M.sc. - Chemistry
M.sc. - Chemistry
d) Evaluate : Gmix and : Smix if the gases, 1 mole helium, 3 moles neon, 2
moles argon and 2.5 moles xenon are mixed at 25°C.
[4325]-101 2
SECTION - II
Q4) Attempt any three of the following : [15]
a) What is enzyme catalysis ? Derive Michaelis - menton equation for enzyme
catalyzed reactions.
b) Compare transition state theory and collision theory for the rate of
bimolecular reaction.
c) Why do certain reactions end into explosion ? Explain their mechanism.
d) Which are the techniques for studying kinetics of fast reactions ? Discuss
any one of them.
e) Distinguish between order and molecularity of a reaction. Write the general
expression for order and half-life of a reaction.
Q5) Attempt any three of the following. [15]
a) Derive Eyring equation for reaction rates.
b) Write a note on potential energy surface.
c) Derive the vibrational contribution to the molar entropy and Gibbs free
energy of the system.
d) Distinguish between Maxwell Boltzman and Bose-Einstein statistics.
e) What are diffusion controlled limits ? Derive the equation for diffusion
controlled reactions.
Q6) Solve any two of the following. [10]
a) Calculate the rotational contributions to entropy and free energy for
oxygen gas at 25°C and 1 atmosphere pressure. The moment of inertia
(I) of O2 gas is 1.9373 x 10-46 kg m2.
b) Calculate the molar residual entropy of a crystal in which the molecules
can adopt six orientations of equal energy at ok.
c) The relaxation time for the fast reaction is 10 μs and the equilibrium
constant is 1x10-3. Calculate the rate constants for the forward and
backward reactions.
d) The decomposition of urea in 0.1 m HCl occurs according to the reaction
NH2CONH2+2H2O 2NH !4 + CO 32 #
The first order rate constant for this reaction at 71.2°C is 2.77 x 105 min1
with the frequency factor 1.38 x 1013 S1. Calculate the entropy of
activation at 71.2°C
vvv
[4325]-101 3
Total No. of Questions : 6] SEAT No. :
a) Predict the intensity distribution in the hyperfine lines of the ESR spectrum
of CD3.
b) Explain the rule of mutual exclusion and its converse. Sketch and explain
the polarizability ellipsoids of the various modes of vibration of CO2
molecule. Which of these are Raman active ?
d) Calculate the population of the first excited level if the ground state has
1000 molecules at 29K. ( E=4.005 × 10-23 J molecule-1)
[4325]-201 2
SECTION - II
Q4) Attempt any three of the following : [15]
a) Explain different types of G.M. counters.
b) How will you determine the steady state concentration of radicals?
c) Describe the working of Fricke dosimeter. What precautions must be
taken while using it ?
d) Explain the terms i) tracks, ii) spurs, iii) -rays and iv) stopping power.
e) What is separation factor ? Explain electromagnetic method for separation
of isotopes.
Q5) Attempt any three of the following : [15]
a) What is natural nuclear reactor ? Discuss Oklo phenomenon and the
Oklo reactor.
b) How are uranium and plutonium recovered from spent fuels?
c) Discuss Indias three phase nuclear energy programme.
d) What is diffusion phenomenon ? Discuss zone-diffusion technique to
determine diffusion coefficient.
e) How is 14C obtained naturally and artificially ? Give different steps involved
in transformation of 14C from fossils into benzene.
Q6) Solve any two of the following. [10]
a) 10.0 ml KBr solution tagged with radioactive bromine was titrated with
0.01M AgNO3. Addition of 2.5 ml of titrant followed by removal of
AgBr precipitate decrease in activity from 12500 counts for 5 min to
6000 counts for 6 min. Calculate the amount of bromine in original solution.
The detector gave background counts 100 for 10 min.
[Given At.wts. of Ag=108, N=14, O=16, K=39 and Br=80]
b) Potassium - 40 (t1/2 = 1.3 x 109y) constitutes 0.012% of the potassium in
nature. Human body contains 0.35% potassium by weight. Calculate the
radioactivity resulting from potassium-40 decay in a 70 kg man.
c) When single atom of 235U undergoes fission energy obtained is 200 MeV.
Calculate the power released during the fission of 1 kg 235U in 1 day.
vvv
[4325]-201 3
Total No. of Questions : 5] SEAT No. :
d
b) If  = 3x2 and B̂ = , then show that AB ˆˆ.
ˆ ˆ BA
dx
[4325]-301 2
b) Discuss with a suitable example, how the forbidden band gap can be
determined by studying optical properties of semiconductors.
c) Discuss the mechanism of diffusion in solids.
d) Give briefly the occurance of elastic and plastic deformations in solids.
e) Explain the mechanism of a photographic process.
Q4) Attempt any three of the following : [15]
a) Discuss the factors that affect the progress of a Chemical change in
solid-solid reactions.
b) Explain the origin of colour centres in ionic crystals.
c) The fast growing faces are eliminated whereas slow growing faces persist
in a crystal - prove this statement on the basis of geometrical consideration.
d) Write a note on Brillouin zones.
e) Draw and describe the various α-t plots for the decomposition of a
single solid.
Q5) Solve any two of the following : [10]
a) The number of free electrons in a monovalent crystal is 1019 per cm3 at
300K. Calculate the Fermi energy (Eo) in eV.
[4325]-301 3
Total No. of Questions : 6] SEAT No. :
[4325]-302 2
SECTION - II
Q4) Attempt any three of the following : [15]
a) Discuss the working of Vande Graaff generator.
b) What are the basic components of a particle accelerator ? Explain the
function of each component.
536 E s2
c) What is Szilard-Chalmer reaction ? Derive the expression E= .
A
d) What you understand by the term intrinsic and extrinsic semiconductor ?
Explain the working of surface barrier detector.
e) Explain with suitable example retention in organic compounds.
Q5) Attempt any three of the following : [15]
a) Discuss the free radical theory of radiolysis of water.
b) Explain the various stages of interaction of radiations with biological
cells.
c) Enlist various natural and man made sources of radiations. Describe the
procedure for safe handling of these sources.
d) Distinguish between somatic and genetic effects of radiations.
e) What are the after effects of chernobyl nuclear accident ?
