Describe briefly applications of DTA. d) Write a short note on liquid phase chemiluminescence. e) What is basic difference between DSC and DTA? Explain briefly any one type of DSC instrument. [4923] - 33 3 Q5) Attempt any three of the following: [15] a) Explain the principle of voltammetric analysis and describe different excitation signals used in voltammetry. b) What is potentiostat? Explain the working of potentiostat. c) Draw and explain flow-sheet diagram for photoluminescence apparatus. d) Describe in brief any one coulometer. e) Write a note on electro chemiluminescence. Q6) Solve any two of the following: [10] a) 1 g sample containing Cu and Ag nitrates were heated in TGA apparatus. The weight recorded at 400 and 700oC are 0.72 g and 0.56 g respectively. Calculate percentage of Cu and Ag in given sample (At. wt.: Cu = 63.54, Ag = 107.87, N = 14, O = 16]. b) Constant current coulometry was used to assay a solution containing Fe2+. To ensure 100% current efficiency the assay was performed in 0.1 M cerium (III) sulfate - sulfuric acid solution. At the end point of titration 25ml sample, a controlled current of 6.45 mA had flowed for 3 min 40s. Calculate the concentration of Fe2+ in the sample. c) In an ESCA an electron was found to have a kinetic energy of 1073.5 eV. When MgKα source was empolyed (λ = 0.98900 nm). The electron spectrometer had a work function of 14.7 eV calculate the binding energy for the emitted electron. What would the K.E. have been if Al Kα source had been used (λ = 0.833 nm). l [4923] - 33 l 4 l Total No. of Questions : 5] P1958 SEAT No. : [4923] - 34 M.Sc. PHYSICAL CHEMISTRY CH - 314 : Polymer Chemistry (2008 Pattern) (Semester - III) [Total No. of Pages : 3 Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE Answer books. 2) All Questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION - I Q1) Attempt any three of the following: a) Distinguish between chain and step polymerisation. b) Describe entropy of heat of mixing of polymer solution. c) Write a note on thermosetting and thermoplastic polymers. d) Define the following terms: e) i) Polymer ii) Degree of polymerisation iii) Hetrochain polymer iv) Configuration v) Co-polymer. [15] Explain, why Nylon - 6 is highly crystalline? Q2) Attempt any three of the following: [15] a) Derive copolymer equation. b) Describe Flory-Krigbaum theory of dilute polymer solution. c) Discuss the elastomer forming properties of a polymer. d) Explain how mechanical properties can be used in physical testing of polymer. e) Define glass transition temperature (Tg) and describe any one method of its determination. Q3) Solve any two of the following: [10] a) Calculate the viscosity at C = 0.40 g/dl, H = 0.33, M = 120000, K = 1.2 × 104 and α = 0.72. b) Calculate xn , xw and weight fraction of xn - mers when linear step polymerization is 99% complete. [4923] - 34 2 c) The molecular weight of polymer is determined by sedimentation equilibrium method. It was found that the aqueous solution was 1-7 times as concentrated at a distance 10cm from the axis of rotation at a distance 7 cm. Calculate the molecular weight. (Given - Rotor speed = 6000 rpm, t = 25oC, ρ = 1.2 g/cc and V = 0.6). SECTION - II Q4) Attempt any four of the following: [20] a) Describe the use of DTA technique in the analysis of polymer. b) Describe the compression molding with neat diagram. c) Write a note on -Microscopic analysis of polymers. d) Define - Viscosity, inherent viscosity and intrinsic viscosity. e) Explain how nmr and esr spectroscopy useful in analysis of polymer. f) Discuss the conduction mechanism in conducting polymer. Q5) Attempt any four of the following: [20] a) Discuss the elastomer forming properties of polymer. b) What is Rheology? Discuss the viscous flow phenomenon and its mechanism in polymers. c) Describe sedimentation velocity method to determine the molecular weight of polymer. d) What are the different types of spinning technique? Why is melt spinning preferred over the others? e) Discuss the kinetics and mechanism in block co-polymers. f) Describe the process of vulcanization with suitable example. l [4923] - 34 l 3 l Total No. of Questions : 4] P1959 SEAT No. : [Total No. of Pages : 3 [4923] - 35 M.Sc. PHYSICAL CHEMISTRY CH - 315 : Special Topics in Physical Chemistry (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE Answer books. 2) All Questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION - I Q1) Attempt any four of the following: [20] a) What are basic criteria for sensors? b) Write charge balance, mass balance and proton condition an thiosulphate in 0.4 m H2S2O3 solution. c) Classify sensors according to type of output signals and materials used. d) Find the fractions of H2C2O4, HC2 O−4 and C2 H 24− Given pH = 11.59, K a = 0.053, K a = 5.37 × 105 1 2 e) Explain catalysis in gas phase with suitable example. f) Discuss catalysis in concentrated strong acid solution. Q2) Attempt any four of the following: [20] a) Explain the influence of hydrogen and water vapour on the properties of semiconductor ceramics. b) Explain properties of conducting electrodes for operation of sensors. c) Define the terms activity, selectivity, stability inhibitor and catalyst. d) Explain catalytic cycle for acetal hydrolysis in aqueous acid medium. e) Write proton condition for H2CO3 and CH3COOH. f) Write the charge balance for 0.1M HCN and 0.1 M NaCN. [4923] - 35 2 SECTION - II Q3) Attempt any four of the following: [20] a) Give an account of scanning tunneling microscope. b) State and explain the characteristics of a passively smart materials. c) Calculate wavelength of an electron emitted in cathod ray tube operating at 10,000V. d) Differentiate between smart materials and intelligent materials. Describe any one method of preparation of an intelligent composites. e) Describe briefly pachinko machine. f) Describe briefly carbon nonotubes. Q4) Attempt any four of the following: [20] a) What are azeotropes? Describe one such system. b) What are the applications of nonogels? c) Write a note on fullerences. d) Write a note on constant boiling liquids. e) Explain the principle of steam distillation. f) How are rubber like ceramics prepared? Discuss their applications? l [4923] - 35 l 3 l Total No. of Questions :4] P1960 SEAT No. : [Total No. of Pages :3 [4923]-36 M.Sc. - II INORGANIC CHEMISTRY CH -326: Organometallic Compounds of Transition Metals and Homogeneous Catalysis (2008 Pattern) (Semester - III) Time : 3 Hours] Instructions to the candidates: 1) All questions are compulsory and carry equal marks. 2) Draw a neat diagram /figure wherever necessary. 3) Figures to the right indicate full marks. 4) At.No:Cr-24, Mn-25, Fe-26, Co-27, Ni-28, Cu-29. Q1) Answer any four of the following. [Max. Marks :80 [20] a) What are metal carbonyls? Explain various methods of preparation of metal carbonyls. b) What do you mean by Tollmans cone angle? How are they determined? State their importance in organometallic chemistry. c) Give the formal oxidation state of metal, d electron count, total valance electron & number of M-M bonds if any for the following complexes. i) [μ-CO(η4-C4H4)Fe (CO)]2 ii) Cp Mn (CO)3 iii) [CpCo (CO)2 (μ-CO)] iv) [Ru (pph3)2 Cl (NO)] v) [η6-C6H6 Mo(CO)3]+ d) What are metal carbenes? Give the synthesis of Fischer and Schrock carbene complexes. e) Discuss the catalytic cycle for oxo process using cobalt complex as a catalyst. P.T.O. Q2) Attempt any four of the following. [20] a) Give an account of reactions of organometallic complexes. b) Give the systematic classification of η5- cyclopentadienyl compounds. c) Complete the following reactions. i) [Cp(CO)2 Fe-CH3] + pph3 ⎯⎯ →? ii) Co2 (CO)8 + C2F4 ⎯⎯ →? iii) hv [Mn (CO C6H4me-P) (CO)5] ⎯⎯ →? iv) Mn2 (CO)10 + H2 ⎯⎯ →? v) → ? Mo (CO)6 + CH3 CN ⎯⎯ d) Discuss Wackers process of oxidation of olefins with the help of catalytic cycle. Explain the role of cocatalyst. e) Explain typical reactions of [(η6-C6H6)2Cr]. Q3) Answer the following (any four): [20] a) Discuss the general features of homogeneous catalysis and list out the various commercial applications of homogeneous catalysis. b) Give an account of use of organometallic compounds as activating and protecting agents. c) Discuss the mechanism of suzuki coupling reaction with suitable example. d) Give an overview of use of organometallic compounds in medicine. [4923]-36 2 e) What is EAN rule? Which of the following complexes obey EAN rule? i) [(η5-C5H5)2 MoH2] ii) [Co2 (CO)8] iii) [H Rh CO (pph3)2] iv) [Co (η5-C5H5)2] Q4) Write a note on (any four): [20] a) Tollman catalytic cycle. b) Metal phosphine complexes. c) Fluxional behaviour of organometallic compounds. d) Organometallic compounds as electrophile & nucleophile. e) Environmental aspects of organometallic compounds. O [4923]-36 O 3 O Total No. of Questions :4] P1961 SEAT No. : [Total No. of Pages :2 [4923]-37 M.Sc. II INORGANIC CHEMISTRY CH-330: Coordination Chemistry Magnetism and Reaction Mechanism (2008 Pattern) (Semester - III) Time : 3 Hours] Instructions to the candidates: 1) All questions are compulsory and carry equal marks. 