Experiment 3

Fourier Transform Infrared Spectroscopy (FTIR)

Introduction

The use of electromagnetic radiation to investigate chemical structure, behaviour and

concentration is a large and important field of chemistry. There are many important
instrumental methods of chemical analysis that rely on the interaction between light and
matter to probe chemical structure. You have have already used visible spectroscopy in a
previous lab to determine the concentration of an unknown solution. In this lab you will see
how infrared (IR) spectroscopy can be used to give information about the covalent bonds in a
molecule.

FTIR spectroscopy is one of the measurement techniques for collecting infrared

spectra. Instead of recording the amount of enegy absorbed when the frequency of the
infrared light passes through the sample to produce the inteeferogram (measured signal). In
order to absorb IR radiation, a molecule must undergo a net change in dipole moment aas a
consequence of its vibrational or rational motion. Nearly all molecules containing covalent
bonds will show some degree of IR absorption. The only exception is the diatomic molecules,
such as hydrogen, nitrogen and oxygen in whih there is no net change in dipole moment
when they vibrate or rotate. The IR spectra of polyatomic covalent compounds are often
exceedingly complex, consisting of many absorption bands. The relative positions of atoms in
a molecule are not exactly fixed. The positions fluctuate continuously as a consequence of
different types of the vibrational motion of molecules. The bonds in a molecule act like tiny
springs and, like springs, vibrate with a characteristics frequency. These frequency fall in the
infrared region of the electromagnetic spectrum. By passing IR radiation through a sample
and observing what frequencies are absorbed, it is possible to deduce what types of chemical
bonds are present in the molecule.
There are two fundamental types of vibration.

1) Stretching: Involves a continuous change in interatomic distance along the axis of the
bond between the two atoms.
2) Bending: Characterized by a change in the angle between two bonds.

To identify your compounds you will examine your spectrum for the presence (or
absence) of absorption peaks such as from the table below. Note that the typical units for
IR absorbance are not nanometers, but wavenumbers, where the label is cm -1. The
interpretation of infrared spectra involves the correlation of absorption bands in the
spectrum of an unknown compound with the known absorption frequencies for types of
bonds. This table will help you become more familiar with the process. Significant for the
identification of the source of an absorption band are intensity (weak, medium or strong),
shape (broad or sharp), and position (cm-1) in the spectrum.

IR spectroscopy has been employed for both qualitative and quantitative analysis. A
particular group of atoms gives rise to characteristic stretching frequencies in the IR
spectra. Thus, an IR spectrum of an organic compound provides a unique fingerprint and
is distinguished from spectra of other compounds. Identification of an organic compound
involves two steps.

1) Determine what functional groups are most likely present.

2) Detailed comparison of the spectrum of the unknown with the spectra of pure
compounds that contain all the functional groups found in the first step.
Objectives

1) To prepare the ATR

2) To carry out a qualitative analysis of an organic compound (benzoic acid) using ATR
3) To identify IR absorption peaks and the corresponding functional groups of an
unknown solid/solid/powder.

Apparatus

FTIR-ATR accessory

Chemicals

Benzoic acid, methanol, unknown (solid)

Procedure

1) Crystal surface was cleaned before making a measurement

2) Pure cotton was used by dipping it with some solvent (methanol) to clean the crystal
3) The crystal surface was dried completely before measurement
4) Negative bands may be seen if the crystal was not properly cleaned
5) ‘Instrument setting’ was selected as required. The recommend number of scans is ‘16’
for ATR accessory
6) ‘Background scan’ was first obtained before sample measurement
7) Entered sample name, description required
8) If sample was liquid, a drop of liquid sample was placed on the crystal surface and
scan.
9) If the sample was not liquid, place it over the crystal surface and use pressure arm to
apply pressure. Spectrum can only be acquired if there was contact between the
sample and crystal surface. The depth of penetration by the IR beam into the sample
typically 1 to 3 microns only.
10) Sample was scanned to acquire the spectrum once the previewed spectrum was of
acceptable quality.
11) Raw spectrum was automatically saved.
12) Baseline drift of the raw spectrum was corrected by using ‘Data Tune-up’ function in
the ‘process’ menu
13) Further processing using the ‘ATR correction’ function in the ‘process’ menu will be
corrected for the uneven depth of penetration by different wavelengths. The ATR
corrected spectrum resembles spectrum obtained with the normal transmission
accessory.
14) The ‘contact’ settings for the ATR correction for the liquid sample is ‘0’ while for
solid samples was either ‘1’ or ‘2’
15) The ATR was cleaned by sing organic solvents and get ready for another sample
Result
3076.4 cm-1 : O-H (Carboxylic Acid) , 3400 cm-1 - 2400 cm-1 (broad)