Q6) Solve any two of the following : [10]
a) Find out thickness of lead needed to decrease the activity of Co-60
source from 25,000 cpm to 4000 cpm. Given: e = 0.211 b/e, Z of Pb = 82,
A of Pb = 207, density of Pb = 11.35 g cm-3.
b) Find out dose due 200 mci CS-137 radiation source at a distance of 3
meters. Given : gamma energy = 0.67 MeV.
c) A radiation worker is exposed to following doses of radiations in 6
months.
1 mrad due to -particles
1 mR due to particles
0.01 Gy due to rays.
Find out his effective dose. Is it permissible ?
vvv
[4325]-302 3
Total No. of Questions : 6] SEAT No. :
a) Define and explain the terms isotopic abundance and excitation function.
c) Explain the parameters which govern the sensitivity of the NAA technique.
c) Explain the cylindrical mirror analyzer used in ESCA with a neat labelled
diagram.
e) What are the types of detectors used in mass spectrometry ? Explain the
Faraday Cup detector with a neat labelled diagram.
[4325]-303 2
b) Aluminium is to be used as windows for a cell for x-ray absorption
measurements with the Ag K W line. The mass absorption coefficient for
aluminium at this wavelength is 2.724 cm2/g, its density is 2.699 g/cm3.
What maximum thickness of aluminium foil could be employed to
fabricate the windows if no more than 3.5% of the radiation is to be
absorbed by them ?
SECTION - II
[4325]-303 3
Q6) Solve any two of the following : [10]
c) A 0.6025 g sample was dissolved and the Ca2+ and Ba2+ ions present
were precipitated as BaC2O4.H2O and CaC2O4.H2O. The oxalates were
then heated in a thermogravimetric apparatus leaving a residue of
unhydrous oxalates that weighed 0.5713 g in the temperature range of
320°C to 400°C and the residue of carbonates that weighed 0.4673g in
the temperature range 580°C to 620°C. Calculate the percentage of Ca
and of Ba in the sample.
[At. wts. : Ba = 137.34, Ca=40, C=12, O=16]
vvv
[4325]-303 4
Total No. of Questions : 5] SEAT No. :
e) Define the term glass transition temperature (Tg) and describe any one
method of its determination.
[4325]-304 2
c) The relative viscosities of a fraction of polystyrene of Mn= 275000,
dissolved in tetralin at 293K were
SECTION - II
d) What are the techniques used for the production of reinforced plastics.
Explain any one technique with neat diagram.
f) Explain the terms: Tenacity, Crimp, Denier, moisture regain and fibre
with reference to textile.
vvv
[4325]-304 3
Total No. of Questions : 4] SEAT No. :
P.T.O.
1
SECTION - I
2
Q4) Attempt any four of the following : [20]
a) Describe the phase diagram of the water system.
b) Describe the anomalous properties of nanoparticles.
c) Write a note on carbon nanotubes.
d) Describe the principle of preparing tunable smart materials.
e) Write a note on rubber like ceramics.
f) Describe the chemical methods of preparing nano particles.
vvv
[4325]-305 3
3
Total No. of Questions : 4]
4
SECTION - I
SECTION - II
[4325]-305 2
5
d) Explain the mechanism of polymer degradation by photosensitizer
additives.
e) How do the modern agricultural practices pollute the soil ?
f) What are soil indicator plants ? Discuss these in detail.
vvv
[4325]-305 3
6
Total No. of Questions : 4] SEAT No. :
P656 [4325]-306 [Total No. of Pages : 2
M. Sc. - II Semester-III
INORGANIC CHEMISTRY
CH - 326 : Organometallic Compounds of Transition
Metals and Homogeneous Catalysis
(2008 Pattern)
P.T.O.
b) What is catalysis ? Why do T.Ms acts as catalyst ? Give two examples
of homogeneous catalyst.
c) Discuss in detail production of aldehyde by wacker process.
d) Process a structure of (C5+15)3 Ni3(CO)2 based on IR data. Does each
Ni atom obey the 18 e rule?
e) What haptacities are possible for the following ligands:
i) C2H4 ; ii) Cyclopentadienyl, iii) C6H6 ; iv) Butadiene ;
v) Cyclo octatetraene.
i) Cp (CO)3 Re + Br2 → ?
***
[4325]-306 2
Total No. of Questions : 4] SEAT No. :
P657 [4325]-307 [Total No. of Pages : 2
M. Sc. - II Semester-III
INORGANIC CHEMISTRY
CH - 330 : Coordination Chemistry, Magnetism and Reaction Mechanism
(2008 Pattern)
P.T.O.
Q3) Attempt any FOUR of the following. [20]
a) What is conjugate base dissociation mechanism ?
b) Discuss in brief isomerisation of octahedral complexes.
c) Discuss the mechanism of electron transfer reaction with reference to
the inner-sphere reaction.
d) Which isomer can you obtain from the following synthetic pathways ?
Give precise explaination and correct structure of the product.
−
i) +NH3
[PtCl 4 ]-2 ⎯⎯⎯ +NO 2
→ ? ⎯⎯⎯ →?
ii) +Cl
[Pt(PR 3 ) 4 ]+2 ⎯⎯ ⎯ +Cl
→ ? ⎯⎯ ⎯ →?
e) Explain in brief Anation reactions.
iii) ZZX ?
(CH3)3 B + N (CH3)3 YZZ
iv) BF3 + F- → ?
v) C-2(CO)6 + Py → ? + ?
***
[4325]-307 2
Total No. of Questions : 4] SEAT No. :
P658 [4325]-308 [Total No. of Pages : 2
M. Sc. - II Semester-III
INORGANIC CHEMISTRY
CH - 331 : Structural Methods in Inorganic Chemistry
ii)
given : IH = 1/2 ; IN = 1
d) How is Mössbauer Spectroscopy useful to characterise oxidataion states
of tin in organotin compounds.
e) Sketch the energy level diagram and transitions for a quadrupole nucleus
P.T.O.
