Experiment Infrared Spectrometry: Sampling Methods and Quantitative Analysis

2013-19846; 2013-67188
September 30, 2016
I.

Abstract
Infrared Spectroscopy is the analysis of infrared light interacting with a molecule;
it is extensively used in the field of organic and inorganic chemistry where it is
used to determine functional groups in molecules. Infrared spectra may be
obtained from samples in all phases, solids, liquids and gas. The IR spectra of a
plastic sample, alpha-naphthol, acetone and acetic acid were analyzed. The data
obtained were compared with the theoretical results and the functional groups of
the samples were evaluated and confirmed. The thin film sample, alphanaphthol, and liquid sample, acetone showed erroneous results.
II. Keywords: Vibrational motion, Electric dipole moment, Infrared active, wavelength
III. Introduction
fingerprint region. The functional region
contains the peaks that amounts to certain
Infrared spectroscopic techniques
functional groups found in the sample
from its early beginning, continues to be a
compound. The fingerprint region contains
complementary, widely used research tool
series of hard complex peaks which are
in the hands of physicists and chemists for
hard to examine. (Hunt, 2016)
structure elucidation. Compounds are
In this experiment. Samples of liquid,
subjected to infrared radiation which causes
solid and gas were prepared using standard
a
vibrational
motion,
causing
an
methods and spectres were measured
absorbance. The absorbance coming from
using an infrared spectrometer. The
the infrared spectrometer is plotted with
functional groups of each sample were then
respect to wavenumbers. IR techniques
determined.
when combined with intesity measurements
can be utilized for quantitative analysis.
IV. Experimental
Plastic Sample
A small piece of plastic sample was
cut and squeezed on a thin paper container
appropriate for the sample holder. The
spectrum of the plastic was measured
directly.
Solid Samples

Figure 1. The vibration of a molecule even if it

is nonpolar, can result in an oscillation of the
dipole
which
can
interact
with
the
electromagnetic field (Atkins & Paula, 2006)

Wavenumbers are wavelengths

converted
into
centimeters
and
reciprocated. The graph of an Infrared
spectroscopy has two parts. These parts
consist of the functional region and the

Alpha-naphthol was used as the

solid sample. A small amount of alphanaphthol was dissolved using hexane. The
dissolved solution was placed in a KBr
drilled Disk and was exposed to open air
until hexane fully volatilized. The KBr drilled
Disk was placed in an appropriate sample
holder and the spectrum of the sample was
measured. Another sample of alphanaphthol was prepared using the Nojul
method. A small amount of alpha-naphthol

Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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was placed in a mortar and pestle. A drop of

Nojul solution was placed. The sample was
grinded until the mixture turned into a pastelike solution. The mixture was then spread
into the KBr drilled disk. The KBr disk was
placed in an appropriate sample holder and
the spectrum of the sample was recorded.
Liquid samples
Acetone sample was prepared by
squeezing the sample into two KBr disks
and was filled until no air bubbles occur.
The disk with a pressure holder was placed
in a sample holder and the spectrum of the
sample was measured.
Gas samples
Glacial acetic acid sample was
dropped in a glass cylinder with both sides
KBr disk. The sample was left to evaporate
inside the glass container. After evaporation,
the glass cylinder was placed in a sample
holder and the spectrum of the sample was
then measured.
V. Results and Discussion

2004); these vibrations are said to be

infrared active. (Atkins & Paula, 2006)
On the other hand , some vibrations
do not affect the molecules dipole moment,
for instance the stretching motion of a
homonuclear diatomic molecule; therefore
they neither absorb nor generate radiation:
such vibrations are said to be infrared
inactive. (Atkins & Paula, 2006)
The basic components of an IR
machine are: 1) IR source, 2) beam splitter,
3) monochromator, 4)
transducer, 5)
detector. The IR light exits the source and
becomes split into two beams, where one is
directed to the sample and the other to the
reference. The intensity of the beam is
measured by dividing the intensity emitted
by the intensity observed. (Rupawalla,
Singh, Johl, Reid, & Mulleague, 2016)
Some important IR are for example
OH stretch: Not hydrogen-bonded (3600
cm-1) and hydrogen-bonded (3100-3200 cm1)
and the rest are shown in Tables 1, 2 and
3. (Field, Sternhell, & Kalman, 2008)

The portion of the infrared region

has a wavelength range from 2500 to
16000 nm; wherein, the photon energies
associated with this region are not large
enough to excite electrons, but may induce
vibrational and rotational excitation of
covalently bonded atoms and groups.
(Reusch,
2013)
Therefore,
Infrared
Spectroscopy deals with the vibrational
motion of the molecule and radiation coming
from
the
infrared
region
of
the
electromagnetic spectrum. (Hunt, 2016).
The gross selection rule for a
change in vibrational state that is caused by
the absorption or emission of radiation is
that the electric dipole moment of the
molecule must change when the atoms are
displaced relative to one another. Thus for
molecules to show infrared absorptions, it
must possess a varying electric dipole
moment during vibrational excitation (Stuart,
Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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Table 1. Carbonyl (C=O) IR Absorption

Frequencies in Common (Field, Sternhell, &

Kalman, 2008)
Table
2.
Characteristic
IR
Absorption
Frequencies for Common Functional (Field,
Sternhell, & Kalman, 2008)
Table 3. IR Absorption Frequencies in the
Region 1900 - 2600 cm-1 (Field, Sternhell, &

