SECTION A
I. Define and differentiate between the above
4x3=12
Normalized and Orthogonal wave functions
Eigen value and Eigen function
Eigen value and Most probable value

The heat of vaporization of ether is 25.98 kJ mol-1 at its boiling point 34.5°C. Calculate the rate of change of vapour pressure of ether with temperature at the boiling point. 12
Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the sodium atom. Calculate the ionization energy of sodium in kJ mol-1. 12

Determine the values of (delta)H and (delta)E for the reversible isothermal evaporation of 90·0g of water at l00°C. Assume that water vapour behaves as an ideal gas and heat of vaporization of water is 2·244 kJ g-1. 12
e)Set up Born Haber cycle for determining the enthalpy of salvation of Mg2+ ions from MgCl2 by water. 12

2. The wave function for Is electron of Li is given by
(z312/(rr a8) 1/2)e-Zriao, where as a0 is equal to 52·9 pm.
Calculate the value of radius at which the probability of finding ls electron is a maximum. 20
(bl Metallic sodium crystallises in a body centred cubic lattice and has a density of 1·306 x 103 kg m-3. Calculate the length of the side of the unit cell and the distance between 200 plane d200).
Atomic weight of sodium is 29·99 g mol-1.
Draw molecular orbital diagram for the following molecules and compare bond order, bond length and magnetic properties

CN and CN-

Explain why the bonding in metal cyanides is between metal and carbon. 20

3. (il Derive the Langmuir adsorption isotherm for adsorption of a gas on a solid. Also, mention assumptions involved. 10
Explain the steps involved in the reaction A B C occurring under heterogeneous catalysis. 10

If germanium shows photoconductivity at a wavelength of 1824 nm, calculate the energy gap between the valence band and conduction band in germanium. 20
Discuss the structure and bonding in diborane. 10
Using hybridization, explain what is the shape of XeO3. Explain how VSEPR theory accounts for the distortion. 10
4. Evaluate most probable speed and average speed from Maxwell's relation for distribution of speed in a gas.
Given:

<img src='./qimages/178-4c.jpg'

Calculate (delta)S and (delta)surr for reversibly heating 2 moles of liquid water from to lOO'C at a constant pressure of 1 atm. Treat heat capacity of water independent of T and equal to
4·184 J K 1 g-1. 15

For a pure substance, what is the maximum number of phases that may exist at constant pressure Explain and illustrate. 1O
What are partial molar properties Show that the partial molar free energy is equal to (dh/dni)i 10
Show that for a second order reaction 2A products, the half-life is inversely proportional to the initial concentration of A 10

SECTION B
5. When Cl2 is dissolved in water, it disproportionates, producing c1- ion and HCIO. Find at what H3O+ concentration the potential for the disproportionation changes from a negative value to a positive value, assuming 1·0 atm of pressure and concentration of l·O M for all species except hydronium ions. Given


E0 1·36 and E0 1,63 at 25°C.
Cl c1- HCIO, Clz 12

The value of temperature coefficient, at 300 K for a reaction is 2·8. Calculate the energy of activation of the reaction.
Volume of nitrogen required to cover through monolayer 1 g of silica gel is 0·129 dm3 at 1 atm and 273 K. Calculate the surface area of the gel if each nitrogen molecule occupies an area of 16·2 X 10-lO m2. 12
With the help of P V diagram of NH3 explain the critical temperature.
Explain the term 'overpotential'.
12
12

6. (al Calculate overall voltage output of a hydrogen oxygen fuel cell which shows free energy change (delta G0) at 25"C equal to 273·3 kJ mol-1. Also, write anodic, cathodic and overall reaction taking place in presence of KOH.

Discuss the working of a polarograph. Define E1/2 and id and mention their application in chemical analysis.
(cl Write a short note on ion selective electrodes and their uses.
Describe the relaxation method for studying kinetics of fast reactions.
(el Which compound is called 'inorganic benzene' and why? 12
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7. What are sacrificial anodes How do they inhibit corrosion
A certain system absorbs 3·0 x 1018 quanta of light per second. On irradiation for 10 minutes, 2·0 x 10-3 moles of the reactants was found to have reacted. Calculate the quantum efficiency of the process.
What are the functions of carbonic anhydrase and carboxypeptides Explain.
What molecule is responsible for oxygen transport in molluscs Give its structure.
JO
15
20
15

8. From the following data calculate the solubility product of AgCl at 25°C

Ag O·l M KCI satd. with AgCl O·l M AgN03 Ag

(Given Ecell at 25° C 0.455 log10 2 0.3 14
Explain what is lanthanide contraction.
CuCl2 is coloured but ZnC12 is colourless. Explain. 16
Draw all the stereoisomers of Cl2] and comment on their optical activity.
r.d) Compare the 10 Dq values of the following ions with proper justification (At. No. of Fe and Os are 23, 26 and 76 respectively)

0)6 and
and

Given Constants for use
NA 6·023 x 1023 mo1-1
h 6·625 X 10-34 Js
KR l ·38 x 10-23 J K-1
c 3·0 x 108 ms-1
R 8·314 J K-1 mol-1