Q3) Attempt the following (any four) [20]
a) The TG plot of 2.89 mg of sample containing MgSO4.7H2O shows a
single step at on set temperature ~378°k corresponding to formation of
MgSO4.H2O. The mass loss in the step was 0.59 mg. Determine the
percentage of MgSO4.7H2O in the sample.
given At.Wts: Mg = 24.312; S = 32.064; H=1.008; O=15.999
b) Compounds of some elements are used in NMR as shift agents. Which
are these elements ? Explain the use of shift agents in NMR.
c) With the help of ray diagram explain the principle of TEM.
d) How can we determine rate constants of different redox reactions using
cycle voltametry.
e) NMR is an excellent tool to study Metal phosphine compounds Justify
the statement.
***
[4325]-308 2
Total No. of Questions : 4] SEAT No. :
P659 [4325]-309 [Total No. of Pages : 2
M. Sc. - II Semester-III
INORGANIC CHEMISTRY
CH - 332 : Bio-Inorganic Chemistry :
Inorganic Elements in the Chemistry of Life
P.T.O.
Q3) A) Attempt any five: [15]
a) What kind of ionizing radiations are useful in radiopharmaceutical
applications ?
***
[4325]-309 2
Total No. of Questions : 6] SEAT No. :
P660 [4325]-310 [Total No. of Pages : 3
M. Sc. - II
ORGANIC CHEMISTRY
CH - 350 : Organic Reaction Mechanism
SECTION-I
Q1) Attempt any four of the following. [12]
a) Explain the evidences to support NGP.
b) Butane 2, 3-dione exists exclusively in keto form, where as 1,2 -cyclopentane
dione is 100% enolised. Explain.
c) The ionisation constants of 3 and 4 cyano benzoic acids at 300C are
2.51 x 10-4 and 2.82 x 10-4 respectively. Benzoic acid has ionisation
constant ka of 6.76 x 10-5 at 300C. Calculate m and m p for the cyano
substituent.
d) Predict the sign of Hammett ( ) sigma constant for following substituents
giving reasons.
+
P-OH, P-NO2, m-OCH3, m- Nme3
e) Explain the importance of non-linear Hammett Plots.
P.T.O.
Q3) Predict the products with mechanism for any four of the following. [16]
hv, meOH ?
THF
a) O
O
N2
O O
b) Et 2Zn/CH2I2
?
-
OEt ?
+ PhCHO
c) +
N
CH3
Cl
H2O
: ?
+
d)
e) O ?
COOH
Et3N, Stetter Catalyst
SECTION - II
Q4) Explain any four of the following. [12]
a) Thiamine Pyrophosphate is a natural acyl ion equivalent.
b) Explain the observed enol contents of the following.
1, 3 - cyclohexane dione 95%
1, 2 - cyclopentane dione 99%
33%
[4325]-310 2
d) Ethanolysis of proceeds with total inversion,
a)
b)
c)
d)
e)
***
[4325]-310 3
Total No. of Questions : 6] SEAT No. :
i) B3N3H6
c) Classify any two of the following molecules into appropriate point group
Justify it.
i) In Cl52−
ii) PCl5
iii) AsH3
P.T.O.
d) Give the properties of irreducible representations for C4v point group
label the irreducible representations with appropriate Mülliken symbols.
Given:character table for C4v.
a) Sketch and explain the following symmetry elements in BF5 molecule and
classify it into appropriate point group.
Given:
Eg 2 0 -2 0 0 2 0 -2 0 0
[4325]- 102 2
Q3) Answer the following: [10]
a) 42001 b) 41002
c) 51201 d) 51002
a) C 4v b) Td
c) D4h d) D 4d
a) SnCl2 b) IF7
c) IF5 d) PCl5
a) BF5
b) SO2
c) Pyridine
d) NF3
b) What are Weiss indices? Explain with suitable examples. Draw (3 2 1) and
(0 0 1) planes in cubic system.
[4325]- 102 3
Character table for C4v point group
rotations
A1 1 1 1 1 1 z x2+y2,z2
A2 1 1 1 1 1 Rz
B1 1 1 1 1 1 x2y2
B2 1 1 1 1 1 xy
C2 V E C2 σV1 σV2
E E C2 σV1 σV2
C2 C2 E σV2 σV1
[4325]- 102 4
SECTION - II
e) Sulphur oxoanions.
i) XeF4
ii) B5 H9
iii) Si3O96
v) IF5
[4325]- 102 5
b) Attempt any five of the following: [5]
a) K3 C60 b) K4 C60
c) K 16 C60 d) K10C60
iii) The correct statement for (CH3)3 N and (SiH3)3 N are -----
a) B12 H2
12
b) B12 H12
[4325]- 102 6
v) Alkali metals in liquid ammonia are blue in colour because -------
vi) Which one of the following is the correct set of number of lone pair of
electrons in XeF2, XeF4 and XeF6 respectively?
a) 0, 1, 2 b) 1, 2, 3
c) 3, 2, 1 d) 2, 1, 0
+++++++
[4325]- 102 7
Total No. of Questions : 6 ] SEAT No. :
SECTION - I
P.T.O.
Q2) Write short notes on any three of the following : [12]
b) Jone's reagent.
c) Wolf rearrangement.
Q3) Predict the products and suggest the mechanism for any four of the
following : [12]
a)
b)
c)
d)
e)
[4325] - 203 2
SECTION - II
a)
b)
c)
d)
e)
IR
c) Assign the chemical shift for the following.
0.9 d 7 Hz 6H
1.5 d 7 Hz 3H
1.85 m 1H
2.45 d 7Hz 2H
[4325] - 203 3
3.6s 3H
7.1d 8Hz 2H
7.3d 8Hz 2H
d) Calculate l max for the following compound
Q6) Deduce the structure of any three of the following using spectral data and
justify your answer. [12]
a) M.F : C8 H8 O2.
UV : 250 , 260, 265 nm (Î220, 250 , 200).
IR : Very broad band between 2700 3300, 1700, 1600 (w). 1500,
920 cm1.
H1 NMR : 3.5 ( 12mm, s).
7.2 (30 mm, s).
