BITS Pilani Hyderabad Campus

Second semester 2019-2020

CHEM F-111
14.02.2020
Assignment -2 question pool

Lecture-9 to Lecture-13 and Thermochemistry (self study). Students are advised to work
on all the problems given below. The portions that will be covered for assignment-2 has
been given in a separate notice.

Q1. The radial part of wavefunction for a 2p electron in hydrogen atom is

R2,1(r) = (1/26)(1/ao)3/2(r/ao)e-r/2ao
(i) Give expression for radial distribution function.
(ii) Calculate the most probable radium (in terms of ao)
(iii) Calculate the maximum value of radial distribution function (in terms of ao).
(iv) Sketch the radial distribution function.

Q2. Prove with an example (say, He atom) that the orbital approximation in many-electron
atoms would be exact if there were no interactions between electrons.

Q3. (i) Write the electronic configuration of the V2+ ion. (ii) What are the possible values of
the total spin quantum numbers S and Ms for this ion?

Q4. Write the wavefunctions (without normalization constant) corresponding to the (i) MS = 0-
triplet, (ii) MS = 1-triplet, (iii) MS = -1-triplet, and (iv) singlet states arising from the excited
state electronic configuration, 1s12s1 of helium atom.

Q5. (i) What atomic terms are possible for the electronic configuration, ns1np1?
(ii) Which term is likely to lie lowest in energy?
(iii) Give the possible term symbols for (a) Sc: [Ar]3d14s2, (b) I: [Kr]4d105s25p5
(iv) Write the lowest energy term symbol in case of (a) and (b).

Q6. Determine (i) the lowest energy term arising from the ground state electronic configuration
of Co2+, (ii) all possible levels and corresponding term symbols of this term and (iii) number
of states belonging to the lowest energy level of this term.

Q7. (i) What values of J may occur in the term 2H? (ii) How many states (distinguished by the
quantum number Mj) belong to each level?
Q8. (i) Consider electronic transition from [Ne]3p1 to [Ne]3s1 state of sodium atom. What are
possible term symbols of the states involved in this transition?
(ii) Show the possible transitions and comment on whether the transitions are allowed or not.
Q9. Write down the unnormalized valence bond wavefunctions (with spin part) for the  bond
and any one of the two  bonds in P2 molecule (denote two phosphorus atoms as A and B and
two electrons as 1 and 2). Neglect hybridization in P atoms and assume that only three p-
orbitals of each of the P atoms are involved).

Q10. Some chemical reactions proceed by initial loss or transfer of an electron to diatomic
species. Which of the molecule N2, NO, O2, F2, and CN would you expect to be stabilized by
(a) the addition of an electron to form AB-, (b) the removal of an electron to form AB+?

Q11. Draw MO diagram of CO molecule. Write the MO electronic configuration. Calculate

bond order. Indicate HOMO and LUMO in CO molecule.

Q12. A molecule of the type AB has normalized valence bond wavefunction, ψ = 0.889ψcov +
0.458ψion. What is the chance that in 2000 inspections of the molecule, both the electrons of
the bond will be found on one atom?

Q13. (i) Determine the normalization constant of the sp2 hybrid orbitals, h1 = s + 21/2py and h2
= s + (3/2)1/2px - (1/2)1/2py.
(ii) Show that the normalized hybrid orbitals, h1 and h2 do not overlap i.e they are mutually
orthogonal to each other.
(Given that s, px and py orbitals are each normalized to 1).
(iii) Do mention the angle between these two hybrid orbitals?

Q14. Calculate the work done by 2 moles of an ideal gas during the expansion from 2 atm. at
0 oC to 1 atm. at 27 oC against a constant pressure of 1 atm. If for the gas Cp = 5 cal./mole deg,
find also the ΔU, ΔH, and Q for the process.

Q15. The mole of an ideal monoatomic gas initially at STP experiences a reversible process in
which the volume is trebled. The nature of the process is unspecified, but ΔH = 8.314 kJ and q
= 5.2 kJ, Calculate the final temperature, pressure, and ΔU and W for the process. Let the gas
be taken to the same final condition by a process involving a reversible isochoric and then
isothermal change, calculate the ΔH, ΔU, q and W for this sequence.

Q16. (i) Standard enthalpy of vaporization of water at 100 oC is 40.66 kJ mol-1. Calculate the
standard internal energy of vaporization of water at 100 oC; (ii) The standard reaction
enthalpies, rHo of the following two reactions are known:
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g), rH1o = -26.8 kJ mol-1
FeO(s) + CO(g)  Fe(s) + CO2(g), rH2o = -16.5 kJ mol-1
Calculate rHo of the following reaction: Fe2O3(s) + CO(g)  2FeO(s) + CO2(g).

Q17. Enthalpies of formation of CO2 (g) and H2O (l) under standard condition are -94.8 and -
68.3 kcal/mole respectively. If the enthalpy of combustion of acetaldehyde is -279.07
kcal/mole, find its enthalpies of formation.