2) Neat diagrams must be drawn wherever necessary 3) Use of logarithimic tables and calculator is allowed. [Max. Marks :80 Q1) Attempt Any Four of the following: [20] a) Explain why certain Ni (II) complexes show anomalous magnetic moments. b) What are magnetically diluted and concentrated systems. c) Explain the experimental magnetic moment of the following ions. i) Ti3+ μB . m. expt = 1.7 to 1.8 B.m. ii) Co2+ μB.m. expt = 4.1 to 5.2 B.m. [Given:- atomic no. of Ti=22 and Co=27] d) e) Explain the terms. i) Magnetic domain. ii) Canting. Draw the crystal field splitting of d orbitals of a central metal ion in symmetric octahedral, tetrahedral and tetragonal complexes. Q2) Attempt Any Four of the following: [20] a) Write about super exchange model for an antiferromagnetic interaction. b) Write a note on High spin-Low spin equilibria. P.T.O. c) Explain the extent of exchange interaction in the Cu2o2 ring system is greater than that in Cr2o2 ring system. d) What are mixed valence compounds? How they are classified? e) Explain the terms:i) Spin pairing. ii) Antiferromagnetic material. Q3) Attempt Any Four of the following: [20] a) Explain the main reaction types with suitable examples. b) Give in brief an account of π -bonding theory of trans effect. c) Write a note on anation reaction. d) Explain conjugate Base mechanism with reference to octahedral cobalt (III) complexes. e) Differentiate between Associative and Dissociative mechanism. Q4) Attempt Any Four of the following: [20] a) Discuss the mechanism of electron transfer with reference to outer- sphere reactions. b) Write a note on oxidative addition reactions. c) Discuss in brief recemization of trischelate complexes. d) Explain the various steps involved in photographic process. e) Complete the following chemical equations. i) (CH3)3B+ N(CH3)3 R ii) BF3+ F → iii) CH3Mn (Co)5 + PPh3 → iv) [Fe(CN)6]4-+ [Ircl6]2- → v) ? [PtCl4]2- ⎯ ⎯→ + ? ⎯ ⎯→ S S S [4923]-37 2 Total No. of Questions :4] P1962 SEAT No. : [Total No. of Pages :2 [4923]-38 M.Sc. II INORGANIC CHEMISTRY CH-331: Structural Methods in Inorganic Chemistry (2008 Pattern) (Semester - III) Time : 3 Hours Instructions to candidates: 1) All questions are compulsory. 2) Draw neat diagrams wherever necessary. 3) Figures to the right indicate full marks. 4) Use of log tables and calculators is allowed. Q1) Answer the following: (any four) [Max. Marks :80] [20] a) Explain the principle of NQR. b) What is a shift reagent? Which elements are used as shift reagents? How are they used? c) Explain with suitable examples the effect of. i) Heating rate. ii) Furnace atmosphere iii) Sample weight on TG curves- d) Explain the procedure to determine the different redox processes using cyclic voltametry. e) i) State selection rule for ESR. ii) State Braggs Law. Q2) Attempt any four: [20] a) Explain the instrumentation of DSC. b) Differentiate between SEM and TEM. c) What are miller indices? Compute the miller indices for faces & having intercepts as. P.T.O. i) 1 1 ,1, 3 2 ii) 2, 5 , 3 ii) 1 2 , ,∞ 2 3 d) Predict the ESR for D2 molecule. e) What do you understand by isomer shift in Mossbauer spectroscopy? Explain. Q3) Attempt any four : [20] a) NiSO4 7H2O degrades in three stages. Draw the thermogram and write the equations indicating the changes taking place. b) Explain what is meant by cathodic and anodic current? c) With the help of suitable examples discuss the selection rules of ESR and NMR. d) (i) Define the following terms. (1) Quadrupole splitting. (2) Epa & Epc. (3) g value in ESR. (ii) Which changes cannot be determined by TGA? e) How are the structures of Hypophosphorus and phosphorous acids determined using 19FNMR spectroscopy. Q4) Write short notes on: (any four) a) Braggs Law. b) Differential Thermal Analysis. c) Zero field splitting. d) TEM. e) Applications of Thermal techniques. S S S [4923]-38 2 [20] Total No. of Questions :4] P1963 SEAT No. : [Total No. of Pages :3 [4923]-39 M.Sc. II INORGANIC CHEMISTRY CH-332: Bio -Inorganic Chemistry Inorganic Elements in the Chemistry of Life (2008 Pattern) (Semester - III) Time : 3 Hours Instructions to the candidates: 1) All questions are compulsory. 2) All questions carry equal marks. Q1) Answer any four: [Max. Marks :80] [20] a) Discuss the types, structures and functions of copper proteins with one example each. b) Write the balanced reaction for oxidation of water at PS II. Explain with the help of S4 cycle, the steps involved in water oxidation. c) Explain with suitable examples different binding interactions of metal complexes with DNA. d) What are radiopharmaceuticals? Which techniques are used to monitor the α − and β− particles emitted from radiopharmaceuticals? e) Illustrate with a neat diagram the structure and function of enzyme carbonic anhydrase. Q2) Attempt the following (any four): [20] a) What is the principle of magnetic resonance imaging? How it is useful in clinical diagnosis? Write down the structures of at least two complexes that are used as MRI contrast agents. b) With the help of a neat diagram, explain the active site structure of enzyme urease. Name the metal ion present at the active site and the substrate for the enzyme. c) Give a detailed account of the oxidative cleavage of DNA by metal complexes with special emphasis on the types of radicals involved and selectivity towards nucleobases. P.T.O. d) e) Enlist the coenzymes of Vit. B12. Write down the reactions for the conversion of i) Mercury to methyl mercury. ii) Homocysteine to methionine. Name the copper proteins involved in i) Oxygen transport. ii) Oxygenation. iii) Oxidase activity. iv) Electron transfer and v) Antioxidative function Q3) Attempt any four: [20] a) What are the desired properties of metal complexes to act as MRI contrast agents? b) c) Match the following: Function i) Formation of methylmercury ii) Production of ammonia iii) Peptide bond cleavage iv) Electron transfer v) Water oxidation Draw the structures ofi) DOTA ii) [Fe-EDTA]2iii) iv) d) [4923]-39 Metal ion involved Ni Mn Cu Zn Co Oxyhemocyanin Cu+ (phen)2 v) Active site in Manganese catalase Fill in the blanks with the correct option: i) In blue copper oxidases, the by product is _______. 1) H2O 2) H2O2 3) H2 4) OOH 2 ii) e) iii) The polypyrrole ring present in Vit. B12 is _______. 1) Porphyrin 2) Chlorin 3) Protoporphyrin 4) Corrin _____enzyme isolated from erythrocytes was earlier known as erythrocuprein. 1) Cu-zn SOD 2) Urease 3) Catalase 4) Tyrosinase iv) Hydrogenases are enzymes that catalyze 2- e oxidation of _______. 1) CH4 2) H2 3) H2S 4) H2O v) The number of Cu and Fe ions present at the active site of cytochrome c oxidase are ____ and ____ respectively. 1) 2 and 3 2) 2 and 2 3) 3 and 2 4) 3 and 3 In developing any therapeutic radiopharmaceuticals, the choice of the radionuclides will depend on which factors? Q4) Write short notes on (any four): a) Important structural features of Vit. B12. b) Hydrogenases. c) Zn-fingers and other gene regulatory zn-proteins. d) Manganese peroxidases. e) Enzyme tyrosinase. S S S [4923]-39 3 [20] Total No. of Questions : 6] P1964 SEAT No. : [Total No. of Pages : 3 [4923]-40 M.Sc. - II ORGANIC CHEMISTRY CH - 350 : Organic Reaction Mechanism (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate full marks. 3) Answers to the two sections should be written in separate answer books. SECTION - I Q1) Attempt any four of the following: [12] a) Halogenation of unsymmetrical dialkyl ketone in acid and base catalysed conditions give different products. Explain. b) Explain the neighbouring group participation by heteroatoms. c) Discuss the generation and stability of carbenes with suitable examples. d) Give the synthetic applications of Henry reaction. e) Explain the significance of σ and ρ . Q2) Predict the products with mechanism in any four of the following: [16] a) b) P.T.O. c) d) e) Q3) Write notes on any three of the following: a) Kinetic isotope effect to determine reaction Mechanism. b) Use of pyridoxal in reductive amination. c) Crossover experiments. d) Dieckmann cyclisation. [12] SECTION - II Q4) Suggest the mechanism in any four of the following: a) b) c) [4923]-40 2 [16] d) e) Q5) Answer any four of the following: [12] a) Explain linear and non-linear Hammett plots. b) Discuss Newmann rule of six with an example. c) Explain the sandmeyer reaction with a suitable example. d) Explain the reduction of pyruvic acid by NADH. e) Substitution at β -position reduces the rate of hydrolysis in AAC2 mechanism. Explain. Q6) Answer any four of the following: [12] a) The pka of a p-chlorobenzoic acid is 3.98, pka of benzoic acid is 4.19. Calculate σ for P-Cl group. b) Which of the following is more acidic? Justify. c) Predict, which of the following will undergo epoxide formation readily. Explain. d) How will you prove the formation of cyclopropanone as an intermediate in Favorskii rearrangement. Explain. e) Thioester hydrolysis occurs more rapidly than ordinary ester hydrolysis. Explain. E [4923]-40 E 3 E Total No. of Questions : 6] SEAT No. : P1965 [Total No. of Pages : 5 [4923]-41 M.Sc. - II ORGANIC CHEMISTRY CH - 351 : Spectroscopic Methods in Structure Determination (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicates full marks. 