MS3014 tutorial
Infrared spectroscopy
4
Recap: IR spectroscopy
1. Introduction to infrared spectroscopy
o Principles of IR spectroscopy
o Infrared spectrometer
o IR spectrum
2. Molecular motions due to IR absorption
o Possible types of molecular vibrations
o Degree of freedom in molecules
o Detectable motions under IR
o Overtones and coupled interactions
3. Data analysis and applications of UV-VIS 2
1. (i) Calculate the total degree of vibrational freedom for water (H2O). Sketch all
possible vibrations of this molecule.
Water is a non-linear molecule with 3 atoms.
So total degree of freedom for water = 3N – 6 = 3(3) – 6 = 3
Symmetric stretch Scissoring bend Asymmetric stretch
3
(ii) Draw the IR spectrum of water, assigning the peaks to the vibrational modes
identified in (i).
Transmittance (%)
4
(iii) If the frequency of radiation absorbed by a molecule is 2.5 x 1013 Hz, at what
wavenumber (cm-1) would this absorption appear in an IR spectrum?
c = λv 1
and v=
λ
v 2.5 ×1013 4 −1
v= = 8
= 8.33×10 m
c 3×10
−1
= 833cm
5
2. Which molecule (A – D) would its symmetric C=C stretch occur at the lowest
wavenumber? Justify your answer.
A B C D
Since we are all talking about the same C=C bond in all 4 molecules, we will
need to consider the effect of coupled interactions.
Of all 4 molecules, molecule B has the least bulky side group, and hence
would require the lowest energy to stretch the C=C bond.
Since energy is proportional to wavenumber, the C=C stretch in B will occur the
lowest wavenumber. (Molecule D will have the highest)
6
1 k
When do we use v= ?
2π c µ
When we are comparing
between dissimilar things!
7
3. A molecule has strong fundamental bands at the following wavenumbers:
C-H bending at 730 cm-1
C-C stretching at 1400 cm-1
C-H stretching at 2950 cm-1 6.1.3.2 Mechanical anharmonicity
Harmonic oscillator model : V=kx2/2 Hook’s law
In real molecules, the potential curve is not harmonic.
Determine the wavenumbers of the possible combination and overtone bands that
Harmonic ppotential assumption
p is only
y valid when r is very
y close to re.
As r is away from re, potential is deviated from the Hook’s law.
can be observed in a typical spectral region of 400 – 4000 cm-1.
Overtones are multiples of the fundamental frequencies: =3
3
=2
1st overtone of C-H bending = 730 x 2 = 1460 cm-1 (and 2190, 2920, =1
3650) =0
1st overtone of C-C stretching = 1400 x 2 = 2800 cm-1
1st overtone of C-H stretching = 2950 x 2 = 5900 cm-1 (out of range) fundamental
t
transition
iti
overtones
Combination bands are sum of fundamental wavenumbers:y
Due to mechanical anharmonicity.
Vibrational selection rules for IR and Raman transitions are changed to
= 1, 2, 3, ...
Possible combination bands are:
730 + 1400 = 2130 cm-1 Due to mechanical anharmonicity, vibrational term values and wavefunctions are
730 + 2950 = 3680 cm-1 modified.
Potential curve becomes anharmonic
1400 + 2950 = 4350 cm-1 (out of range) 1 2 8
V (x) kx V (x) De [1 exp( ax )]2 : Morse potential
2
4. You are asked to coat the surface of a material with a layer of proteins. You performed
FTIR and obtained spectra of (a) uncoated material, (b) protein-coated material and (c)
pure protein solution as shown below.
Is your coating method successful? Justify your conclusions.
• If you look at (b), you can see peaks at 1658 and 1558
cm-1 that were absent in (a) but characteristic of (c)
• These extra peaks correspond to amide I and II bands,
which appear in the 1700-1600 cm-1 and 1510 -1580
cm-1 regions respectively.
• Amide I is associated with the C=O
stretching vibration in the protein
backbone, while Amide II results primarily
from N-H bending vibration (40-60%).
• Based on this data, I will conclude that my
coating method is in fact successful. 9
5. The following shows the IR spectrum of formaldehyde (H2C = O). What vibration is
responsible for the peak at wavenumber 2850 cm-1?
A. asymmetric stretch of CH2
B. scissoring of CH2
C. symmetric stretch of C=O
D. rocking of C=O
1 k
Recall the equation: v =
2π c µ
1. Stretches usually occur at higher wavenumbers than bends (bends require less energy).
Hence, we are only left with the two stretches (i.e., CH2 v.s. C=O).
2. Since wavenumber is inversely proportional to reduced mass, CH2 has a smaller reduced
mass, so its likely to have a higher wavenumber than C=O stretch. Hence, wavenumber at
2850cm-1 is due to asymmetric stretch of CH2 (Answer A) 10
Lecture learning outcomes
You should be able to:
1. describe the working principles of infrared spectroscopy and general
features of an IR spectrum;
2. identify possible types of molecular motions and calculate the degrees
of freedom for any given molecule;
3. analyze infrared spectra (i.e., identify functional groups & their
vibration modes); and
4. identify suitable applications for IR spectroscopy (i.e., know limitations
of technique)
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OH
stretch
Transmittance
Ethanol
CH2 bend
CH stretch C-O stretch
Wavenumber (cm-1) 12
Ethanol OH
stretch
Transmittance
CH2 bend
CH stretch C-O stretch
Ethanoic acid
13
What determines intensities of the bands?
Which of the following vibrations will have the HIGHEST wavenumber for a given hypothetical molecule?
Answers: A. Asymmetric stretch of C-O
B. Scissoring of C-H
C. Rocking of O-H
D. Symmetric stretch of C-H
Which of the following applications would you recommend the use of IR spectroscopy?
Answers: A. To quantify the amount of ethanol in a simple mixture of
ethanol and methanol.
B. To quantify the amount of N2 dissolved in a solution
C. To measure the amount of NH deposited on a surface
after a chemical reaction.
D. To determine the molecular structure of an unknown
organic molecule.