12.3 (6 mm, s).
b) C8 H10 O2
IR : 3939 , 1599, 1497 , 1173 cm1.
H1NMR : 2.35 ( t, J= 6 Hz , 10 mm Ex).
3.97 ( q, J = 6Hz, 20 mm).
4.08 (t, J = 6Hz , 20 mm).
6.93 ( d, J = 8Hz, 20mm).
6.97 (t, J =8Hz, 10mm).
7.27 ( t, J = 8Hz, 20 mm).
c) MF : C4 H5 O2 N
UV : Featureless above 210 nm,
IR : 2250; 1750 cm 1
NMR : 3.5 (10 mm, s)
3.8 (15 mm ,s)
d) MF : C7 H14 O
H NMR : 0.9 ( t, 6 H)
1
1.6 ( Sext. 4 H)
2.4 (t, 4 H)
nnn
[4325] - 203 4
: .oN TAES ]4 : snoitseuQ fo .oN latoT
I - NOITCES
]02[ : gniwollof eht fo ruof yna tpmettA )1Q
.sisylana latnemurtsni ni desu smret gniwollof eht nialpxE )a
rewop gnivloseR )ii rewop evisrepsiD )i
doireP )iii
lacimehc rof lufesu era taht snoiger lartceps citengamortcele eht tsilnE )b
.murtceps noitaidar citengamortcele htiw sisylana
m a e b e l g n i s f o g n i k r o w n i a l p x e d n a m a r g a i d c i t a m e h c s w a r D )c
..retemotohportceps
htumsib neewteb demrof xelpmoc eht rof ytivitprosba ralom etaluclaC )d
evag ,xelpmoc fo noitartnecnoc M501 × 7.3 gnivah aeruoiht dna )III(
.mn 074 ta htgnel htap mc 0.1 a ni %3.87 fo ecnattimsnart
na stime edonydhcae dna sedonyd net sah ebut reilpitlumotohp niatrec A )e
noitacifilpma eht etaluclaC .snortcele gnignipmi rof snortcele 2.4 fo egareva
.ebut reilpitlumotohp a fo rotcaf
II - NOITCES
]02[ : gniwollof eht fo ruof yna tpmettA )3Q
cinotorp-non dna artceps ecnanoser citengam notorp neewteb hsiugnitsiD )a
.artceps ecnanoser
RMN fo elpicnirp eht nialpxE ?noissecerp romraL yb tnaem si tahW )b
.yroeht lacissalc no desab ypocsortceps
.noitaxaler ecittal-nipS dna nipS-nipS nialpxE ?noitaxaler yb tnaem si tahW )c
,tnemurtsni zHM 003 a no zH 6 = J ,δ5.4 ta retrauq a ta sraeppa notorp A )d
.seitisnetni evitaler sti evig dna enil hcae fo zH ni noitisop enil eht setacidni
zHM 06 a ni suelcun ralucitrap a fo MPP ni tfihs lacimehc eht etaluclaC )e
ytisned xalF citengam a ta sbrosba suelcun ecnerefer eht fi tnemurtsni
.suelcun naht retaerg hcihw G 360.0 si taht
.)zHM06 ta noitprosba esuac ot deriuqer G00041 suelcun H1 roF :neviG[
2 214-]5234[
xulf citnegam a ta nortcele deriapnu na rof devresbo saw ecnanoser a fi )e
deriapnu rof rotcaf-g etaluclac ,zHG 5.9 fo ycneuqerf a dna T 33.0 ytisned
.nortcdle
SJ 01 × 526.6 = h = tnatsnoc skcnalP :neviG[
43
ïïï
3 214-]5234[
Total No. of Questions : 6] SEAT No. :
SECTION - I
e) Menthyl chloride on treatment with NaOEt gives only one product whereas
neo-menthyl chloride gives two different products. Explain.
P.T.O.
Q2) Write short notes on any three of the following : [12]
a) Crown ether
b) Jacobsen reaction
d) SET mechanism
a)
b) meso-2, 3-dibromobutane
c)
d)
SECTION - II
a)
b)
[4325] - 103 2
c)
d)
e)
[4325] - 103 3
b) Assign R/S to the chiral center.
e) Identify chiral carbons and find total no. of stereo-isomers in the following
compounds.
i) 4-nitrobenzaldehyde ii)
zzz
[4325] - 103 4
Total No. of Questions : 6] SEAT No. :
SECTION - I
a) Work out possible number of micro states for the following systems.
iii) f7 iv) d7
v) 3p1 4p1
b) Determine the ground state term for any two metal ions in the following
complexes.
P.T.O.
c) Determine the spin multiplicities of states arising from +2g2 configuration,
when infinitely strong octahedral field is relaxed to strong field using
Bethes method of decending symmetry, correlation table and direct
product table.
e) The tetrahedral complex [CoCl2 (aniline)2] exibits three d-d bands, the
lowest energy band appearing at 6500 cm1 (γ1) predict the energy of the
γ2 and γ3 bands. (B = 880 cm1).
b) Explain the concept of hole equivalency and mention at least two examples.
ii) Peaks for forbidden transitions are more sharp than those for allowed
transitions.
d) How would you account for the magnetic moments listed against each
of the following complexes.
[4325] - 202 2
e) For complex [CoCl4]2 ion spin orbital coupling constant is 190 cm1.
The γ1 transition is observed at 2940 cm1. Calculate effective magnetic
moment of Co2+ ion in the complexion.
c) Chemilumiescence.
SECTION - II
a) Metals in medicine.
b) Dioxygen transport.
c) Acetylcholine receptor.