3) Answer to the two sections should be written in separate answer books. SECTION - I Q1) a) b) Answer any Four of the following: [8] i) The mass spectrum of 1-Butanol shows peaks at m/t = 56 and 31. ii) How will you distinguish the following pair by PMR? iii) For routine work, 13CNMR spectrum of a compound is run twice. Why? iv) CIMS is used for compounds which show negligible M+ in the EIMS. Explain. v) Deuterated chloromethane shows seven lines in CMR. Explain. Two isomers of C5H8O2 show IR at 1780 cm1. Propose their structures and comment on their splitting pattern with peak areas (ratio). [4] P.T.O. Q2) Answer any four of the following: a) b) [16] Derive the structure and justify your answer. MF : C5H 10O 2 PMR : 4.1 (4H, S) 1.5 (6H, S) CMR : 25(q, strong), 68(t), 95(S) MF : C6H8O2Cl2 PMR : 1.45 (1H, d, 12Hz) 1.60 (3H, S) 2.29 (1H, d, 12Hz) 3.77 (3H, S) CMR : 18, 31, 35, 53, 63, 170 DEPT 90 : No peak DEPT 135 : 18, 53, UP 31 DOWN c) MF : C8H 10O 2 PMR : 2 (1H, bs, exch) 3.8(3H, S) 5 (2H, S) 6.5 (2H, d, J = 7Hz) 6.8 (2H, d, J = 7Hz) CMR : 55(q), 133.5(S), 64(t, mod.), 159(S) 114(d, strong), 129 (d, strong) d) Mass : 138, 137 and 107 MF : C9H11ON IR : 2842, 2720 and 1661 cm1. PMR : 3.1 (24mm, S) 6.7(8mm, d, J = 7.5 Hz) 7.72 (8mm, d, J = 7.5Hz) 9.75(4mm, S) e) Oxidation of compound C4H10O2 gives product with following spectral data. IR : 1770 cm1. PMR : 1.2 (2H, m) 2.5 (2H, m) 4 (2H, m) Mass : 86, 42 [4923]-41 2 Q3) Write short notes on any three of the following: a) Factors affecting geminal coupling constants. b) Various analyzers used in mass spectrometry. c) AMX system in NMR. d) Off-resonance spectroscopy. [12] SECTION - II Q4) a) b) Write the genesis of the ions (any four): i) CH3 (CH2)5=Br 166, 164, 135, 107 ii) n - C6H11N 97, 82, 68, 41 iii) 100, 99, 57 iv) 96, 95, 81, 53, 43 v) 98, 70, 55, 42 [12] An aromatic compound C11H14O. shows following peaks in its mass spectrum. Deduce its structure. [4] M/Z : 162, 134, 119, 91, 77, 71, 43. Q5) a) Assign the chemical shifts to various carbons. [4] 8(q), 17(q), 20(q), 28(t), 29(t), 34(t), 35(t), 49(s), 72(d), 82(d), 85(s), 123(s), 125(s), 135(d), 148(s). [4923]-41 3 b) Assign the chemical shifts and comment on the observed coupling constants and spin-decoupling experiments [C-CH3 and - pH signals are not given]. [8] 1.47(1H, d, 13Hz), 1.82(1H, d, 13Hz) 2.88(1H, dd, 9 and 2Hz) 3.46(1H, d, 8Hz), 3.63(3H, s), 3.94(1H, d, 8Hz) 4.51(2H, S), 5.07(1H, dd, 17 and 2Hz) 5.27 (1H, dd, 10 and 2Hz), 5.56 (1H, ddd, 17, 10 and 9Hz) NOE experiment: Irradiation at Change at 2.88 5.56(ddd) → dd(17,10Hz) 1.82 7% increase at 2.88 Q6) You are provided the spectra of a compound on the adjacent page. Analyse these spectras and arrive at a structure consistent with the data. Justify your structure. [12] [4923]-41 4 E [4923]-41 E 5 E Total No. of Questions : 6] P1966 SEAT No. : [Total No. of Pages : 5 [4923]-42 M.Sc. ORGANIC CHEMISTRY CH - 352 : Organic Stereochemistry (2008 Pattern) (Semester - III) (Old) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate Full marks. 3) Answers to the two sections should be written in separate answer book. SECTION - I Q1) Explain in detail (any Four): [16] a) Difference in two ionisation constants for Cis - cyclohexane -1, 2dicarboxylic acid is 2.42 pK units whereas for trans - cyclohexane 1, 2 - dicarboxylic acid it is 1.75. Explain. b) What is the difference between racemic mixture and racemic compounds? Give one example each. c) Why anti-7-nor bornenyl-p-toluene sulphonate A reacts faster than synisomer B which reacts faster than its saturated isomer C ? d) Explain the stereochemistry at ring junction for compounds (I) and (II). e) One of the isomers of benzene hexachloride undergoes dehydrohalogenation more slowly, by several powers of 10, than the remaining isomers. Explain. P.T.O. Q2) Predict the product/s giving mechanism (Any Four): [12] Q3) Attempt the following [Any three]: [12] a) Write short note on I-strain. b) Draw both the stable conformations of cis-anti-cis perhydrophenanthrene. Calculate their energy and comment on their optical activity. c) Write notes on: d) i) 2-alkyl ketone effect ii) 3-alkyl ketone effect Give conditions for good resolving agent. [4923]-42 2 SECTION - II Q4) Answer any three of the following: [12] a) On the basis of coupling constant explain the stereochemistry of lactone fusion into enhydrin. b) Give the evidence that Cinchonine and Cinchodine have different configuration at C8. c) How the configuration at C9 in quinine is deduced? d) Prove that in codeine C6 OH and C13 C15 bond are trans to each other. Q5) Answer any three of the following: [12] a) With reasons state whether the faces of the carbonyl groups in the following compounds are homotopic, enantiotopic or diastereotopic. b) Calculate the ee and the specific rotation of a mixture containing 6gm of (+)2 butanol and 4gm of () 2 butanol. The specific rotation of enantiometrically pure (+) 2 butanol is +13.5º. c) Write the products obtained by hydride addition from Re and Si faces on following compound. d) Explain the terms: i) Chiral auxillary. ii) Topicity [4923]-42 3 Q6) a) Predict the product/s. Explain the stereochemistry and mechanism in any four of the following reaction: [8] [4923]-42 4 b) Suggest the reagent/s and stereochemistry of the following reactions. (any two): [8] E [4923]-42 E 5 E Total No. of Questions :6] SEAT No. : P1967 [4923]-43 [Total No. of Pages :5 M.Sc. II ORGANIC CHEMISTRY CH-353: Free Radicals, Photochemistry and Pericyclic Reactions (2008 Pattern) Time : 3 Hours] [Max. Marks :80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate full marks. 3) Answers to the two sections should be written in separate answer books. SECTION - I Q1) Suggest suitable mechanism for any four of the following: [12] a) b) c) P.T.O. d) e) Q2) a) b) Explain the detection methods of free radicals. [4] Predict the product/s indicating mechanism in any five of the following: [10] i) ii) iii) iv) [4923]-43 2 v) vi) Q3) a) b) Explain any Two of the following: [6] i) Irradiation of O-xylene yields a mixture of m-and p-xylenes. ii) Free radical chlorination of both n-propyl and isopropyl bromide give the same product, 1-bromo-2- chloropropane. Explain. iii) Cyclobutanone undergoes three types of photo reaction. Write short notes on any two of the following: [8] i) Photo reduction of carbonyl compounds. ii) Intramolecular hydrogen abstractions of carbonyl compounds. iii) Arylation of aromatic rings. SECTION - II Q4) a) With the help of PMO method prove that cope rearrangement occurs preferentially through a chair like rather than a boat like transition state.[6] b) Predict the product/s in any four of the following reactions. Explain their stereochemistry and mechanism. [8] i) Trans - 5, 6 - dimethyl - 1-cyclohexadiene ii) [4923]-43 3 Δ ? ⎯⎯⎯→ iii) iv) v) Q5) a) b) Draw the molecular orbital of pentadienyl system. Comment on their symmetry with respect to C2 axis of symmetry. [4] Explain the mechanism for any four of the following reactions: i) ii) iii) iv) v) [4923]-43 4 [8] Q6) a) Complete the following synthetic sequence indicating all intermediates and reagents required. [6] b) Complete any two of the following synthetic sequences indicating all intermidiates and reagents required. [8] i) ii) iii) EEE [4923]-43 5 Total No. of Questions :4] SEAT No. : P1968 [Total No. of Pages :3 [4923]-44 M.Sc. (Part - II) ANALYTICAL CHEMISTRY CH-390: Electroanalytical and Current Analytical Methods in Industries (2008 Pattern) (Semester - III) Time : 3 Hours [Max. Marks :80 Instructions to the candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic table/ calculator (non-programmable) is allowed. SECTION -I Q1) Attempt any four of the following: [20] a) Explain, How polarographic technique is useful for qualitative and quantitative analysis? b) State the principle of coulometry. Describe the general procedure for coulometric determination at controlled cathode potential. c) Write a critical note on cyclic voltametry. d) A sample of copper ore weighing 2.0 g is dissolved in acid and the copper is electrolysed using constant current of 2.0 amperes at 10 min. Calculate the percentage of copper in the ore. [Given: At.wt. of Cu=63.54] e) Calculate the diffusion current of Cd 2+ ion in a solution having concentration 10.0 mM, if drop time was measured at the rate of 3.47 sec per drop. The mercury flow rate was 1.72 mg per second. [Given: diffusion coefficient of Cd2+=6.7×10-6 cm2 s-1] P.T.O. Q2) Attempt any four of the following: [20] a) State the principle of amperometry. Describe the nature of amperometric titration curves. b) What is stripping voltametry? Explain the purpose of the electrodeposition step in stripping analysis. c) Give Ilkovic equation. Explain the terms involved in it. d) Write a critical note on chrono-potentiometry. e) Estimate the peak current at a scan rate of 25.0 mV/s, for the forward scan of a triangular wave voltamogram at a disk electrode. Peak current of 15.0 μ A was observed at a scan rate of 0.75 V/s , assuming a reversible electro- chemical reaction. SECTION -II Q3) Attempt any four of the following: [20] a) Explain the principle of activation analysis , mention the types of activation, mention the types of activation analysis. Describe the absolute method of neutron activation analysis. b) State the principle