ST.

ALBERT’S COLLEGE ERNAKULAM

UGC-CSIR NET MODEL EXAMINATION DECEMBER 2008
CHEMICAL SCIENCES
PAPER II

Time: 2 hours and 30 minutes

Max. Marks: 200

Question no. 1 shall be compulsory and carries 20 marks. In addition to the compulsory question, the
candidate is required to answer a maximum of 12 questions of 15 marks each. To answer each
question, a candidate will be provided one page each.

1. (a) What do you mean by K-electron capture? Illustrate with one example. What mode of decay
will it undergo if the mass difference of the parent and daughter nuclei is greater than 1.02 MeV.
(b) Show that for an ideal solution, enthalpy of mixing, Hmix = 0
(c) At room temperature the vibrational anti-stokes Raman lines are very weak while the
rotational anti-stokes lines are quite strong. Why?
(d) Convert the bromoaldehyde (A) chemoselectively into the two products 1 and 2
HO R
CHO CHO

Br Br
Br OH
1 A 2 (5 + 5 + 5 +5)
2. (a) Show that for a binary solution of volatile liquids the vapour is richer in the more volatile
component.
(b) Estimate the number of collisions one molecule will make in one second in a gas at 1 atm
pressure and 250C. Collision diameter = 31010. Average speed 400 ms1
(c) Explain the Grothuss mechanism which accounts for the abnormal conductance of hydrogen
and hydroxide ions in aqueous medium. (5 + 5 + 5)
3. (a) Depict graphically the Maxwell distribution of velocities of gas molecules and obtain
expression for the most probable velocity
(b) For the reaction 2NO2(g)  N2O4(g) , G0(298) =  4000J mol1 and H0(298) =  57000J mol1.
Estimate KP at 500 K (10 + 5)
4. (a) Calculate the potential at 298K of the following cell
Zn/ZnCl2 (m=0.01),   = 0.708)Ag ClAgAgClZnCl2 m=0.1, = 0.502Zn
(b) Suggest a synthetic method for the following transformation

OMe OMe

(10 + 5)
5. (a) Write the most stable conformation of the following compound and explain the basis of your
of your prediction.
Me
O F

O F
Cl
 (b) What are the allowed electronic transitions in [CrF6]3 ? Which of these transitions will give
the10Dq value?
(c) Draw the simple Lewis structures for the following anions: thiosulphate, dithionite, dithionate
(6 + 6 + 3)
6. (a) In the reaction 2NH3 N2 + 3H2, initially 0.80 mol of NH3; 0.70 mol of H2 and 0.40 mol of
N2 are present. At a later time t, 0.55mol of H2 is present. Find the extent of reaction and find the
number of moles of NH3 and N2 present at time t.
(b) The equilibrium constant Kp for the reaction H2(g) + S(g) H2S(g) is 20.2 at 9450C and 9.21 at
10650C. Calculate ΔH0.
(c) Show that
∆
(i) KP=Kx(P)Δnand (ii) KP = Kn ∑
where KP, Kx, and Kn are the equilibrium constants in
terms of pressure, mole fraction and number moles respectively, Δn is the difference in the sum of
the stoichiometric coefficients of products and reactants (5+5+5)
7. (a) Discuss the stereoisomerism of cis- and trans-1-tert-butyl-2-methyl cyclohexane
(b) Write the conformations of cis- and trans- isomers of 1-bromo-4-t-butyl cyclohexane and
comment on their relative stabilities
(c)
CH3

?
NOMe2
+ (6+6+3)
8. (a) Calculate the mean activity coefficient of 0.01M NaCl in aqueous solution at 25oC.
(b) Obtain an expression for the liquid junction potential in the cell
PtH2(1 bar)HCl(a±)1 HCl(a±)2H2(1 bar)Pt (5+10)
9. Predict the products of the following reactions
Excess Ac2O
100oC, toluene reflux

(a) HO NH2 One equivalent

of Ac2O
Pyridine

O
LiBH4
COOH
(b) CH3O
EtOH

CN
(c) 1. i-Bu2AlH

2. H2O, H+
H
O
Cl H , Pd, BaSO
(d) 2 4

Quinoline
COOMe
(e) BH3, THF
O
N
Ph (5 x 3)
10. Identify the product formed in the following reactions:
O Ph
RNH 1.
(a) A B
Ca, H 2. H2O
O O
NaOEt, EtOH
Br
(b) EtO A B

O
Li, NH3, ROH MeI
(c) B (major product)
A

O
PhMgBr hydrolysis
(d) A B

11. How many signals will be there in the 1H NMR spectrum of each of these compounds
O
N
(b)
(a) N N N

O
MeO OMe
(c) (d) CF3 N
Me2N Me

O
(e) O
12. (a) Predict the structure of the compound formed in the following reaction
O
OMe ?
+

(b) Discuss the mechanism of the above reaction.

(c) Two isomeric products A and B are expected in the following reaction. Which are they?
Which is the most stable isomer? Give reasons.
O
+ O A + B

O
(d) Careless attempts to carry out a Claisen rearrangement on the allyl ether A often gives the
compound shown instead of the expected product. What is the expected product? Give the
mechanism of formation of the expected product.

