Time Allowed: 3 hours Maximum Marks: 300
Candidates should attempt Question Nos. 1 and 5 which are compulsory, and any three of the remammg questions selecting at least one question from each Section Assume suitable data lf conSidered necessary and mdicate the same clearly

SECnONA
Answer any three of the folloWlng (20x3=60)
1.(a)Set up and solve the Schrodinger equation for particle in one-dimenslOnal box.

(b)Briefly discuss M.O. theory. Explain the formation of H2 molecule on the baSiS of this theory.

(c)Write the electronic configuration of NO molecule
(i)WhatlS its bond-order?
How many unpaired electrons are present?
What will be the bond-order of NO?
Will the bond-length be shorter or longer than

What are liquid-crystals? Mention their characteristics Which substances generally behave as liquid-crystals?

Explain Frenkel and Schottky defects in a crystal, with a suitable example

(ii)What do the indices Ci a set of planes passing through the lattice stand for? Draw the sets of planes,
ViZ 100 and 110, passing through the lattice points of the crystal
(b)Derive the Van der Waal s equation of state for real gases What are the units of Van der Waals constants?

(c)Define the terms critical temperature, critical pressure and critical volume How are these constants determined experimentally?

3.(a)The enthalpy of neutralization 0f NH4OH and HCl iS -51.46 kl/mole Calculate the enthalpy
of ionsation of NH4OH. Assume that the enthalpy of neutralization of a strong acid With a strong base is -55.9 kJ/mole
Discuss the entropy change in reversible and irreversible processes. Comment on the statement. Entropy of the universe is always increasing

Explain Nernst heat-theorem. How does it lead to the enunciation of the Third Law of Thermo dynamics? How can the latter be verified experimentally?


The vapour pressure of ice system at 00075°C iS 458 mm and at 0° C lS 759.8 mm of Hg. Calculate the molar heat of fusion of ice. Given that the specific volumes of ice and water at 0° C are 10907 cc and 10001 cc respectively Density of Hg at O°C 136 g per cc
(b)Explain the terms: upper consolute temperature and lower consolute temperature, conjugate solution and tie-line as applied to the solubility of partially miScible liquids
(c)Give an account of Debye-Huckel theory of strong electrolytes. Discuss its Significance
SECTION B

Answer any three of the folloWing (20x3=60)
Considering the following electrochemical cell
Fe, Fe+2 (0.1 Cd+2 (0.01 Cd,
(i)write the cell reaction,
(ii)calculate the EMF 0f the cell,
determine the direction 0f the spontaneous reaction and
(iv)calculate the equilibrium constant of the reaction
(b)Derive the rate equations for the consecutive reaction and parallel reaction.
Derive the kinetics of the photo chemical reaction H2 Br2 HBr

(d)Derive expression for the BET adsorption isotherm What is the application of this equation?

6.(a)Explain the theories of heterogeneous catalysis(20)
(b)Discuss the stability of cyclopentadienyl complexes Give suitable examples containing carbonyl and nitrosylligands
(c)The activation energy of a reaction in the absence and in the presence of catalyst are 75.24 ld/mole and 50.14 kJ/mole respectively How many times will the rate of the reaction grow in the presence of the catalyst in the reaction proceeds at 25°C?
7.(a)Discuss the chemistry of photosynthetic pro case in green plants

(b)What are actinides? Explain the oxidation state and complex forming tendency of actinides

(c)What are the main features of valence-bond theory? Point out its short comings

8.(a)What is meant by stability of a complex ion? On what factors does the stability of a complex ion depend? Explain WIth suitable examples.

(b)Discuss any four types of chemical reactions that take place in liquid-ammonia

(c)Explain the structures of Fe2(CO)9, Re2(CO)l0 and Fe3(CO)12 Show that the metal atoms in these carbonyls obey inert gas rule.(20)