of isotope dilution analysis. Explain, How isotope dilution analysis is used to assess the volume of blood in a patient. c) Discuss the principle of radiometric titrations. Draw and describe the nature of radiometric titration curve, only when titrant is radioactive. d) The transmittance of unknown sulphate sample was 75%, the cell pathlength was 1.0 cm and the turbidity coefficient of the sample was 4.88×10-3 lit mg-1 cm-1. Determine the concentration of sulphate in ppm of unknown sample. e) Calculate the percentage of penicillin in the mixture, when 1 lit. mixture was assessed for its penicillin content, 2 mg of labelled penicillin with an activity of 8000 counts for 5 min was added to this mixture. After thorough mixing 0.5 mg of pure crystalline penicillin was isolated which gave an activity of 3000 counts for 10 min. [4923]-44 2 Q4) Attempt any four of the following: [20] a) Give the criteria to prefer turbidimetry or nephelometry as an analytical tool. Describe with suitable example any one important application of turbidimetry in analytical chemistry. b) Draw a neat labelled TGA curve. Discuss the effect of particle size and furnace atmosphere on the nature of TGA curve. c) Give the construction, properties and working of optically transparent electrodes. d) Write a note on differential scanning calorimetry. e) The thermal curve of a 120 mg sample contained a mixture of CaC2O4; H2O ( Mol. wt.=148.12) and thermally stable salt had mass loss of 7.5 mg at temperature about 140°C corresponds to vaporisation of water. Determine the percentage of CaC2O4; H2O in the mixture. S S S [4923]-44 3 Total No. of Questions :4] SEAT No. : P1969 [Total No. of Pages :3 [4923]-45 M.Sc. - II ANALYTICAL CHEMISTRY CH-391: Environmental and Analysis of Industrial Materials (2008 Pattern) (Semester - III) Time : 3 Hours] [Max. Marks :80 Instructions to the candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic tables, non-programmable calculators is allowed. SECTION -I Q1) Attempt any four of the following: [20] a) Explain the procedure for estimation of nitrogen from sample of urea. b) Give an analytical procedure for determination of lead from sample of lead glass. c) Explain the term cosmetics. Give the procedure for the estimation of magnesium from cosmetics. d) Explain the term propellent and explosive. Describe analytical method for determination of calcium from propellant. e) A sample of face powder weighing 2.25 gm was dissolved in acid & the solution was diluted to 250 ml. 50 ml aliquot was analysed for SO42- & it gave 0.300 gm of BaSO4, calculate the percentage of sulphate & sulphur from given sample. (Given: At.wt. Ba=137 , S=32, O=16) Q2) Attempt Any four of the following a) [20] What is active ingradient of detergent? How it is determined? P.T.O. b) Define the terms: i) Pigment ii) Binder iii) Vehicle iv) Varnish v) Flash point c) Write a short note on quantitative test of explosives. d) 0.5 gm sample containing MnO2 is heated with conc. HCl liberating Cl2. Then Cl2 was passed through a solution of KI and 33.0 ml of 0.11 M Na2S2O3 is required to titrate the liberated I2. Calculate the percentage of MnO2 in sample. [Given: At. wt. I=127 , Mn=53.93, O=16] e) 0.60 gm sample of ilemenite was fused with potassium persulphate and the mass was extracted with H2SO4 solution. After removal of insoluble matter the filtrate was diluted to 100 ml. From it an aliquot of 50 ml after removal of iron, Ti-cufferon complex was precipitated. After ignition of the precipitate 0.156 gm of titanium oxide was obtained. Calculate the percentage of TiO2 & Ti in the given sample. [Given: At. wt. Ti=47.88 , O=16] SECTION -II Q3) Attempt any four of the following: [20] a) What is steel? Explain the analytical procedure for estimation of nickel from steel. b) Explain the analytical method for estimation of Al2O3 from bauxite ore. c) What are copper base alloys? Explain the method used for estimation of copper. [4923]-45 2 d) 4.250 gm of washing soda was dissolved in distilled water and diluted to 250 ml. A 25 ml aliquot of this solution titrated with 0.1 N HCl using methyl orange as an indicator and gave burette reading of 28 ml. Calculate the percentage of sodium carbonate in given sample. [At. wt. Na=22.98 , C=12 , O=15.99] e) Analysis of the component of 2.00 gm of shipnail, brass yielded 0.068 gm of SnO2 & 0.280 gm of PbSO4. Calculate percentage of each metal in alloy. [Given: At.wt. Sn=118.7 , Pb=207.2 , O=16, S=32] Q4) Attempt any four of the following [20] a) Give an account of estimation of dissolved oxygen. b) Give note on electrostatic precipitator. c) What is sludge? Give any two methods used for disposal of sludge. d) Describe trickeling filter process. e) Explain principle and construction of cyclone separator. S S S [4923]-45 3 Total No. of Questions :4] P1970 SEAT No. : [Total No. of Pages :3 [4923]-46 M.Sc. II ANALYTICAL CHEMISTRY CH-392: Advanced Analytical Techniques (2008 Pattern) (Semester - III) Time : 3 Hours [Max. Marks :80] Instructions to candidates: 1) Answer to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic tables / calculators (non-programmable) is allowed. 5) Use of graph paper is allowed. SECTION -I Q1) Attempt any four of the following: [20] a) State and explain faradays laws of electrolysis. Give its important applications. b) Give the classification of amplifiers on the basis of. i) Coupling and. ii) Frequency response. c) Draw a schematic diagram for operational amplifier. Explain the function of various components. d) Explain the use of Rc circuits as high pass and low pass filters. e) Solve the following. i) Convert 11010 in the binary system to decimal system. ii) Perform the addition 29 + 6 with binary arthimatic. Q2) Attempt any four of the following: [20] a) Write a critical note on continous flow analyzers. b) Draw the outline of microprocessors control in atomic absorption spectrophotometers. P.T.O. c) Write a short note on centrifugal force analyzers. d) Explain the scope of the microprocessor control of potentiometer in analytical Laboratories. e) In a certain transister, the emitter current is 1.20 times as large as the collector. If emitter current is 12 μA. Find base current. SECTION - II Q3) Attempt any four of the following: a) [20] Explain the following termsi) Pressure broadening. ii) Droppler broadening. iii) Plasma. iv) Electron multiplier. b) Mention the element required in micro nutrients for the growth of roots. Explain any one suitable method for determination of copper from the soil sample. c) Compare the atomic mass spectrometry and molecular mass spectrometry with respect to principle and method of analysis. d) Write a note on super critical fluid chromatography. How will you compare SFC to other column chromatography. e) A well water sample is analysed by FES for sodium at 589.5 nm. The emission signal is 4.5 unit as emission scale. A series of standard solution gives the following results. Standard sodium in Emission Reading PPm (ER) 0.2 0.32 1.0 1.40 5.0 6.50 Determine the sodium level in PPm for well water sample. [4923]-46 2 Q4) Attempt any four of the following: [20] a) Write a short note on resonance Ionisation spectroscopy. b) Explain the role of Sfc as an analytical tool in pharmaceutical analysis c) Compare RIA and ELIS. A technique. Explain their relative merits and demerits. d) Write a note on. e) i) Immunoblotting. ii) Immuno electrophoresis. A 400 mg sample of hair from a young child is digested in HNO3- HclO4 and diluted to 25 ml. A 10 ml aliquot is diluted to 25 ml and analysed with cadmium hollow cathode tube. The absorbance reading is 0.15. To a second 10 ml aliquot 1 ml of 0.400 ppm standard cadmium solution followed by dilution to 25 ml and analysis for cadmium the absorbance reading is 0.19 calculate the cadmium content in the hair sample and compare it with the mean value of 3.3 ppm found for children. S S S [4923]-46 3 Total No. of Questions :4] P1971 SEAT No. : [4923]-47 M.Sc. II ANALYTICAL CHEMISTRY CH-380: Pharmaceutical Analysis (2008 Pattern) (Semester - III) [Total No. of Pages :3 Time : 3 Hours [Max. Marks :80] Instructions to candidates: 1) Answer to the two sections should be written in sepatate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of non-programmable calculator / logarithmic table is allowed. SECTION -I Q1) Answer any four of the following: [20] a) How water in pharmaceutical preparation is determined? b) Explain in brief the manufacturing Hazards. c) How is self life estimated? d) Write note on cross- contamination. e) 0.40 g adrenaline [CgH13O3N] sample was dissolved in 50 ml of glacial acetic acid and solution was titrated with 0.1 N Acetous perchloric acid using two drops of crystal violet indicator. The Burette reading was 15.5 ml. Determine percentage of adrenaline in the sample. [Given:- mol. wt. of adrenaline = CgH13O3N = 183.099 gm] Q2) Answer any four of the following: [20] a) What are solutions? Give the classification of solutions used in pharmaceutical preparations. b) Give brief account of Gel and Lotions. c) Discuss limit test for Iron and sulfate. P.T.O. d) Write a note on antibiotic assay. e) An accurately weighed 0.2 gm of phenobarbitone [C12H12 N2o3] sample was dissolved in 30 ml dimethyl for mamide. The solution was then titrated against 0.1 N lithium methoxide solution using quinaldine red indicator. The burette reading was 8.6 ml. Determine the percentage of phenobarbitone in the sample. [Given Mol.wt. of phenobarbitone [C12 H12 N2o3]= 184 gm]. SECTION -II Q3) Answer any four of the following: [20] a) Define sterilization and give membrane sterilization process for pharmaceutical product. b) Explain the different phases in New drug development. c) Write in brief the procedure for determination of thiomersal. d) Give an assay of aspirin. e) 1.2 gm salicylic acid [C10 H80] sample was dissolved in 10 ml of ethanol, to this 50 ml 0.5 M NaoH solution was added and the solution was boiled for 15 minutes. After cooling, the excess of alkali was titrated with 0.5 m Hcl solution using phenol red indicator. The titration reading was 20.1 ml. The blank titration reading was 50 ml. Determine the percentage of salicylic acid in given sample. [At.wt. C=12, O=16, H=1] Q4) Answer any four of the following: a) Explain role of diluents in tablet preparation. b) Give an account on ointment- and creams. c) Give Advantages and Disadvantages of Aerosols. d) What are [4923]-47 i) Sub standard drugs ii) Generic drugs. 