Department of Chemistry, IIT Ropar Mid-semester Examination, 19th September, 2012 CYL101: Structure, Reactivity and Dynamics

Part A Physical Chemistry Solutions (34 Marks) 1. Fill in the blanks: (61) (i) The two approximate methods used to solve Schrdinger equation for many electron systems are Perturbation and variational theorems. (ii) A realistic anharmonic potential can be described in analytical form by Morse. (iii) At the inversion temperature the Joule Thompson coefficient will be zero. (iv) Maximum temperature attained by the flame due to heat liberated by the combustion of fuel under adiabatic condition at constant pressure is Maximum Flame temperature. (v) The entropy of mixing of one mole of O2 and two moles of H2 is 15.8 JK-1. (vi) Energy dependence of rate constant is postulated by RRKM theory. 2. Consider the following mechanism for an enzyme catalysis: (2)

ES E+P E + S k k
k1
k2
1
2

where E stands for enzyme, S for substrate, ES for enzyme-substrate complex and P for product. Derive the rate law for the formation of the product during the initial stages.

r=

k2 k1[ E ]0 [ S ] V [S ] = max k1[ S ] + k1 + k2 [ S ] + K m

3. List the assumptions of Langmuir isotherm in heterogeneous catalysis. (2) Solid surface is homogeneous and has a finite no. of sites Each site can adsorb only one molecule and when all sites are covered resulting in unimolecular layer. Adosrbed molecules do not reach with each other. Rate of reaction is proportional to the fraction of the surface covered at any time. 4. The gas phase rearrangement reaction, Vinyl allyl ether Allyl acetone, has a rate constant of 6.015 105 s1 at 420 K and a rate constant of 2.971 103 s1 at 470 K. Calculate the (2) values of the Arrhenius parameters A, Ea and H# at 420 K. 11 -1 (A = 5 x 10 s ) (Ea = 128 kJmol-1) -1 (H# at 420 K = 124.5 kJmol ) 5. Copper-64 (t1/2 = 12.8 h) is used in brain scans for tumors and in studies of Wilsons disease. Calculate the number of days required for an administered dose of copper-64 to drop to 0.10% of the initial value injected. (2) (5.3 days) 6. At a given temperature, the equivalent conductivity of a 0.1 N solution of weak acid HA is 3.48 mho cm2 and the ionic conductivities of H+ and A- ions at infinite dilution are respectively, 318 and 30 mho cm2. Calculate, a. The dissociation constant of the acid (K = 1.3 X 10-5)
1

b. The pH of the 0.1 N solution.

(pH = 3)

(2)

7. Determine the solubility product of AgBr at 25oC from the following data:
o o = 0.799 V; E Ag = 0.0711 V at 25oC. E Ag + / Ag / AgBr , Br

(2)

(Ksp = 4 x 10-13) 8. The heat capacity of a substance is given by the following equations: Cp(s) = 16.7 10-5 T3 (0 < T < 50 K) Cp(s) = 20.9 Cp(l) = 25.1 (50 < T < 150 K) (150 < T < 400 K) (2)

At the melting point, Hf = 1255.2 Jmol1. Calculate the absolute entropy of the substance in the liquid state at 300 K. (S = 55 JK-1mol-1) 9. Calculate the value of dT/dP for the water-ice equilibrium system at 0oC. Hfus for water is (2) 6007.8 J mol1. (-0.0075 K atm-1) 10. For the reaction at 25oC, Pb(s) + Br2(l) PbBr2(s), G o = 62 kcal and H o = -66 kcal. Calculate the standard entropy of Br2 given the standard entropy values of PbBr2 and Pb to be 38.6 e.u. and 15.5 e.u. respectively. ( S o = 36.1 e.u.) (2) 11. An ideal gas of volume two litres at 0oC and 5 atm pressure is expanded isothermally and irreversibly against a constant pressure of 1 atm. Calculate w, E , H and q in each case.
( E =0; H =0;w= q = 810 J)

(2)

12. Draw the electron probability densities of the hydrogen atom associated with the radial part of the wave function for principle quantum number 3. (2)

13. Write the electronic Hamiltonian for the following quantum systems: (i) H atom

(2)

(ii) H2+ molecule.

14. Calculate the expectation value of the energy of a particle of mass m confined to move in one dimensional box of width a and infinite height with potential energy zero inside the box. The normalized wave function of the particle is n ( x) = (2 / a)1/ 2 sin(n x / a ) where n=1, 2, 3, (2)
En = n2 h2 8ma 2

15. What is Hermitian operator? Prove that the kinetic energy operator is Hermitian.

(2)