O heat O

A (2+3+5+5)
13. (a) Define green chemistry
(b) Discuss the need for green chemistry
(c) What is meant by atom economy?
(d) Which are the twelve principles of green chemistry?
(e) What are solvent free reactions (2+3+2+5+3)
79
14. Pure rotational lines wave number of H Br can be regenerated by the equation
  16.62( J  1)cm1
a. Calculate and draw the rotational energy diagram and spectra showing various transitions
b. At which rotational energy level H79Br will have the highest population at 270C
 c. Which transitions in the absorption and emission spectra will show highest intensity
d. What will be the rotational constant for D79Br
15. (a) Outline the effect of isotopic substitution on rotational spectra of molecules.
(b) Given that the energy of a rigid rotator as EJ = J(J+1)B, find out an expression for the
rotational quantum number Jmax for the most populated level
16. (a)Explain what is meant by proton –coupled spectra and off-resonance decoupled spectra
(b) Predict the approximate 13C chemical shift values for the starred carbon atoms
C*H3C*H = C*H2
(c) At room temperature, the NMR spectrum of cyclohexane shows only a single resonance
peak. As the temperature of the sample is lowered, the sharp peak broadens until at 66.70C
it begins to split into two peaks, both broad. As the temperature is lowered further to 1000C
each of the broad band begins to give a splitting pattern of its own. Explain th origin of these
two families of bands.
(d) Estimate the expected splitting (coupling constant J in Hz) for the lettered protons in the
following compounds

(6 + 3 + 3 + 3)
17. State the rule of mutual exclusion. Illustrate this by taking typical examples of CO2 and H2O
(b) What are the selection rules for the vibrational Raman spectra of a diatomic molecule.
(c) How do the intensities of Stokes and anti-stokes lines compare with each other in the
vibration Raman spectra. (6 + 3 + 6)
18. Sketch the ESR spectrum of cyclopentadienyl radical C5H5
(b) Howmany esr absorption lines do you expect for triphenyl methyl radical
(c) Explain the shifting of g-values in transition metals. (7 + 3 + 5)
19. Construct the group multiplication table for the point group C2V
(b) Explain the term classes in a point group. How many classes are present in the point group
C3V
(c) A molecule contain Cn axis. Do the symmetry operation Cnm and Cnnm belong to the same
class. Another molecule has Cn axis and a C2 axis perpendicular to Cn axis. How many more
C2 axes perpendicular to Cn axis are present. Will the symmetry operations around the C2
axis belong to the same class. (5 + 4 + 6)

20. Which reagent would you use to carry out the following transformations? Do not write the
mechanism.
 (b) Match the following transformations in list I with the name reaction in list II
OH OH A. Diel’s Alder reaction
CHCl3
A. KOH
CHO

NaOH B. Friedel Craft’s Reaction

B. RCONH2 RNH2
Br2
COCH3
AlCl3
C. C. Hoffmann’s Rearrangement
OCOCH3 OH
OMe
OMe
D. AlCl3
D. Reimer Tiemen Reaction
CH3COCl

COCH3
CN CN
E + Heat E. Fries rearrangement

21. (a) The following β-keto acid is highly resistant to decarboxylation. Explain

O
COOH
(b) Explain the difference in reactivities:
Br
NaOEt/EtOH
fast
C(CH3)3 C(CH3)3

Br
NaOEt/EtOH

Very slow C(CH3)3

C(CH3)3
(c) Predict the products in the following reactions:
i. cis-2-aminocyclohexanol ?
ii. trans-2-aminocyclohexanol ? (3+4+8)