2 [20] e) 0.751 gm of Ascorbic acid sample was dissolved in 25 ml of water and diluted to 100 ml. 20 ml of diluted solution was titrated with 0.1 N I2 solution using 1 ml starch solution as an indicator. The titration reading was 1.8 ml. Determine the percentage of ascorbic acid in the given sample [At.wt C=12.011, H=1.008, 0=16] S S S [4923]-47 3 Total No. of Questions :4] P1972 SEAT No. : [4923]-48 M.Sc. II ANALYTICAL CHEMISTRY CH-381: Medicinal Chemistry (2008 Pattern) (Semester - III) [Total No. of Pages :2 Time : 3 Hours [Max. Marks :80] Instructions to candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic tables, non-programmable calculators is allowed. SECTION -I Q1) Attempt any four of the following: [20] a) Write a short note on biological assay of drugs. b) What is a drug receptor? Discuss the elementary treatment of drug receptor interactions. c) Give a brief account of new procedures followed in drug design. d) Discuss the mode of action of novel drug delivery system. e) Discuss the history and development of QSAR. Q2) Attempt any four of the following: a) Write a short note on Free- Wilson analysis. b) Define:- c) i) Drug receptors ii) Pro- drug iii) Drug activity iv) Soft - drug [20] What is a drug? Give the classification of drugs on basis of therapeutic action. P.T.O. d) Write an account of uses of pharmacokinetics in drug development process. e) Enlist the theories of drug activity. Discuss any two theories SECTION -II Q3) Attempt any four of the following: a) [20] Give the process of synthesis of: i) Quinidine. ii) Verapamil. b) Write a short note on cancer chemotherapy. c) Define antibiotics. Give an account of lactamrings antibiotics inhibiting protein synthesis. d) Discuss the mode of action of sulphonamides or ciprofloxacin. e) Write a short note on stereochemical aspects of Psychotropic drugs. Q4) Attempt any four of the following: a) What is a local antifective drug? Discuss with suitable examples. b) Give an account of cardiovascular diseases. c) Discuss mode of action of hypnotics and anti- anxiety drugs. d) Give the process of synthesis of: e) i) Alprazolam. ii) Glutethimide. Give an account of carcinolytic antibiotics and mitotic inhibitors of uracil and mechlorithamine. S S S [4923]-48 [20] 2 Total No. of Questions :6] P1973 SEAT No. : [Total No. of Pages :3 [4923]-51 M.Sc. PHYSICAL CHEMISTRY CH-410: Molecular Structure and Spectroscopy (2008 Pattern) (Semester - IV) (Old) Time : 3 Hours [Max. Marks :80] Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPATATE answer books. 2) ALL questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic tables, calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION -I Q1) Attempt any three of the following: [15] a) Discuss the factors influencing the coupling constant in nmr spectra. b) Explain the principle and mechanism of FT nmr. c) What do you understand by nqr group frequencies? Explain their uses in molecular structure determination. d) Define the terms: Chemical Shift, Larmor frequency. Coupling constant and spin- spin relaxation in nmr. e) Write a note on: 13C nmr spectroscopy. Q2) Attempt any three of the following: [15] a) Discuss the origin of the hyperfine interactions in the esr. b) What is the basic principle of photoacoustic spectroscopy (PAS)? Describe the instrumentation used in PAS. c) What is g- Value? Discuss the factors affecting the g- Value. d) Distinguish between nmr and esr spectroscopy. e) Write the Mc Connell equation and explain the terms their in. Discuss its applications in esr. Q3) Solve any two of the following: [10] a) Find the magnetic field that produces resonance condition for a sample with g- Value 3.1 in esr spectrometer using 30 mm radiation. b) Calculate the nmr frequency of 35Cl in magnetic field of intensity 1.6 T. (Given: I=3/2 , μ=1.06 in units of βn) c) Predict the esr spectrum of napthalene anion. SECTION -II Q4) Attempt any three of the following: a) [4923]-51 [15] What is XRD? Explain the interference of wave motions observed in XRD. 2 b) Give in a brief account of Braggs method used in the elucidation of crystal structure. c) State how the structure factor is used to determine the electron density distribution. d) Discuss the limitations of the electron diffraction method. e) Write an account of diffraction of electrons by gases with special reference to Wierl equation. Q5) Attempt any three of the following: [15] a) Describe with suitable diagram, the uniform field method for measurement of magnetic susceptibility. b) What are the advantages and disadvantages of Faraday method over Gouy method? c) Derive the Langevin formula for molar diamagnetic susceptibility. d) What is electron diffraction? Give its applications. e) Define the terms: diamagnetism, paramagnetism, ferrimagnetism and ferromagnetism. Q6) Solve any two of the following: [10] a) Calculate the unit cell length of sodium chloride cubic crystal having density 2.163 gcm-3. b) Calculate the volume and mass paramagnetic susceptibilities of a sample of complex salt with five unpaired electrons at 273k. (Given: density =2.87 gcm-3, molar mass=324.4 gmol-1) e) Calculate the molar susceptibility of pyridine and phenanthroline. Given: χA=C:- 6.0 × 10-6, H:-2.93 × 10-6 Ring N: -4.61×10-6 λ= C in ring:-0.24 × 10-6 C shared by two rings:- 3.07 × 10-6 [4923]-51 S S S 3 Total No. of Questions :6] P1974 SEAT No. : [Total No. of Pages :4 [4923]-52 M.Sc. PHYSICAL CHEMISTRY CH-411: Surface Chemistry and Electro-Chemistry (2008 Pattern) (Old) (Semester - IV) Time : 3 Hours [Max. Marks :80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE answer books. 2) ALL questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic tables, calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION -I Q1) Answer any three of the following: [15] a) Give a critical comparison of various models used for multilayer adsorption. b) What is Gibbs monolayer? Describe PLAWM technique for measuring film pressure. c) Describe volumetric method for studying adsorption of gas on solid. d) Derive two dimensional ideal gas law for film formed on liquid surface. How it is used to determine molecular weight of protein. e) What is catalyst deactivation? Discuss in brief the causes of deactivation. Q2) Answer any three of the following: [15] a) Define detergency and Explain various factors involved in detergent action. b) What is spreading coefficient? Derive the equation for spreading coefficient interms of surface tension. c) What are Zeolites? Give their important applications. d) What is flotation? Explain its mechanism and give its important applications. e) Describe different states of monomolecular films. Q3) Solve any two of the following: a) [10] Following table gives data for adsorption of methane on 1 g of charcoal at 0°C the data obeys the Langmuir isotherm, determine the constants a and Vm in Langmuir equation. P (mm Hg) 100 200 300 400 V (ml) 9.75 14.5 18.2 21.4 [4923]-52 2 b) The mass x of a solute adsorbed per gram of a solid adsorbent is given by Freundlich adsorption isotherm x = kCn where k and n are 0.16 and 0.43 respectively, calculate the amount of acetic acid. (M=60 g/mol) that 1 kg of charcoal would adsorb from 0.84 m vinegar solution. c) The surface tension of ethanol water mixture follows the equation γ =70−0.5C+0.2 C2, where C is ethanol concentration in moles/lit calculate Γ in moles cm2 for 0.5M solution at T=25°C. SECTION -II Q4) Answer any three of the following: a) Describe the structure of water when ion is present in it. b) Show that maximum value of charge on spherical cell is at c) Explain the terms: i) Galvanic potential ii) Outer potential iii) Surface potential iv) Electrochemical potential [15] . d) Derive Einstein equation relating diffusion coefficient and mobility of ion. e) Describe the Gouy-Chapman model for electrical double layer across the interface. Q5) Answer any three of the following: a) Explain the terms. i) Exchange current