Kalman, 2008)

In preparation of solid samples and

liquid samples, KBr plates or NaCl plates
are utilized to suspend the molecule. This is
feasible due to the salt's structural form to

be strongly ionically bonded, and in turn will

not absorb IR light because it lacks the
vibrational capability. (Rupawalla, Singh,
Johl, Reid, & Mulleague, 2016). It is
important to note that these materials are
highly deliquescent and not resistant to
moisture. Therefore they should be cleaned
using nonpolar solvents such as acetone or
hexane and stored in a dessicator.
The atoms in a CH2 group,
commonly found in organic compounds, an
vibrate in six different ways: symmetry and
antisymmetric
stretching,
scissoring,
rocking, wagging and twisting. (Crasto, n.d.)
The spectrum obtained from the
plastic bag sample shown in Figure 2, had
similar results from the theoretical, Figure 3,
wherein C-H stretches, at approximately
2900 cm-1, and C-H scissoring at
approximately 1500 cm-1 were observed.
This is indicative for the molecular structure
of plastic as polyethylene.

Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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140
120
100
80
60
40
20
4000

3000

2000

1000

Figure 2. IR spectrum of plastic sample; A) C-H

stretch B) C-H scissoring

The method of thin film works if a

solid forms a translucent film on the plate.
Solid thin films works well for polymers and
waxy or fatty materials, but in many cases
the film is opaque and thus does not allow a
good spectrum. (Feist, 2001) The data
obtained for alpha-naphthol showed poor
bands as shown in Figure 5. This may have
been due to the preparation technique,
wherein, insufficient amounts of alphanaphthol was transferred onto the KBr plate.
It is expected for the IR spectrum of alphanaphthol to have an aromatic C-H stretch at
around 3000-3100 cm-1 and C-C stretches
in the ring at around 1500 cm-1.
140
120
100
80
60
40
20
4000

3000

2000

1000

Figure 3. Spectrum of Low Density

Polyethylene (LDPE) Trash Bag (Anderson
Materials, 2015)

Figure 5. IR spectrum of solid sample, alphanaphthol; thin film

Figure 4. Molecular structure of alpha-naphthol

Nujol, which is a nonvolatile liquid

paraffin, is utilized as a solvent for sample
preparation of solids due to its low
absorbance in the IR region; thus having an
uncomplicated spectrum as shown in figure
7. If the bands are distorted (show fronting
or tailing) the particle size is too great and
some radiation incident on the mull has
been scattered out of the sample beam
(Christiansen scattering) (Laboratories,

Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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2007)

Figure 6. Nujol, neat, thin film (Crasto, n.d.)

The phenol O-H stretch was not as

strong as seen in Figure 7 if compared to
theoretical results as shown in figure 8. On
the other hand, there is the presence of the
aromatic C=C stretch, overtone bands,
aromatic C-H bending and aromatic C-C
stretching as shown in Figure 7.

Figure 7. Alpha-naphthol; neat; nujol: A) Weak

Phenol O-H stretch, B) Aromatic C=C stretch,
C) Overtone bands, D) Aromatic C-H bending,
E) Aromatic C-C stretching

Figure 8. Theoretical spectrum of alphanaphthol: A) Phenol O-H stretch, B) Aromatic

C=C stretch, C) Overtone bands, D) Aromatic
C-H bending, E) Aromatic C-C stretching (SDBS,
n.d.)

Figure 9. Molecular structure of acetone

The data obtained from the IR

spectrum of acetone showed to be
erroneous sine the peaks were observed to
go up instead of down as shown in Figure
10. Based on the structure of acetone
shown in Figure 9, it is expected to have a
ketone C=O stretch at around 1700-1725
cm-1. This can be seen in the theoretical
result of the IR spectrum of acetone in
Figure 11.

Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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35
30
25
20

circular truncated cone made of glass. Each

end is covered with a KBr or KRS-5 window
that transmits infrared light. (Shimadzu,
2016)

15
10
5
4000

3000

2000

1000

Figure 10. Acetone, neat liquid, thin film

Figure 13. Gas Cells with 5 cm and 10 cm Light

Path (Shimadzu, 2016)

The IR spectra for glacial acetic acid

showed similarities to the theoretical results,
wherein, a broad O-H stretch was observed
and the presence of a C=O stretch as
shown in Figure 13.

Figure 11. Theoretical spectrum of acetone: A)

C=O stretch (SDBS, n.d.)

Figure 14. Glacial acetic acid, utilizing a gas

chamber: A) O-H stretch, B) C=O stretch

Figure 12. Molecular structure of acetic acids

A gas cell, 10 cm in length, is utilized

in the sampling of acetic acid due to its low
boiling point. Gases, or liquids with low
boiling points, allowed to expand into an
evacuated sample cell. The cell body is a

Figure 15. Theoretical spectrum of acetic acid

(NIST, 2016)

Infrared Spectrometry: Sampling Methods and Quantitative Analysis

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VI Conclusion
The IR spectra of the designated
samples, plastic, alpha-naphtol, acetone,
and acetic acid, were obtained however; the
results for some of the sample preparations
showed to be erroneous, namely thin film,
liquid preparation.
In preparing a solid sample using
nujol's method, it is recommended for the
sample to be homogenized. Additionally, the
KBr and NaCl plates should be stored in a
dessicator for future use.
VII Reference
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