Course Number: CHEM F111 Course Title: General Chemistry Marks: 15

Tutorial Problem Set-01 Lecture 1–22 in the course handout

Instructions to the students: The following problems should be solved as home assignment
within a week of distribution. Assignment-01 will be conducted on Thursday (07 Marah 2019) in
a common hour.
Data: Planck’s constant = 6.626 x10-34 Js; Avogadro number = 6.022 x 1023 mol-1. ; Boltzmann Constant =
1.38 x 10-23 J K-1; Relative Atomic Mass of He = 4; mass of electron = 9.1091 x 10-31 kg; Charge of electron =
1.6021 x 10-19C

Assignment-01 (L. No. 11-22)

Q1. (A) Calculate the size of the quantum (energy in kJ mol-1) involved in the excitation of i) a
molecular vibration of period 10-14 s, ii) a pendulum of period 1 s. [4+3 = 7]
(B) What is the de Broglie wavelength of i) a helium atom in a container at 298 K (assume kinetic
energy of the atom is 3/2 kT), ii) an electron accelerated through a potential difference of 1 kV?
[4 + 4 = 8]
Q2. (A) Find the normalization constant for the wavefunction “xexp(-r/2a0)” in three dimensional
space. (Note: r = 0 to ∞ ; ϕ = 0 to 2π;  = 0 to π; dτ = r2 sin dr d dϕ and
∞ 𝑛!
∫0 𝑥 𝑛 𝑒 −𝑎𝑥 𝑑𝑥 = 𝑎𝑛+1 ). [7]

(B) Particle in a box wavefunctions are not the eigenfunctions of the momentum operator;
however, we can determine the average/expectation values for the momentum. Find <p y> = the
average/expectation value for the y-component of momentum, for the 3-D wavefunction

8 1𝜋𝑥 2𝜋𝑦 3𝜋𝑧

𝛹(𝑥, 𝑦, 𝑧) = √𝑎𝑏𝑐 𝑠𝑖𝑛 𝑠𝑖𝑛 𝑠𝑖𝑛 .
𝑎 𝑏 𝑐
𝑥 1 1
(Note: ∫ 𝑠𝑖𝑛2 𝑏𝑥 𝑑𝑥 = 2
− 4𝑏 𝑠𝑖𝑛 2𝑏𝑥 ; 𝑎𝑛𝑑 ∫ 𝑠𝑖𝑛 𝑏𝑥 𝑐𝑜𝑠 𝑏𝑥 𝑑𝑥 = 𝑏
𝑠𝑖𝑛2 𝑏𝑥 ). [8]

Q3. (A) A normalized hybrid orbital 𝜙ℎ𝑦𝑏 is expressed in terms of normalized atomic orbitals,
𝜙2𝑠 , and 𝜙2𝑝𝑧 as 𝜙ℎ𝑦𝑏 = 𝑐2𝑠 𝜙2𝑠 + 𝑐2𝑝𝑧 𝜙2𝑝𝑧 . Determine the coefficients 𝑐2𝑠 and 𝑐2𝑝𝑧 if the
hybridization of 𝜙ℎ𝑦𝑏 is (i) 𝑠𝑝 (ii) 𝑠𝑝2 . [4+4]

(B) Two (of the several) hybrid orbitals generated from linear combination of orthonormal atomic
1 √3
orbitals are expressed as: 𝜙𝑎 = 2 𝜙2𝑠 + 𝜙2𝑝𝑧
2

1 1 2
𝜙𝑏 = 𝜙2𝑠 − 𝜙2𝑝𝑧 + √ 𝜙2𝑝𝑧
2 √12 3

Check whether the hybrid orbitals are orthonormal [3]

Determine the hybridization of the orbitals. [4]
Q4. (A) Determine the ground state term symbol and level of (a) Titanium (Ar,3d2,4s2) and (b)
Phosphorus (Ne,3s2, 3p3) [4+4]
(B) An electron was excited from 2p-subshell to 3d-subshell of carbon atom. Determine all
possible terms arising from the resulting electronic configuration. Identify the ground term and
determine the possible levels for the ground term. [7]
Q5. (A) In CFT in an octahedral complex under ligand field, show that the lowering of the
stabilized orbitals is 0.4ΔO while the raising of the destabilized orbitals is 0.6Δo. [4]
(B) For the [Cr(H2O)6]2+ ion, the mean pairing energy P is found to be 23500 cm-1. The magnitude
of Δ is 13900 cm-1. Calculate the CFSE for the complex in configurations corresponding to high-
spin and low-spin states. Which is more stable? [4]
(C) The enthalpy of hydration of Cr2+ is -460 kcal/mol. In the absence of CFSE, the value for ΔH
would be -435 kcal/mol. Estimate the value of Δ for Cr(H2O)62+. [4]
(D) Distinguish between the possibilities in complex ions of Δ = 0 and CFSE = 0. Give an example
for each. [3]
Q6. (A) A solution of [Ni(H2O)6]2+ is green, but a solution of [Ni(CN)4]2- is colorless. Suggest an
explanation for these observations.
(B) An ion, MII, forms the complexes [M(H2O)6]2+, [MBr6]4-, and [M(en)3]2+. The color of the
complexes, though not necessarily in order, are green, red, and blue. Match the complex with the
appropriate color and justify.
(C) Identify the nature of distortion (elongation or compression) for the following complexes and
justify your answer.
(i) [Cr(CN)6]4- (ii) [Fe(H2O)6]3+ (iii) Ni(H2O)6]2+ (iv) [Zn(H2O)6]2+ [3+4+8]
Q7. Mathematical functions are said to be orthogonal if the integral of their product is zero. (A)
Show that the orbitals h1 = s + px + py + pz and h2 = s - px - py + pz are orthogonal. Each atomic
orbital individually normalized to 1. Also, note that: (i) s and p orbitals are orthogonal and (ii) p
orbitals with perpendicular orientations are orthogonal. (B) Show that the sp2 hybrid orbital (s +
21/2p)/31/2 is normalized to 1 if the s and p orbitals are each normalized to 1.
(C) A normalized valence bond wavefunction turned out to have the form Ψ = 0.889Ψ cov +
0.458Ψion. What is the chance that, in 1000 inspections of the molecule, both electrons of the bond
will be found on one atom? [5+5+5]
Q8. The wavenumbers of pure rotational lines of HBr are represented by the equation γ~ = (16.9 J)
cm-1, where J has integral values. Calculate: (A) The moment of Inertia, (B) The internuclear
distance of HBr. (C) Rotational frequency and the period of rotation for the rotational quantum
number 1. (D) Which rotational energy level has the highest population at 298 K? [4+3+4+4]
Q9. (A) The compound CH3CH=CHCHO has a strong absorption in the ultraviolet at 46950 cm-1
and a weak absorption at 30000 cm-1. Justify these features in terms of the structure of the
compound. [7]
(B) Radiation of wavelength 268 nm passed through 1.5 mm of a solution that contained benzene
in a transparent solvent at a concentration of 0.080 mol/dm3. The light intensity is reduced to 22%
of its initial value (so T = 0.22). Calculate the absorbance and the molar absorption coefficient of
the benzene. What would be the transmittance through a cell of thickness 3.0 mm? [8]