density. ii) Over potential. iii) Equilibrium potential. iv) Transfer coefficient. b) Discuss the local cell theory for corrosion of metals. c) With neat diagram describe any one example of fuel cell. [4923]-52 3 [15] d) e) Give one example of each type of electrosynthesis. i) Anodic oxidation. ii) Cathodic reduction. Derive Tafel equation from Butler-Volmer equation from Tafel equation. Q6) Solve any two of the following. [10] a) A 800 ml of 0.2M Na3PO4 is mixed with 200ml of 0.4M ZnCl2. Calculate the ionic strength of solution assuming complete dissociation. b) The diffusion coefficient of K+ in 0.1M KCl at 25ºC was measured with a radioactive tracer Na* as D = 1.3 × 109 m2s1. Calculate the electric mobility of K+ in this solution. c) The following reaction may be made to operate in fuel cell at 298K. CH4 + 2O2 U CO2(g) + 2H2O(l) ΔH 298 = 890.2 kJmol1, ΔG 298 = 818.0 kJmol1. Calculate: i) The number of electrons transfered overall in cell reaction. ii) The reversible emf of the cell at 298 K. iii) The maximum efficiency of cell. E [4923]-52 4 E E Total No. of Questions :4] P1975 SEAT No. : [Total No. of Pages :3 [4923]-53 M.Sc. PHYSICAL CHEMISTRY CH-414: Biophysical Chemistry and Related Techniques (Old) (2008 Pattern) (Semester - IV) (Optional) Time : 3 Hours] [Max. Marks :80 Instructions to the candidates: 1) Answers to the TWO sections should be written in SEPARATE answer books. 2) ALL questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table, calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION -I Q1) Attempt any four of the following: [20] a) Calculate the pH of 2 litres of a solution containing 5 cc 5 M acetic acid and 5 ml 1M Sodium acetate (pKa=4.75) b) Explain role of caldesmon in muscle contraction. c) Discuss ATP metabolism in cell biology. d) Explain tests of proteins. e) Distinguish between primary and secondary proteins. f) Write a note on reverse osmosis. Q2) Attempt any four of the following: [20] a) Explain proteolysis and chaperonins. b) Calculate Rrms for a polymer having 1250 monomer units and 1400 nm long. c) Explain the Pauling structure of proteins. d) Distinguish between Rrms and Rrmp. e) Write a note on blood buffering system. f) What are flickering clusters? Explain with a diagram. SECTION -II Q3) Answer any four of the following: [20] a) Using the unit membrane model, explain the structure of the cell membrane. b) Discuss briefly the factors affecting enzyme activity. c) What is all or none law? Explain. d) What are biopolymers? State their characteristics and applications. e) What is enzyme inhibition? Explain briefly reversible inhibition. f) Derive Michaelis- Menton equation for enzyme catalysis. [4923]-53 2 Q4) Answer any four of the following: [20] a) Describe viscosity method to determine the molecular weight of biopolymers. b) Discuss the applications of circular dichroism. c) Write a note on helix- cell transitions. d) How is the molecular weight of a protein determined by gel electrophoresis? e) Explain how the ions are transported through a cell membrane. f) Write a note on optical rotatory spectroscopy. S S S [4923]-53 3 Total No. of Questions :4] P1976 SEAT No. : [Total No. of Pages :3 [4923]-54 M.Sc. PHYSICAL CHEMISTRY CH-415: Special Topics in Nuclear Radiation Chemistry ( Old 2008 Pattern) (Semester - IV) Time : 3 Hours [Max. Marks :80] Instructions to the candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are COMPULSORY. 3) Figures to the RIGHT SIDE indicate FULL marks. 4) Use of logarithmic table, calculator is ALLOWED. 5) Neat diagrams must be drawn WHEREVER necessary. P.T.O. SECTION -I Q1) Attempt any four of the following: [20] a) Define in vivo diagnosis. How is it achieved using radio- isotopes. b) Write a note on technitium generator. c) Discuss the principle and procedure of positron Emission Tomography technique. d) Which radio- isotopes are used in food processing? What are the advantages of radiation processing of food? e) Describe the method of separation of uranium isotopes. Q2) Attempt any four of the following: [20] a) Explain CNO bicycle. b) Give classification of meteorites. c) Give an account for solid and gaseous radioactive waste management. d) Draw and explain the layered structure of a star after nucleosynthesis. e) Explain the terms cosmology, nucleosynthesis and sand process. SECTION -II Q3) Attempt any four of the following: [20] a) Discuss neutralization radiometric titration with a neat labelled diagram. b) Discuss the phenomenon of radiolysis of hydrocarbons. c) What is the necessity of thin targets? How are they prepared? d) Write a note on carries. e) Give an account of experimental set up of neutralization reactions using radioactive kryptonates. [4923]-54 2 Q4) Attempt any four of the following: [20] a) Explain the procedure for determination of beam energy. b) Define chain types and chain reactions. c) 20 cc of zinc ions labelled with 65Zn were titrated with 0.001 m dithiozene. Addition of 2 cc of titrant followed by extraction of complex showed drop in activity from 10200 for 5 minutes to 1700 cpm. Calculate the concentration of zinc ions in terms of molarity. d) Explain competition technique giving example. e) Define radical scavenging. Explain it with a suitable example. S S S [4923]-54 3 Total No. of Questions : 4] SEAT No. : P1977 [Total No. of Pages : 2 [4923]-55 M.Sc.-II INORGANIC CHEMISTRY CH-430 : Inorganic Polymers and Heterogeneous Catalysis (2008 Pattern) (Semester-IV) Time : 3 Hours] Instructions to the candidates: 1) All questions are compulsory. 2) All questions carry equal marks. 3) Neat diagrams should be drawn wherever necessary. [Max. Marks : 80 Q1) Answer Any Four: [20] a) Explain the formation of SO2 using vanadium catalysts. b) How are metal nanoparticles stabilized in solution? c) What is meant by adsorption isotherm? Explain one adsorption isotherm with reference to hetero-catalyst. d) What is meant by Turn Over Frequency? What is its significance? e) Explain the importance of surface area and porosity of heterogeneous catalysts. Q2) Attempt Any Four: [20] a) Write an account on Heteropolyanions of Molybdenum. b) Differentiate between physical and chemical adsorption. c) Highlight the structural pecularities of different SN compounds. d) How do x-ray diffraction and SEM techniques help to understand the structure of catalysts? e) Discuss the different methods of preparing supported metal catalysts. P.T.O. Q3) Answer Any Four: [20] a) Write an account on applications of zeolites in catalysis. b) Discuss the structure and electrical conductivity of polythiazyl ion using MOT. c) What do you understand by the term supported metal catalyst? Comment on the importance of selection of support and its role in catalysis. d) Find out the number of framework electrons in [Mo(CO)16] and predict its structure. e) Explain the importance of heterogeneous catalysis in Food and petroleum industry. Q4) a) b) c) Match the following: [20] NiO polymerization H2SO 4 associative chemisorption CO dehydrogenation CH4 catalyst precursor H2S dissociative chemisorption Complete the following equations: i) B3 N 3H 6 + HCl → ? ii) CO/NaOH/NeOH NeOH [PtCl6 ]−− ⎯⎯⎯⎯⎯ ⎯ → ? ⎯⎯⎯ →? Δ iii) anhy. (PNCl 2 )3 +C6 H 6 ⎯⎯⎯ →? AlCl3 iv) P4 H10 + H 2 O → ? Write notes on Any Two: i) MCM - 41 catalyst. ii) Polycationic compounds. iii) Metal oxides as catalysts. [4923]-55 2 Total No. of Questions : 4] SEAT No. : P1978 [Total No. of Pages : 2 [4923]-56 M.Sc.-II INORGANIC CHEMISTRY CH-431 : Material Science (Semester-IV) (2008 Pattern) Time : 3 Hours] Instructions to the candidates: 1) All questions are compulsory. 2) Neat diagrams must be drawn wherever necessary. 3) Figures to the right indicate full marks. 4) Use of logarithmic tables and calculators is allowed. Q1) Attempt Any Four of the following: [Max. Marks : 80 [20] a) Explain the origin of Valence Band and Conduction Band on the basis of band energy level diagram. b) Define nanomaterials. Properties of nanomaterials are size dependent. Justify. c) How is crystal structure affected by dehydration? Explain the removal of water during solid-state dehydration reactions. d) State different applications of Ficks Law of diffusion. e) Define coherence length. Explain the classification of superconductors with graphical representation and examples. f) What is asphalt? What are chemical composition ranges for asphalt? Where is it obtained? Q2) Attempt Any Four: [20] a) Describe the Czochoraiskii method for obtaining single crystal of germanium. b) In germanium energy gap is 0.75 eV. What is the wavelength at which it will start absorbing light? P.T.O. c) Find the drift velocity for an electron in silver wire of radius 1mm and carrying a current of 2 amperes. (Density of silver is 10.5 gm/cc; Avogadaros number = 6.023 × 1023). d) Define ferromagnetism. The saturation magnetisation of FCC and simple cubic iron is 1700 kA/m2 and 1600 kA/m2 respectively. Calculate the net magnetic moment per iron in the crystal. Lattice constant of FCC or simple cubic iron is 2.87 AD . e) Derive the expression of curie law. f) Explain the different applications of Biomaterials. Q3) Attempt Any Four: [20] a) What is photo conductivity? With the help of band energy diagram explain the phenomenon of photoconductivity. b) Discuss the principle underlying the operation of thermocouples and refrigerators. c) What is difference between softwood and hard wood? Describe the different layers in the cross section of a tree stem. d) Give the different applications of superconducting materials. e) Write an account on different types of magnetism. f) What is a Hysteresis loop? Explain the types of Hysteresis loops. Q4) Write notes on (Any Four): [20] a) n-p-n transistors. b) Luminiscence. c) Schottkey and Frenkel Defects. d) Pervoskites. e) Portland cement. f) Silicate glasses. [4923]-56 2 Total No. of Questions : 9] SEAT No. : P1979 [Total No. of Pages : 4 [4923]-57 M.Sc.