[4325] - 202 3
d) Detoxification of mercury.
a) [2Fe - 2S]+2
b) Tyrosine
c) Aquocobalmin
d) Deoxy hemoglobin
e) Siderophore
f) Flavin
[4325] - 202 4
[4325] - 202 5
[4325] - 202 6
zzz
[4325] - 202 7
: .oN TAES ]6 : snoitseuQ fo .oN latoT
I - NOITCES
]8[ : gniwollof eht fo ruoF yna rewsnA )a )1Q
.O.T.P
snoitisop enil esohw tetrauq BA na fo mpp δ ni tfihs lacimehc eht etaluclaC )b
]4[ .RMN zHM 001 a ni 282 ,092 ,292 ,003 era )zH( ztreh ni
2
O6 H5 C : F.M
mc 6971
1
: RI
)s(871 )s(351 )d(89 )t(43 )q(21 :RMC
4
O 61 H7 C : F.M
1
mc 0111 : RI
001 ,).rtS( 15 ,53 :RMC
)pu(001 dna 15 ,)nwod(53 :531 TPED
)H2 ,zH7 ,t(5.4 )H21 ,s(3.3 )H2 ,zH7 ,t(8.1 : RMP
4
O 6 1 H0 1 C : .F.M
mc 5271
1
: RI
)w,s(551 )w,s(521 )rts,t(06 )rts,q(02 )rts ,q(21 :RMC
)w,s(561
)H4 ,zH7 ,q(3.4 )H6 ,s(0.2 )H6 ,zH7 ,t(3.1 :RMP
2 113-]5234[
atad nevig eht morf erutcurts eht ecudeD )e
3
O 01 H5 C : .F.M
mc 3171
1
: RI
971 ,57 ,23 ,91,61 :RMC
pu 57 ,23 ,91 ,61 :531 TPED
tnesba 971
)H1 ,m(1.2 )H3 ,zH7 ,d(1.1 )H3 ,zH7 ,d(59.0 :RMP
).hcxe ,H2 ,langis daorb(0.8 ot 5.5 )H1 ,zH6 ,d(1.4
.EON fo snoitacilppA )b
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]8[ : ruof yna rof snoi eht fo siseneg eht nialpxE )a )4Q
)i
)ii
)iii
3 113-]5234[
96 ,48 ,211 )vi
swohs edixo enelyhte dna enezneb fo noitcaer tfarc ledcirf fo tcudorp ehT )b
]4[ .emas eht fo siseneg eht etirW .29 = z/m ta kaep gnorts a
devresbo eht no tnemmoC .snotorp suoirav ot stfihs lacimehc eht ngissA )a )5Q
]8[ .stnemirepxe ecnanoser elbuod dna stnatsnoc gnilpuoc
)H9 ,s(63.3
)H1 ,m(30.4
: tpxe gnilpuoced-nipS
zH2 & 5.9 )dd( → )m(30.4 segnahc 29.3 δ ta noitaidarri )i
: tpxe EON
.%7 yb δ 68.1 ta langis eht ecnahne 61.1 δ ta noitaidarri
4 113-]5234[
)d(4.56 )t(0.94 )q(7.44 )t(8.52
nevig atad RMP eht gnisu noitcaer fo ecneuqes gniwollof eht etelpmoC )c
]4[ : woleb
: atad RMP
)H1 ,zH51 ,d(0.7 )H1 ,zH 51 ,d(4.6 )H9 ,s(71.1 )H9 ,s(1.1 : A
)H1 ,zH 9.1 & 7.71 ,dd( 17.2 )H9 ,s(31.1 )H9 ,s(80.1 : B
)H1 ,zH01 & 9.1 ,dd(83.4 )H1 ,zH 01 & 7.71 ,dd(52.3
5 113-]5234[
6 113-]5234[
ïïï
7 113-]5234[
Total No. of Questions : 6] SEAT No. :
SECTION - I
Q1) Answer any four of the following : [16]
a) Discuss the dipole moments of cis and trans 1,2- dibromo cyclohexane.
b) Which form of bicyclo [3.3.1] nonane is more stable? Why?
c) Explain isomers of perhydrophenanthrene and their stability.
d) Bicyclo [2.2.2] octane - 2, 6 - dione (A) does not show acidic properties
while camphonic acid (B) does not readily undergo decarboxylation.
e) Why trans decaline is more stable than cis decaline. Explain with stereo
structure.
Q2) Predict the product in any four of the following and explain stereochemical
principles involved. Justify. [12]
a)
b)
P.T.O.
c)
d)
e)
SECTION - II
Q4) Answer the following (any three) : [12]
a) How NMR spectroscopy is used to find stereochemistry of lactone fusion
in enhydrin?
b) In cinchonine and quinine C8C9 bond and C3Vinyl bond are on the
same side. Explain.
c) Predict the product and explain stereochemistry of the product.
[4325]-312 2
Q5) Attempt any four of the following : [12]
a) Assign Re/Si configuration of each Sp2 hybridized carbon in following
compound.
b) With reasons, state whether the faces of the carbonyl groups in the
following compounds are homotopic, enantiotopic or diastereotopic.
Q6) a) Predict the product/s and write stereochemistry of the following reaction
(any four) : [8]
i)
[4325]-312 3
ii)
iii)
iv)
v)
i)
ii)
iii)
ïïï
[4325]-312 4
Total No. of Questions : 6] SEAT No. :
Q2) Predict the product/s indicating mechanism in any four of the following:[12]
a)
b)
P.T.O.
c)
d)
e)
Q3) a) Suggest suitable mechanism for any five of the following : [10]
i)
ii)
iii)
iv)
v)
vi)
[4325]-313 2
SECTION - II
Q4) a) Draw the correlation diagram for disrotatory conversion of allyl carbonium
ion to cyclopropyl carbonium ion and predict whether the reaction is
thermally or photochemically allowed. [6]
b) Predict the products in any four of the following. Explain the
stereochemistry and mechanism. [8]
i)
ii)
iii)
iv)
v)
Q5) a) Using the Aromatic Transition state concept predict whether the π4s +
π2s cycloaddition reaction is thermally or photochemically allowed. [4]
b) Explain the mechanism for any four of the following : [8]
i)
ii)
iii)
iv)
[4325]-313 3
v)
i)
ii)
iii)
ïïï
[4325]-313 4
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) Distinguish between Voltammetry and Polarography.
b) Explain the following terms and give their significance in Polarographic
analysis.
i) Limiting current
ii) Polarographic maxima
iii) Condenser current
c) Explain construction and working of rotating platinum microelectrode.