22. (a) The emf of the cell AgAgCl(s)KCl(aq)Hg2Cl2(s)Hg is 0.045V at 298K and the temperature
coefficient is 3.38104VK1. What is the reaction taking place in the cell and what are the Gibbs
energy, enthalpy and entropy changes at 298K.
( )
(b) Show that, − = (Gibbs-Helmholtz equation involving partial molar properties)
,
(10 +5)
23. (a) A surface has some fraction θ of the total number of available sites N on which gas molecules
can be adsorbed. It is found that the rate of change of adsorption is proportional to the pressure p
and to the concentration of the available vacant sites. The rate of decomposition is proportional to
the number of adsorbed species. Show that at equilibrium,
= . What is the constant K?
 (b) Calculate the vapour pressure of toluene at 100oC assuming that Trouton’s rule is obeyed. The
boiling point of toluene is 110 oC.
(d) Show that Joule-Thomson expansion is adiabatic as well as isenthalpic.
(7+3+5)
24. (a) State the Onsager reciprocity relation in mathematical form. Will the Onsager reciprocity
relation be valid for a situation when the fluxes have different tensorial character?
(b) In the case of electro-osmosis, mass flux J and I are given by
J = L11ΔP + L12Δϕ
I = L21ΔP + L22Δϕ
Where ΔP is the pressure difference and Δϕ is the potential difference across the membrane.
∆
Show that = −
25 (a) It is well known that the ratio of the number of neutrons to protons decides the so-called “belt
of nuclear stability”. Show this by drawing a graph. Using this explain the decay process
involving , .
(b) What is the order of radioactive disintegration process? Derive the relation between half-life
and decay constant.
(c) A sample of 100 mg of radioactive nuclide decay to 81.85 mg of the same in exactly 7 days.
Calculate the decay constant for this disintegration and the half-life of this nuclide.
26. (a) The formation of cadmium(II) complexes with chloride anion exhibits the successive
equilibrium constants K1 = 1.56, K2 = 0.54, K3 = 0.05, and K4 = 0.46. Suggest an explanation why
K4 > K3.
(b) Suggest a mechanism for the reaction:
[Fe(CN6)]4 + [Mo(CN)8]3  [Fe(CN6)]3 +[Mo(CN)8]4
(c) What is the basis of Ziegler-Natta polymerization? Is Ziegler-Natta system homogeneous?
What is the active metal species in the system? What is the role of Al(C2H5)3 in the catalytic
process? (3 + 7 + 5)
27. (a) Starting from xenon and fluorine and other appropriate reagents, how would you prepare
potassium perxenate? Using VSEPR theory, predict the probable structure of perxenate ion.
(b) Thallium triiodide is isomorphous with ammonium triiodide (NH4)I3. Explain.
(c) In what way the structure of SnF4 differs from the structure of other tetrahalides?
(d) Suggest a method for making [ClF2] and predict its structure
28. (a) Give the selection rules (in terms of quantum numbers) for the following spectroscopic
transitions.
Vibrational, Pure rotational for linear molecule, NMR, EPR
(b) Sketch the vibrational modes of a linear molecule X-M-X and indicate the IR active and IR
inactive ones.
(c) Give the expression relating rotational constant B to moment of inertia. If B = 10 cm1, give
the rotational energy of this molecule in cm1 for rotational quantum numbers J = 0, 1, 2, 3
(d) Show by use of potential energy curves for ground and excited electronic states, the sequence
of steps leading to phosphorescence.
29. (a) For a second order reaction 2A P, show that t1/2 ∝ where t1/2 is the half-life and [A0] is
[ ]
the initial concentration.
(b) The equilibrium constant (K) for the elementary reaction, C2H6(g) 2CH3(g) at 1000K is 1.30
x 1013 mol1 and the rate constant for the forward reaction (k1) is 1.57 x 103 s1. Write the rate
law and calculate the rate constant for the reverse reaction (k1).
(10 + 5)
30. (a) Calculate the entropy of mixing and Gibbs energy of mixing of 5 moles of component A and 5
moles of component B at 270 C
(b) Show that if an engine takes up heat Q from a sink at a temperature T2 and gives to a source at
a temperature T1 without any work, the process would violate the principle of S(universe)≥0.
(10+5)
31 (a) Draw a correlation diagram for disrotatory opening of a cyclobutene to buta-1, 3-diene. Predict
the outcome of the reaction in the ground state
(b) Predict the products formed in the following pericylic reactions

h ?
(i)

+ O ?
(ii)
O
32 (a) Using FMO explain why cyclopentadiene undergoes thermal cycloaddition reaction with
acrolein to give preferentially the endo product.
(b) Benzocyclobutene reacts with maleic anhydride when heated at 2000C to give the single
product shown below. Write the mechanism for this reaction:
O O

+ O O

O O
(8+7)
33 (a) Butadiene contains four π electrons each of which moves freely from one end of molecule to
the other. Treat the molecule as a one dimensional box whose length is equal to the length of the
carbon chain plus half the C-C bond length on either side. The average C-C bond length is 0.14
nm. Calculate the positions of maximum and minimum electron density in the molecule
(b) Show that the probability of finding a particle in a one-dimensional box of length L in the
region x =L/4 to 3L/4 is ½ if n is even and ½ + (1)k/nπ if n is odd (n= 2k+l, where k = 0,1,2,3...)
(8+7)
34 (a) CH3COCH2COCH3 exists mostly in enol form whereas CH3COCMe2COMe exists almost
exclusively in keto form. Why?
(b) Phenol exists more in enol form than in keto form. Why?
(c) Solvents with high polarity enhances the rate of SN1 reaction but retards SN2 reaction. Why?
(d) CCl4 does not react with either Ag+ or OH. But SiCl4 reacts vigorously with water. Why?
(3+4+4+4)
35. Identify A, B, C, D and E
Me PCl5 KMnO4
NH3
H2SO4
A B C D E
SO3 H3O+
SO3H
(5x3=15)
36 Deduce the structure of the organic compound from the following spectral data:
MF: C11H12O2
UV: max=290 (weak, max=15)
IR: 1738(s), 1550 (m-w), 1668 (m-w), 1252 (s), 746 (s) cm1
MS: 43 (base peak), 116, 139, 176
NMR:  = 2.1(s, 3H), 4.72 (d, 2H), 6.62 (d, 1H, J = 6.8), 6.29(m 1H, J = 6.8), 7.09 – 7.53 (cluster
of peaks, 5H )
13
C NMR:  = 171, 136, 134, 129, 128, 126, 123, 65, 21 (15)