-II INORGANIC CHEMISTRY CH-445 : Inorganic Applications in Industry, Biotechnology and Environmental Chemistry (2008 Pattern) (Semester-IV) Time : 3 Hours] Instructions to the candidates: 1) Attempt any two sections from the following. 2) Both sections should be written in the same answer book. 3) All questions are compulsory. 4) Figures to the right indicate full marks. 5) Neat diagram must be drawn wherever necessary. 6) Use of logarithmic table/calculator is allowed. [Max. Marks : 80 SECTION-I (Inorganic Applications in Industry) Q1) Attempt Any Three of the following: a) b) [15] What is meant by term pigment? Explain the following properties of inorganic pigments. i) Colour and tints. ii) Reactivity with vehicle. iii) Hiding power. iv) Chemical resistance. Explain the methods for electroplating of precious metals. P.T.O. c) Explain how such complexes as prussian blue and ferrocene modify the behaviour of electrodes in electroplating. d) Draw a cross section of typical tree. Explain various layered with functions. Q2) Attempt Any Three of the following: [15] a) How are the redox centres ligand to PVP electrode coating? Explain the effect of increasing the positive potential of the platinum electrode on electro deposition. b) What are the main types of synthetic fibre? Explain any one with production and properties. c) Explain two methods of electroplating of Tin. d) A piece of wood containing moisture weights 174.3 gm and after oven drying its constant weight is 156.5 gm. What is its percentage moisture content? Give your comment on the quality of wood. Q3) Write notes on Any Two: [10] a) Yellow pigment. b) Alloy plating. c) Production of portland cement. SECTION-II (Environmental Chemistry) Q4) Attempt Any Three of the following: [15] a) Describe how nitrogen can be removed from the waste water by biological treatment. b) Compare aerobic treatment process with an anerobic treatment process. [4923]-57 2 c) Draw a schematic diagram of a phosphoric acid fuel cell (PAFC). What reaction occurring at the cathode and anode. Show overall reaction. d) What does tertiary treatment in a sewage treatment plant removes the waste stream? Q5) Attempt Any Three of the following: [15] a) Will geothermal energy ever be a major source of energy world wide? Explain. b) How do you differentiate between active and passive solar heating system? c) Define pE. What is the range of pE in natural water? A sample from lake gave a pE = 10.5 does the lake favour oxidation? d) List four forms of biomass. What is the energy yield obtained from burning? List the advantage and disadvantage of using biomass as a source of energy. Q6) Write short notes Any Two: [10] a) Chemical oxygen demand. b) Electrodialysis. c) Wind power. SECTION-III (Biotechnology) Q7) Attempt Any Three of the following: [15] a) With any two examples explain how biotechnology is related to other branches of science and technology? b) Describe the process of producing food from fungi. [4923]-57 3 c) Give the stages involved in tissue culture. d) Describe the steps involved in the synthesis of insulin from clone DNA segment. Q8) Attempt Any Three of the following: [15] a) Give an overview of chemical reactions involved in the production of biohydrogen. b) What is renin? Describe an experiment to demonstrate the effect of different factors on the action of renin of milk. c) How are variations induced in plants? Explain one method in detail. d) Write an account on production of lactic acid. Q9) Write short notes on Any Two: [10] a) Applications of single cell proteins. b) Vaccines. c) Gasohols. [4923]-57 4 Total No. of Questions : 6] SEAT No. : P1980 [Total No. of Pages : 4 [4923]-58 M.Sc.-II ORGANIC CHEMISTRY CH-450 : Chemistry of Natural Products (2008 Pattern) (Semester-IV) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate full marks. 3) Answers to the two sections should be written in seperate answer books. SECTION-I Q1) Outline the steps involved in the following synthetic sequence. Indicate the reagent used and discuss the mechanism and stereochemistry (Any Four). [16] a) b) c) d) e) P.T.O. Q2) Give evidences to establish the following (Any Three): [12] a) Structural isomerism in podophyllotoxin and pieropodophyllin. b) The presence of C-8 and C-9 methyl and their stereochemistry in Hardwickiic acid. c) Spectral and chemical evidences for the presence of lactone ring in camptothecin. d) Presence of α, β -unsaturated acid in Hardwickiic acid. Q3) Answer Any Two of the following: [12] a) Complete the steps in the following synthesis. b) Arrange the following reagents in proper sequence. Explain the steps giving mechanism. Reagents: i) Grubbs cat. DCM. ii) (Boc)2O, Et3N, THF [4923]-58 2 CF3COOH, DCM 4-bromo-1-butene, K2CO3, CH3CN iv) I) PTsOH, H2O, MeOH II) TBDPS Cl, DMAP, imidazole, DCM. Complete the following synthetic steps. Explain the mechanism of each step. iii) c) I) II) SECTION-II Q4) Outline the steps involved in the biogenesis of the following (Any Four): [16] a) b) c) d) e) [4923]-58 3 Q5) Answer Any Three of the following: a) Give the biosynthesis of b) Outline the steps involved in the following biogenetic conversion. c) Write the steps involved in the following conversion. [12] FPP → Squalene. d) Give the steps involved in the following conversion: Q6) Answer in detail Any Two of the following: a) b) c) [4923]-58 4 [12] Total No. of Questions : 6] SEAT No. : P1981 [Total No. of Pages : 4 [4923]-59 M.Sc.-II ORGANIC CHEMISTRY CH-451 : Synthetic Methods in Organic Chemistry (2008 Pattern) (Semester-IV) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate full marks. 3) Answer to the two sections should be written in separate answer books. SECTION-I Q1) Explain Any Four of the following: [12] a) In the synthesis of 1, 2-dicarbonyl compounds umpolung approach is involved. b) CuCl2 is used in Wackers oxidation reaction. c) Advantages of urethane protection in peptide synthesis. d) Selectivity in reactivity of B2H6, disiamyl borane and 9-BBN by giving suitable examples. e) Uses of Pd(OAC)2 in organic synthesis. Q2) Predict the product/s with mechanism in Any Four of the following: [16] a) b) P.T.O. c) d) e) Q3) Write short notes on Any Four of the following: a) Linear and convergent synthesis. b) Sonogashira coupling. c) F-moc protecting group in solid phase synthesis. d) Uses of Fe(CO)5 in organic synthesis. e) Acetone can be used for the protection of OH groups in sugar. [12] SECTION-II Q4) Explain Any Four of the following: [12] a) Use of any transition metal complex in achieving nucleophilic aromatic substitution smoothy. b) Use of Mannich reaction in preparation of exomethylene ketones. [4923]-59 2 c) The stabilized ylides may be converted to trans-alkene in Wittig-Horner reaction. d) Synthesis of phthalic acid from benzoic acid using lithiation reaction. e) 1-propene could be easily converted to heptane-4-one using organoborane approach. Q5) a) How will you carry out the following transformations (Any Two): [6] i) ii) iii) b) Identify (A) and (B) in the following reaction sequences (Any Two): [6] i) ii) iii) [4923]-59 3 Q6) Using retrosynthetic analysis suggest a suitable method to synthesise the following (Any Four): [16] a) b) c) d) e) [4923]-59 4 Total No. of Questions : 7] SEAT No. : P1982 [Total No. of Pages : 4 [4923]-60 M.Sc.-II ORGANIC CHEMISTRY CH-452 : Heterocyclic Chemistry, Chiron Approach and Medicinal Chemistry (2008 Pattern) (Semester-IV) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory. 2) Figures to the right indicate full marks. 