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 If conSidered necessary and mdicate the same clearly
I
SECnONA
Answer any three of the following (20x3=60)
What are orthonormal wave functions? Nonmalise the following wave function for a particle in a one-dimensiOnal box
Define molecular partition function. What iS its importance? Calculate the transiational contribution to the intemal energy of an ideal gas and show that its heat capacity iS 3/2 R
Obtain the expressiOn for the entropy of mixing of two ideal gases with and moles respectively at the same temperature and pressure
What iS the entropy of mixing of one mole of oxygen with one mole of nitrogen at 25°C, assuming they are ideal gases?
write the expression for the activity of 2-1 electrolyte in terms of its molality and mean 10mc activity coefficient
Calculate the activity coefficients y. and y±, and activity for 0.001 molal sodium chloride in water at 25°C (Take Debye-Huckel constant A 0 509

What are concentration cells? Show that the e.m.f of an amon-reversible cell with transference iS <img src='./qimages/1148-2a.jpg'>(30)
The vapour pressure of water iS 23.75 torr at 25°C and 760 torr at 100°C What will be the heat of vaponsation?
3 What do the indicles of a set of planes passing through the lattice stand for? What iS the Importance of these planes? Draw two sets of planes VIZ., 110 and 010, passing through the lattice pOlnts of the crystal What is the perpendicular di stance d between 222 planes of a cubic unit cell?
Define "relaxation-time" How is it related to the rate constant of the first-order reaction? The "relaxation-time" for a reversibl e first-order reaction iS 10 micro second, and the equilibrium constant iS l.Ox 10g. Find K1 and K1.(30)
Define heterogeneous catalySiS. What are the various steps involved in it? Derive the rate equatiOn for the Simple surface catalysed reaction involving a single reactant and a single product
What is reSidual entropy? Why certain substances like CO and N2O are associated with residual entropy even at OK?
SECTION B
5.Answer any three of the following
(20x3=60)
What do you understand by the term "superacid"? Give two chemical properties to Justify this nomenclature

(b).On doping non -conducting pale-green ruckel oxide with a small amount of lithium oxide, not only its colour chanles to grey-black but it also becomes a semiconductor Explain(0)

solution of shows an absorption maximum at 20,300cm-1. with the help of crystal-field theory, predict the number of absorption bands in the viSible spectrum of the above species. Give reason to support your answer
Write the general expreSSiOn for filling of electrons in 4f block elements. Justify the statement that oxidation state donunates the chemistry of lanthanides Do some members of this senes exhibit other oxidation states as well? Explain giving reasons
6.(a)Discuss the principle of polarographi c analySiS. What are the advantages 0 f usmg a droppmg mercury electro de over conventi onal electrodes? Why is it necessary to remove any dissolved oxygen before carrying out voltammeinc studies?
(b)What do you understand by an oXidative addition reaction? How does it differ from an msertion reaction? Explain giving two examples of each type supported by chemical equatiOns(20)
Describe the important shuctural features of ferrodoXin molecule What iS its role in photo­syntheSiS?
mew eff. values for the H.S Fe(11) octahedral complexes are in the range of 5.1 5.7 B.M while p5 value iS
only 4.90b.m why?
(b)Diammine dichioroplatinum exists in two geometrical forms -one of the forms iS a well-known anticancer agent. Given that the transeffect of Cl NH3, outline the steps of preparation of anyone of the two isomers

Draw the MO energy level diagram for CO and discuss the bonding feature(20)

Magnetic moment of lanthanides cannot be calculated based only on spin quantum number but by using quantum number J. Explain
"Ammnium hydroxide iS a base in aqueous medium but an acid in liquid ammonia" -Justify this statement uSing suitable examples