CHEMISTRY 603

“FUNDAMENTALS OF MOLECULAR SPECTROSCOPY’

Take-home examination, October 1, 2019
Profs. M. Harrington and I. S. Butler
Due date (hard copy, show your working): October 15, 2019

1.

You performed a cyclic loading tensile test on a piece of material with a cylindrical
shape (diameter = 8.5 mm) and a length of 11 cm. Calculate the material stiffness,
yield stress, yield strain, hysteresis and resilience of the material based on the
load-displacement curve above.
2. A silk fiber produced by a newly discovered spider species was cut into three
identical pieces and tested at three different extension rates resulting in the
different stress-strain curves shown above.

(a) This is an example of what type of mechanical deformation? Explain your

reasoning.

(b) (Describe two different mechanical testing methods you could use to further
investigate your answer from part a. What would you expect to observe
when using these two methods if your hypothesis is correct?
3. The synthesis of the five-coordinate [Fe(CO)4I]- ion has been reported. It exhibits
three infrared-active bands in the CO stretching region at 2062w, 2003w and
1975m cm-1. There are four idealized structures possible for this ion – two trigonal
bipyramidal ones and two square-pyramidal ones. Which structure would be most
consistent with the observed infrared data. What other vibrational measurements
could you to do to help confirm your proposed structure?

4. The vibrational data (cm-1) for the fundamental vibrations of CH335Cl are given
below.

Infrared (vapor) Raman (liquid)

3041.8 (s) 3036 (m, depol)
2966.2 (vs) 2955 (vs, pol.)
1454.6 (m) 1446 (w, depol)
1354.9 (s) 1370 (vw, pol)
1015.0 (m) 1016 (w, depol)
732.1 (vs) 709 (vs, pol)

(a) What are the symmetries, spectroscopic activities and vi numbers of these
vibrational modes?

(b) There are five additional bands observed in the vapor phase infrared spectrum
at 2878.8, 3978.9, 4046.0. 4229.4 and 9690 cm-1. How would you explain the origin
of these extra bands?

5. Here are two questions involving the Teller-Redlich product rule for isotopic
vibrational shifts.. Make sure to read through the notes that you were given.

(a) The vibrational spectra of H2O and D2O vapor have been well studied over the
years. The data (in cm-1) are listed below. Can you predict the position of the v2
band of D2O from these data?

H2O vapor D2O vapor

v1 3756.7 2671.5
v2 1594.6 ?
v3 3755.6 2788.0

(b) The observed infrared-active fundamentals (cm-1) of CD335Cl are listed below.
Predict the position of the missing fundamental, v3?

v1 2161 v5 1058
v2 1029 v6 1029
v3 ?
v4 2286
6. The infrared spectrum of (𝜂 5-C5H5)Mn(CO)2(SMe2) in n-hexane is shown below.
(Hint: Think about conformational isomerism.)

(a) There are four main bands observed at 1949(m), 1941(s), 1885(m) and
1871(s) cm-1. Account for the observation of these four bands.

(b) Suggest the origin of the very weak bands in the spectrum.