Time Allowed: 3 hours Maximum Marks: 300
Candidates should attempt Question Nos. I 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

I
SECnONA
Answer any three of the following
What are the criteria to be met for the formation of molecular orbitals? Describe the bonding in N2, according to MO theory

Substantiate the statement that "Hybndization does not enter explicitly into MO theory bur mixing of orbitals does occur as in VB theory", taking the example of BeH,

Describethe X-ray diffraction techruque for the detenmnation of crystal structure

Explain and bring out the Significance of radius ratio rule, lattice energy Madelung constant and Born-Haber cycle (20

How does a glass electrode develop potential in the solutions of vatying hydrogen n concentrations, and how1sPH measured?

Describe the principle and techniuque of amperomelly and the estimation of lead by this technique(20)

Calculate the potential of the following cell and indicate whether it iS galvanic or electrolytic Cu| 2 Ag
The standard reducti on potentials are
E0AG= 0.799 V and EOC0=337 V
For a consecutive unimolecular reaction through the formation 0f an intermediate as in the reaction
A SET UP RATE LAWS.
for the vaRIAtion of concentration with time.
(ii)when ka»kb and
(iii)for steady state approXimation
Calculate the quantum yield for the photochemical reaction in which 4-heptanone on irradiation with 315 run radiation, with power output of 50 W for 90 s under the condition of total absorption. produces 2 8 m.mol. of ethane(15)
Derive Langmuir adsorption isotherm. How will you find out the isostenc enthalpy of adsorption?
What iS meant by CFSE? Discuss CFSE in weak and strong field cases for various d" configurations
What are chelate complexes? What are the various factors influencing the stability of chelate complexes?
SECTION B
Answer any three of the folloWlng
DeRIve the equation for calculating the entropy change for the ISothennal expanSiOn of a
(b)derive the nernst heat theorem.
discuss upper and lower critical solution temperatures,with examples. explain the thermodynamic interpretations ofthe upper critical solution temperature.
Derive ClausiUs-Clapeyron equation for the variation 0f vapour pressure with temperature

Explain the principl construction and uses 0f hydro gen-oxygen fuel cell and itS advantages(20)
Explain the factors that influence the stabil1zation of tetrahedral/octahedral co-ordination in the formation of complexes
Explain the technique of cyclic voltammetiy and the significance of peak potential, WeNe slope and reversibility

Discuss the magnetic and spectral properties of lanthanides. How are they different from those 0f d-block elements?

Describe the modem methods adopted for the separation of the lanthanides Discuss the important oXidation states of lanthanides
describe the photo syntheic pro cess and the role of cytochrome C

What are the important reactions of liqUid ammonia and liquid sulphur dioxide as non­aqueous solvents

Discuss the preparation properties and uses of carbonylate anions

Define enthalpy and its implications in thermo chenuslly How will you evaluate an enthalpy change using a differential scanrung calonmeter?