What are advantages of it over DME?
d) The diffusion coefficient for Tl + is 2.00 × 105 cm2/s, where as for Cd 2+
is 0.72 × 105 cm2/s. If a 1.00 × 103M solution of Cd 2+ gives a diffusion
current of 8.15 µA, predict the diffusion current for 1.5 × 103M Tl+
under the same conditions.
e) Anodic stripping voltammetry is used for the analysis of copper in a sea
water sample using standard addition method. When a 50 ml sample is
analysed it gave a peak current of 0.886 µA. A 5.00 µdm3 spike of 10
ppm Cu2+ is added to the sample and the resulting peak current is 3.52
µA. Calculate the concentration of Cu2+ in ppm in the given sample of
sea water.
P.T.O.
Q2) Attempt any four of the following : [20]
a) Write a critical note on cyclic voltammetry.
b) What are nano-materials? Explain its general applications.
c) What are amperometric titrations? Explain the estimation of zinc by EDTA
using this technique.
d) Draw schematic diagram of cell used in coulometric titration. Discuss
the application of coulometry for complexometric titration.
e) A solution containing 0.50 g of nickel as Ni2+ requires 20 minutes for
complete deposition of nickel at 1.50A. Calculate the quantity of electricity
required.
[At. Wt - Ni = 58.7]
SECTION - II
Q3) Attempt any four of the following : [20]
a) Explain the following terms :
i) Specific activity.
ii) Neutron flux.
iii) Neutron capture cross section.
b) What is the principle of a radiometric titration? Discuss the nature of the
titration curve of calcium by EDTA with solid radioactive silver iodate as
an indicator.
c) State and explain the principle of isotope dilution analysis. Give its
applications.
d) The vitamin B-12 content of multivitamin tablet was determined by
dissolving 10 tablets in water. The solution was transferred to 100 ml
volumetric flask and diluted to volume. A 50 ml portion was removed
and treated with 0.5 mg of radioactive vitamin B-12 having an activity of
572 cpm. After homogenization, the vitamin B-12 in the sample was
isolated and purified, producing 18.6 mg with an activity of 361 cpm.
Calculate the amount of vitamin B-12 per tablet.
e) 53.8 mg steel sample was analysed for its manganese content by neutron
activation, 68.5 mg standard steel sample containing 0.9% manganese
was irradiated along with the sample in neutron source and counted under
same experimental conditions. Activities of sample and the standard
counted for 5 minutes were 16597 and 21983 counts respectively.
Calculate the percentage amount of manganese in the steel sample.
[4325]-314 2
Q4) Attempt any four of the following : [20]
a) Explain the principle and instrumentation of Nephelometry. Give the
typical applications of nephelometric method.
b) Explain the principle of DTA technique with suitable example. Describe
the terms exotherm and endotherm in DTA.
c) Draw a schematic diagram of a modern thermo balance and discuss the
significance of each component.
d) Explain the construction and working of optically transparent electrodes.
e) The mass 250 mg hydrated sample of disodium hydrogen phosphate
decreases to 153 mg after heating to 150ºC by TGA. What is the number
of water of hydration in hydrated sample?
(Given: At.Wt. Na = 23, P = 31, H = 1, O = 16).
ïïï
[4325]-314 3
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) Give the analytical procedure for the estimation of Potassium from
fertilizer.
b) What are colouring constituents of glass? How is iron estimated from
coloured glass?
c) Explain the general scheme of analysis of soap.
d) Enlist the constituents of face powder. Describe the method for estimation
of chloride from sample of face powder.
e) Phosphate containing detergent weighing 0.57 gm was ignited to red hot
to destroy organic matter. The residue was dissolved in hot HCl and
gave H3PO4, the phosphate was precipitated as MgNH4PO4. 6 H2O by
addition of Mg+2 ions followed by aqueous ammonia. After filtration,
washing, drying and ignition at 1000ºC, weight of residue, Mg2P2O7 was
0.441 gm. Calculate percentage of phosphorous in the given sample.
[Given: At. wt: P = 30.97, Mg = 24.31, O = 15.99]
P.T.O.
c) Describe any one method for determination of calcium in propellant.
d) Borosilicate glass weighing 0.308 gm was fused with sodium carbonate
in platinum crucible, and the melt was converted into boric acid by suitable
process. Mannitol is added in whole solution and titrated with 0.110 N
NaOH using para nitrophenol as an indicator, and 29.40 ml of alkali
required for complete neutralisation.
Calculate percentage of B2O3 in sample of glass.
[Given At. wt : B = 10.81, O = 15.99]
e) 1.507 gm of sample of Brass was dissolved in acid mixture and the
solution was diluted to 250 ml. 150 ml aliquot was used for determination
of Cu and Zn. Copper was determined electro gravimetrically. Weight of
copper deposited after electrolysis is 0.615 gms. Zinc was determined
gravimetrically as Zn2P2O7. The weight of residue was 0.435 gm. Calculate
percentage of Cu and Zn.
[Given : At. wt: Zn = 65.38, P = 30.97, Cu = 63.54, O = 16]
SECTION - II
Q3) Attempt any Four of the following : [20]
a) What is steel? Explain the analytical procedure for the estimation nickel
from steel.
b) Explain the analytical procedure for estimation of calcium from Dolomite
ore.
c) Outline the analytical procedure for the determination of any one of the
following.
i) Ti from ilemenite ore.
ii) Si from bauxite ore.
iii) Cu from cupronickel alloy.
d) 4.510 gm washing soda was dissolved in distilled water and diluted to
250 ml, A 25 ml aliquot of this solution was titrated with 0.110 N HCl
using Methyl orange as an indicator, gave burette reading 30 ml. Calculate
percentage of Na2CO3 in given sample.
[At. wt. Na = 22.98, C = 12, O = 15.99]
e) Analysis of the components of 2.110 gm of shipnail brass yielded 0.0685
gm SnO2 and 0.2824 gm PbSO4. Calculate percentage of Sn and Pb in
alloy.
