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1. Zinc is an important micronutrient in human metabolism. Illustrate the role of Zinc in our respiratory system. (3)
2. Compare the aromaticity of naphthalene and 1, 6–Methano[10] annulene. (3)
3. Arrange the following carbonyls in the order of increasing CO bond order: diene Mo(CO)₃, (Py)₃Mo(CO)₃, (Ph₃As)₃Mo(CO)₃, (Ph₃P)₃Mo(CO)₃, (PhPCl₂)₃Mo(CO)₃, (PCl₃)₃Mo(CO)₃. Justify your answer. (3)
4. Graphically represent and explain the phase-transformation as vapour pressure-temperature curves for a substance undergoing mesomorphic change. (3)
5. The amount of chloride ions present in a solution was determined using precipitation titrations against a standard solution of AgNO₃ with K₂CrO₄ as indicator. The results obtained are 19.8, 20.2, 19.4, 19.0, 18.9, 21.1 and 23.3 g/L. Determine if the value 23.3 can be rejected. Qcritical for 7 observations at 90% confidence is 0.51. (3)
6. Draw the Tanabe-Sugano diagram for d⁶-octahedral system and discuss the utility of the same. (4)
7. Explain how the Curie point of Iron can be deduced using Mössbauer spectroscopy. (4)
8. How can the nanomaterials be classified on the basis of dimensions ? Give examples. (4)
9. Derive the molecular term symbol for the ground state of B₂. (4)
10. Express the BET adsorption isotherm mathematically and graphically. Explain the different types of
adsorption isotherms based on the BET equation. (4)
11. Derive down the general equation for molecular partition function from Boltzmann distribution
and comment on the physical significance. (4)
12. Explain the regioselectivity in the thermal reaction of a ketene with an olefin on the basis of FMO treatment. (4)
13. Predict the stereochemistry of the product formed on the hydroboration of 1-octyne followed by hydrolysis and coupling with Z-vinyl bromide in toluene with Pd(O) catalyst and KOH. Write the mechanism for the reaction. (4)
14. Predict the product of condensation between acetaldehyde and benzophenone in presence of a small amount of a base, NaOH. Justify your answer. (4)
15. The electronic spectrum of [Cu(H₂O)₆]²⁺ is given below.
[Graph of % adsorption against ν̄ (cm⁻¹), with ticks at 5000, 10000 and 15000.]
Explain the reason for this unsymmetric band formation. (4)
16. Aᴵᴵ[B₂ᴵᴵᴵ]O₄ spinels are compounds in which tetrahedral sites are occupied by divalent cations and octahedral sites are occupied by trivalent cation. Account for the formation of inverse spinels when one of the cation is a transition metal. (5)
17. Illustrate Cram's rule with the stereochemistry of reaction between 2-phenylpropanol and
methyl magnesium bromide. (5)
18. Use Hammett plots to deduce the sensitivity of an ester hydrolysis reaction to the electronic
effects. (5)
19. The ¹H NMR spectrum of a compound with formula C₁₀H₁₂O₃ showed the following peaks: δ: 1.4 ppm, triplet, (3.5, s), (4.00, q), (6.8, d), (7.2, d), (12.5, a broad peak). The DEPT–135, DEPT–90 and normal ¹³C peaks are tabulated below:
¹³C | DEPT 135 | DEPT 90
15 | +ve | Nil
40 | −ve | Nil
63 | −ve | Nil
115 | +ve | +ve
125 | Nil | Nil
130 | +ve | +ve
158 | Nil | Nil
179 | Nil | Nil
Deduce the structure of the compound. (5)
20. Derive Gibbs-Duhem equation. (5)
21. Describe primary and secondary kinetic isotopic effect. How can it be used for mechanistic studies ? (5)
22. Set up Hückel Secular Equation and HMO diagram for 1, 3-butadiene. Calculate the delocalization
energy (5)
23. Explain the use of calixarenes as molecular receptors. (5)
24. Construct the character table for PH₃ molecule symmetry. (5)
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