3) Answers to the two sections should be written in separate answer books. SECTION-I Q1) Explain the following (Any Four): [12] a) Pyridine is a stronger base than pyrimidine. b) Indole undergoes electrophilic substitution at 3 position than at 2 position. c) Why glycerol and not directly acrolein is used in the skraup quinoline synthesis. d) 4-chloro-3-nitro pyridine hydrolyses readily under milder conditions. e) Furan can not be directly alkylated under friedel crafts alkylation conditions. Q2) a) Give applications of supramolecular chemistry in medicine, data storage and processing. [4] b) Predict the product/s in Any Four of the following: [12] i) P.T.O. ii) iii) iv) v) Q3) Suggest the mechanism of Any Two of the following: [6] a) b) c) Q4) a) Write note on Any One of the following: i) Bischler indole synthesis. ii) Fiest Benary Furan Synthesis. [4923]-60 2 [3] b) Identify A, B, C, D from the following: [3] SECTION-II Q5) Answer Any Three of the following: [12] a) Glucose and mannose give the same osazone as fructose. Explain. b) Two Ruff degrations on an aldohexose give an aldotetrose which on oxidation with HNO3 gives mesotartaric acid. What can be the family configuration of the aldohexose? c) Write a short note on Kiliani-Fischer synthesis. d) D-sugars exist in 4C1 conformation while L-sugars in 1C4 conformation. Explain with suitable examples. Q6) a) Write the retrosynthesis for () Multistriatin. [4] b) How will you convert D-mannitol into (R) as well as (S) - Epichlorohydrin. [4] c) What is mutarotation? [2] d) Predict the products for any three of the following. [6] [4923]-60 3 i) ii) iii) iv) Q7) Answer Any Three of the following: [12] a) What is green chemistry? Discuss the need for green chemistry. b) Explain the active transport of drug absorption. c) Calculate the atom economy of the following reaction. Explain the efficiency of the reaction. H3C CH = CH CH3 + → H Br H3C CH2 CHBr CH3. d) Explain various processes involved in elimination of a drug. [4923]-60 4 Total No. of Questions :4] P1983 SEAT No. : [Total No. of Pages :2 [4923]-61 M.Sc. -II ANALYTICAL CHEMISTRY CH-481: Bioanalytical and Forensic Science (2008 Pattern) (Semester - IV) Time : 3 Hours] [Max. Marks :80 Instructions to candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic table/ non-programmable calculator is allowed. SECTION- I Q1) Attempt any four of the following: [20] a) What is Pasteurisation? How is it verified? b) Describe the method used for estimation of caffeine from coffee. c) Give the analytical method for estimation of CO2 from baking powder. d) Explain irradiation method of food processing. e) A sample of saccharin tablet (1.25 gm) was dissolved in water and titrated with 0.1 N NaOH. It required 0.90 ml titrant. Calculate the percentage of saccharin in the sample. (mol. wt. of saccharin =183.2) Q2) Attempt any four of the following: [20] a) Discuss the microkjeldahl method for estimation of proteins. b) Give the principle and procedure in determination of phosphatase. c) Discuss the chemistry of vitamin C with respect to structure, source and principle of estimation. d) Describe the method used for estimation of free amino acids. e) Sample containing 32.5 gm was subjected to Tanner method and titre value obtained with 0.01 M NaOH was 9.2 ml. Calculate the amount of SO2 in the sample). (At. wt. S=32 , O=16) P.T.O. SECTION- II Q3) Attempt any four of the following: a) [20] Define the termsi) Opium derivatives ii) Cannabis iii) Coca leaf iv) Medicinal cannabis b) Explain the process of obtaining rectified spirit from non-bonded manufactury. c) Write a note on LSD. d) Explain building arrangement in non-bonded laboratory. e) Give the rules related to export of medicinal and toilet preparation containing alcohol. Q4) Attempt any four of the following: [20] a) State the principle for determination of barbiturates by procedure type A. Explain its procedure in detail. b) Give the procedure for determination of benzodiazapines. c) Give detail procedure for absorption and elution of cocaine. d) State principle of determination of caffeine. Discuss the procedure in detail. e) Sample containing drugs was analysed by TLC. When distance travelled by solvent was 19.1 cm and heroin, caffeine, amphetamine, metamphetamine and barbiturates gives Rf values 0.151cm, 0.212cm, 0.432cm, 0.643cm and 0.735cm respectively. Calculate distance travelled by heroin, caffeine, amphetamine, metamphetamine and barbiturates. . S S S [4923]-61 2 Total No. of Questions : 4] SEAT No. : P1984 [Total No. of Pages : 3 [4923]-62 M.Sc.-II ANALYTICAL CHEMISTRY CH-490 : Analytical Spectroscopy (2008 Pattern) (Semester-IV) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) Answers to the two sections should be written in separate answer books. 2) All questions are compulsory and carry equal marks. 3) Neat diagrams must be drawn wherever necessary. 4) Use of logarithmic table/non-programmable calculator is allowed. SECTION-I Q1) Attempt Any Four of the following: [20] a) What is quantization of energy? Draw the energy level diagram for molecule. b) What are transducers? Explain with schematic diagram principle and working of pneumatic detector. c) What is satellite peak? Explain the mechanism that leads to satellite peaks. d) An ESCA electron was found to have kinetic energy of 1052.6 eV, when D ejected with Al, Kα source (λ = 8.34 A ) and measured on spectrometer with work function of 8.8 eV. Calculate the binding energy of electron. [Given: Plancks constant = 6.625 × 1034 Js, c = 3 × 108 m/s]. e) Beryllium (II) forms a complex with acetylacetone having molecular mass 166.2 g mole1. Calculate the molar absorptivity of complex of solution 2.34 ppm has a transmittance of 45.5%, when measured in a 1.00 cm cell at 295 nm. P.T.O. Q2) Attempt Any Four of the following: [20] a) Explain the principle of X-ray absorption spectroscopy. Discuss the flat crystal monochromator with block diagram. b) Write a note on gas phase chemiluminescence. c) Describe the Braggs method for crystal analysis. d) Explain the following terms: e) i) Singlet and triplet state. ii) Intersystem crossing. iii) Resonant fluorescence. D A crystal of topaz was exposed to Kα line of copper at 1.542 A diffracted at an angle of 34.65° relative to the crystalline surface for first order diffraction. Calculate the spacing between adjacent layers of nuclei in the crystal. SECTION-II Q3) Attempt Any Four of the following: [20] a) What is Larmor precession? Discuss the classical theory of NMR spectroscopy. b) What is Relaxation? Explain spin-spin and spin-lattice relaxation. c) Write a note on nuclear overhauser effect. d) A compound shows NMR at 220 Hz downfield from TMS peak in spectrometer operating at 60 MHz. Calculate the value of chemical shift in ppm relative to TMS. e) Calculate the ratio of 13C nuclei in the upper energetic level to the lower energetic level at 27°C in a magnetic field that has flux density of 25000 G. [Given: μN = 0.70216 NM, βN = 5.05 × 1031 JG1]. [4923]-62 2 Q4) Attempt Any Four of the following: [20] a) Describe with suitable examples the applications of ESR spectroscopy in qualitative and quantitative analysis. b) Draw a schematic diagram of SEM. Describe how the image of a surface of solid sample is obtained using a finely focussed beam of electrons. c) Explain, John-Teller effect in copper (II) complex described in ESR spectroscopy. d) Discuss ENDOR and ELDOR techniques in ESR spectroscopy with suitable example. e) If a resonance was observed for an unpaired electron at a magnetic flux density of 0.34 T and frequency of 9500 MHz. Calculate g-factor for unpaired electron. [Given: Plancks constant = 6.625 × 1034 Js, Bohr magneton = 9.285 × 1024 JT1] [4923]-62 3 Total No. of Questions : 4] SEAT No. : P1985 [Total No. of Pages : 3 [4923]-63 M.Sc.-II ANALYTICAL CHEMISTRY CH-491 : Polymer Technology (2008 Pattern) (Old Course) (Semester-IV) Time : 3 Hours] [Max. Marks : 80 Instructions to the candidates: 1) All questions are compulsory and carry equal marks. 2) Answer to the two sections should be written in seperate answer books. SECTION-I Q1) Attempt Any Four of the following: a) Explain intermolecular forces in polymers. b) Write a note on bulk and suspension polymerisation. c) Explain mechanism of free radical polymerisation. d) Give method of preparation and uses of e) i) Polycarbonates. ii) Cellophane. [20] Explain role of flame retardants, colorants and curing agents in polymer processing. Q2) Attempt Any Four of the following: a) Explain effect of radiation on polymer degradation. b) Explain kinetics of free-radical polymerisation. [20] P.T.O. c) Write a note on initiator. d) Explain polycondensation polymerisation. e) Complete the following polymeric reactions. i) ii) iii) iv) v) SECTION-II Q3) Attempt Any Four of the following: [20] a) Describe in detail the cryoscopic method for determination of average molecular weight of polymer sample. b) Explain the terms: i) Tear resistance. ii) Glass transition temperature. iii) Vapour permeability. iv) Fatigue test. v) Calendering. [4923]-63 2 c) Draw a typical DSC and DTA thermograms for a crystalline polymer showing the glass transition, crystallisation and thermal degradation. d) Explain different types of intermolecular forces present in polymers. e) 0.692 gm of CTPB sample was dissolved in 25 ml mixture of ethyl alcohol and toluene [1:3]. The solution was titrated with 0.119 N alcoholic NaOH solution. The burette reading was 5.9 ml. Calculate Mn of a polymer sample. [Given: functionality = z]. Q4) Attempt Any Four of the following: [20] a) Give an account of wet spinning process. b) What is viscose? Discuss the various steps involved in obtaining Rayon. c) What is vulcanisation? Explain it giving atleast four examples. d) Explain the term compounding. What are the ingradients used in compounding process? Give the role of each ingradient. e) When a certain polymer sample contains 200 molecules with molecular weight 104, 250 molecules with molecular weight 105, 300 molecules with mole. wt. 103 and 50 molecules with 107. Find total Mn and Mw for given polymer sample. [4923]-63 3
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