[Given: At. wt. Sn = 118.7, Pb = 207.2, S = 32, O = 16]
[4325]-315 2
Q4) Attempt any four of the following : [20]
a) Explain the method of determination of hexavalent chromium from waste
water.
b) Write note on (any one) :
i) Cyclone separator.
ii) Anaerobic decomposition.
c) How SOx is generated? Give its hazardous effects on materials. How is it
controlled?
d) Explain the terms COD and BOD. How is COD estimated from Waste
water?
e) Write note on safety measures in industries.
ïïï
[4325]-315 3
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) State and explain Faradays laws of electrolysis. Give its important
application.
b) Explain the following terms :
i) Resistor.
ii) Conductance.
iii) Capacitors.
iv) Inductors.
v) Transformers.
c) What is rectification? Describe the working of a diode as a full wave
rectifier.
d) Write a critical note on Flow injection analyzers.
e) Calculate the binary equivalent of 7497 and decimal equivalent of
1110001011.
[4325]-316 2
c) Explain the role of Supercritical Fluid Chromatography as an analytical
tool in pharmaceutical analysis.
d) Explain clinical applications of radioimmuno-assay of Esterogen.
e) 5 ml sample of blood was treated with trichloroacetic acid to precipitate
proteins. After centrifugation the resulting solution was brought to pH 3
and extracted with 2 ml portion of methyl isobutyl ketone containing the
organic lead complexing agent. The extract was aspirated directly into
an air acetylene flame and yields absorbance 0.532 and 0.290 5ml of
aliquot of standard solution containing 0.400 ppm and 0.600 ppm of
lead were treated in same way yielding absorbance 0.396 and 0.599
calculate ppm of lead in blood sample.
ïïï
[4325]-316 3
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) Discuss, the unadequate storage conditions and their effects on
pharmaceutical products.
b) Write a note on prediction of shelf- life of pharmaceutical products.
c) Explain any one method for biological assay of Insuline.
d) Give limit test for arsenic.
e) Write a note on dry heat steralisation.
ïïï
[4325]-317 2
Total No. of Questions : 6] SEAT No. :
ii)
iii)
[4325]-401 2
c) The ESR spectrum of Cu2+ in Cs C2O4. H2O shows four lines of equal
intensity at 268.9 mT, 282.3 mT, 295.5 mT, and 307.2 mT. Determine
the effective spin and nuclear spin of Cu2+.
SECTION - II
Q4) Answer any three of the following : [15]
a) Give a brief account of Braggs method used in the elucidation of crystal
structure. State its limitations.
b) Compare the usefulness of XRD and electron diffraction techniques.
c) State and explain the phase problem observed in XRD. Outline the
techniques to overcome it.
d) Define the structure factor and relate it to the reflection intensities in X-
ray diffraction pattern.
e) State and explain X-ray diffraction and interference of wave motions.
ïïï
[4325]-401 3
Total No. of Questions : 6] SEAT No. :
SECTION - I
Q1) a) Explain the following (any three) : [9]
i) Thiophene is resistant to ring opening than furan & Pyrrole.
ii)Indole on reaction with chloroform in alkali gives 3-chloroquinoline
as one of the product.
iii) Purine (pKa 8.9) is much more acidic than imidazole or
benzimidazole.
iv) Pyridine N-oxide readily undergoes electrophilic substitution at the
4-position.
b) Give applications of Supramolecular Chemistry in medicine, data storage
and processing. [3]
i)
ii)
P.T.O.
iii)
iv)
v)
vi)
Q3) a) Write notes on (any two) : [4]
i) Hantzsch Pyridine synthesis.
ii) Use of Thiourea in thiazole synthesis.
iii) Fiest Benary furan synthesis.
b) Suggest suitable mechanism for any two of the following : [6]
i)
ii)
iii)
i)
ii)
iii)
[4325]-410 2
SECTION - II
Q4) Answer any three of the following : [12]
a) Write 1C4 and 4C1 conformation of D-Mannose and L-mannose
b) Two isomeric compounds A & B having MF C4H8O4 gives following
reactions.
i) Both A & B forms oximes.
ii) Both A & B forms triacetate.
iii) A on oxidation with HNO3 gives optically inactive acid while B
gives optically active acid. Deduce the structure of A & B.
c) Write Ruff degradation of aldopentose to aldotetrose.
d) Comment on stability of D- Gluco Furanose and D-Gluco pyranose
with special note on anomeric effect.
i)
ii)
iii)
iv)
[4325]-410 3
Q6) a) Describe the basic principles of green chemistry. [4]
b) Calculate the % atom economy for following reaction. [2]
ïïï
[4325]-410 4
Total No. of Questions : 6] SEAT No. :
[4325]-402 3
Calculate the transfer coefficient and exchange current density for
hydrogen/hydrogen ion equilibrium at nickel cathod in the given medium
at 298 K.
c) Calculate the Zeta potential in Helmholtz double layer in a solution having
dielectric constant 78, ionic charge density 1015esu and separation between
the Helmholtz layer is 105 cm.
ïïï
[4325]-402 4
Total No. of Questions : 4] SEAT No. :
[4325]-403 2
Q4) Attempt any four of the following : [20]
a) Describe the diffraction method for determination of molecular weight
of a biopolymer.
b) State the principle of X-ray diffraction. How is it used to determine the
molecular weight of an asymmetric macromolecule?
c) What is Electrophoresis? State its types. Explain any one.
d) Discuss the theory of optical rotatory dispersion.
e) Discuss the applications of circular Dichroisn.
f) What are micelles and bilayers? Differentiate between these.
ïïï
[4325]-403 3
Total No. of Questions : 5] SEAT No. :
[4325]-404 2
d) Explain the necessity of thin targets and techniques for their preparation.
e) Write a note on carriers used in nuclear reaction.
f) Discuss Sworski and Schwarz relationships for the yield of molecular
products and the solute concentration.
ïïï
[4325]-404 3
Total No. of Questions : 4] SEAT No. :
P.T.O.
Q3) Answer any Four : [20]
a) Explain the use of X-Ray Diffraction technique for determining the structure
of zeolites.
b) Explain the significance of volcano diagram in heterogeneous catalysis.
c) Write an account on Heteropolyanions of Molybdenum.
d) Explain the role of sulphides as catalysts.
e) Explain the following terms :
Polysilylenes, Silicones, Silicon rubber and Feldspar.
ïïï
[4325]-405 2
Total No. of Questions : 4] SEAT No. :
P.T.O.
Q3) Attempt any Four of the following : [20]
a) What is hysteresis loop? Saturation magnetisation of F.C.C. iron is 1750
KA/m2. Calculate the net magnetic moment per iron atom in the crystal.
Given : Lattice parameter of F.C.C. is 2.87ºA
and 1BM = 9.273 × 1024 A/m2.
b) Derive the expression of Curie law.
c) In Ge energy gap is 0.75 eV. What is wavelength of which starts
absorption of light?
d) Calculate the conductivity of pure silicon at room temp. when
concentration of carrier is 1.6 × 1010 per cm3, Take µe = 1500 cm2/V.S
and µn = 500 cm3/V.S.
e) In an n-type semiconductor, the fermi level lies 0.3 eV below the
conduction band at room temp. If the temp. is increased to 330ºK. Find
the position of fermilevel. (Room temp = 300ºK)
ïïï
[4325]-406 2
Total No. of Questions : 9] SEAT No. :
SECTION - I
Inorganic Applications in Industry
Q1) Attempt any three of the following : [15]
a) What is meant by term pigment? Explain the following properties of
Inorganic pigments.
i) Colour and tints.
ii) Reactivity with vehicle.
iii) Resistance to light.
iv) Chemical resistance.
b) Explain the methods for electroplating of precious metals.
c) Give an account of preparation of copper dyes from O-hydroxy diaryl
azo compounds and O-halogeno-O-hydroxy diaryl azo compounds.
d) Explain the microstructure of soft and hard wood.
Q2) Attempt any three of the following : [15]
a) What is the difference between a pigment and dye? Explain the use of
chromium in dyeing of wool using azo dyes? Give the structure of the
compounds involved.
P.T.O.
b) How are redox centers to PVP electrode coating? Explain the effect of
increasing the positive potential of the platinum electrode on
electrodeposition.
c) Which types of isomerisms are seen in chromium and cobalt complexes
of tridentate azo compounds? Explain any one type of isomerism.
d) Explain two methods of electroplating of tin.
[4325]-407 2
c) Draw a schematic diagram of a Phosphoric Acid Fuel Cell (PAFC).
What reactions are occurring at the cathode and anode? Show over all
reaction.
d) What is meant by point and nonpoint sources of pollution? Give an
example of each.
ïïï
[4325]-407 3
Total No. of Questions : 6] SEAT No. :
SECTION - I
Q1) a) Outline the steps involved in the following synthetic sequences. Indicate
the reagents and discuss the mechanism and stereochemistry involved
(any three) : [12]
i)
ii)
iii)
iv)
P.T.O.
b) Explain the importance of Navasakas boron template methodology in
construction of molecule X already possessing four contiguous
stereogenic centres. [4]
Q3) a) 3', 4'- demethyl podophyllotoxin has the following structure. [6]
[4325]-408 2
SECTION - II
Q4) a) Discuss the transamination reaction and the role of pyridoxal phosphate
in the reaction. [4]
b) Suggest biogenetic scheme for any three of the following : [12]
i)
ii)
iii)
iv)
[4325]-408 3
Q5) Answer any two of the following : [12]
a) Indicate the position of label in each step and in the final product from
the following biogenetic conversion.
b) Indicate the position of label in each step and in the final product from
the following biogenetic conversion. [6]
ïïï
[4325]-408 4
Total No. of Questions : 6] SEAT No. :
ii)
iii)
a)
P.T.O.
b)
c)
d)
e)
i)
ii)
iii)
SECTION - II
Q4) a) Explain any two of the following : [6]
i) Olefination by Petersons reaction.
ii) Acyl anion equivalent can be prepared from enol ethers.
iii) Synthetic applications of tetracarbonyl ferrate dianion.
[4325]-409 2
b) Explain the use of any two of the following : [6]
i) Sonogashira coupling in organic synthesis.
ii) MOMCl and MEMCl
iii) Bu3SnH
Q5) a) Complete the following transformation using the reagents given below.
Arrange the reagents in proper order (any two) : [6]
i)
ii)
iii)
i)
ii)
iii)
iv)
[4325]-409 3
Q6) Using retrosynthetic analysis, suggest a suitable method to synthesize of the
following (any four) : [16]
i) ii)
iii) iv)
v) vi)
ïïï
[4325]-409 4
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) How is benzoic acid estimated from food sample?
b) Write note on Sweetening tablet.
c) What is Pasteurization? How is it verified?
d) Describe analytical method for estimation of pectin content from Jam.
e) Sulphite containing food sample 31.8 gm was subjected to Tanner method
and the titre value obtained with 0.01 M NaOH was 8.9 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 : [20]
a) How are barbiturates isolated from biological samples by procedure A.
b) State the principle and explain the procedure for extraction of caffeine
from biological sample.
c) Outline Procedure Type B for isolation and identification of
amphetamine.
d) How is heroin isolated from sample?
e) Biological sample was analysed for amphetamine content using gas
chromatographic method, which gives following observations :-
i) Internal standard concentration = 1.6 µg/ml.
ii) Peak height for amphetamine = 8.3
iii) Peak height for amphetamine in standard reference solution = 4.30.
iv) Peak height for standard in specimen = 2.5.
v) Peak height for internal standard in reference solution = 1.62.
vi) Volume correction factor = 0.6.
Calculate the concentration of amphetamine in the given sample.
ïïï
[4325]-411 2
Total No. of Questions : 4] SEAT No. :
ïïï
[4325]-412 2
Total No. of Questions : 4] SEAT No. :
SECTION - I
Q1) Attempt any four of the following : [20]
a) How polymers are classified on their morphological behaviour?
b) Write a note on Emulsion polymerisation.
c) Derive kinetic rate equation for living chain polymerisation.
d) Discuss the effect of radiation on Teflon.
e) What is polymer degradation? Explain degradation by high energy
radiation.
i)
ii)
P.T.O.
iii)
iv)
v)
ïïï
[4325]-413 3