2820.2 cm-1 : O-H (Carboxylic Acid) , 3400 cm-1 - 2400 cm-1 (broad)

2554.5 cm-1 : O-H (Carboxylic Acid) , 3400 cm-1 - 2400 cm-1 (broad)

1676.42 cm-1 : C=O (Carboxylic Acid) , 1730 cm-1 - 1650 cm-1 (strong)

1453.43 cm-1 : C=C-C (Aromatic Rings) , 1500 cm-1 - 1450 cm-1 (asymmetric stretch)

1323.45 cm-1 : C-O (Carboxylic Acid) , 1320 cm-1 - 1210 cm-1 (medium)

1288.31 cm-1 : C-O (Carboxylic Acid) , 1320 cm-1 - 1210 cm-1 (medium)
Questions

1) Explain why a background spectrum must be run before obtaining the sample
spectrum.
- So that you can subtract the background spectrum from the sample’s measurement, to
get the actual sample’s spectrum

2) Why must ‘neat’ liquid and not aqueous solution be used on salt plate?
- We must use neat liquids because it is easier in preparation because no mixing is
required. The aqueous solution will dissolve the salt plates.

Discussion
The purpose of the experiment is to carry out a qualitative analysis of an organic compound
(benzoic acid) using ATR and to identify IR absorption peaks and the corresponding
functional groups of an unknown solid/solid/powder. In this experiment, benzoic acid was
used to determine its IR absorption peak plus. Based on the spectrum that have been read by
the ATR on the computer, our result for graph was not accurate due to error in terms of
handling the accessory well because of the peaks that were mostly shifted away from its
absorption range but we manage to identify the absorption range by determine the functional
group available in the compound. Such as aromatic rings, and carboxylic acid. The error was
caused by over-twist the knob on top of the ATR machines, which gives reading to the
computer of the absorption. Nevertheless, an unknown compound has been used to identify
its IR absorption peaks too. It is said that the unknown is an aspirin sample, because of the
peaks that form was look-alike. In this experiment, we only focus on the known compound,
benzoic acid where the result was obtained and listed at the result section. There are many
type of bond involves in this experiment, such as O-H, C=O, C=C-C and C-O. Furthermore,
the cause of the peaks form mostly on the right side is the different type of molecular bond
and due to type of vibrational.
Conclusion

In this experiment, we can make a conclusion that by using FTIR-ATR methods, we

can carry out a qualitative analysis for organic compound such as benzoic acid. We can also
identify IR absorption peaks and the corresponding functional groups of an unknown solid or
liquid or powder. Other that, we can also conclude that some errors have happen during this
experiment. So, to avoid and minimize this error we should follow all off the step in the
procedures.

References

Curk, M. C., Peledan, F., & Hubert, J. C. (1994). Fourier transform infrared (FTIR)
spectroscopy for identifying Lactobacillus species. FEMS Microbiology Letters, 123(3),
241–248. https://doi.org/10.1111/j.1574-6968.1994.tb07231.x

Kellner, R., Fischb�ck, G., & Minich, C. (1986). FTIR-microscopy versus FTIR-ATR-
spectroscopy for the analysis of multilayer polymer films. Mikrochimica Acta, 88(5–6),
271–279. https://doi.org/10.1007/BF01206720

Millan-Oropeza, A., Rebois, R., David, M., Moussa, F., Dazzi, A., Bleton, J., … Deniset-
Besseau, A. (2017). Attenuated Total Reflection Fourier Transform Infrared (ATR FT-
IR) for Rapid Determination of Microbial Cell Lipid Content: Correlation with Gas
Chromatography-Mass Spectrometry (GC-MS). Applied Spectroscopy, 71(10), 2344–
2352. https://doi.org/10.1177/0003702817709459

Tantishaiyakul, V., Phadoongsombut, N., Wongpuwarak, W., Thungtiwachgul, J.,

Faroongsarng, D., Wiwattanawongsa, K., & Rojanasakul, Y. (2004). ATR-FTIR
characterization of transport properties of benzoic acid ion-pairs in silicone membranes.
International Journal of Pharmaceutics, 283(1–2), 111–116.
https://doi.org/10.1016/j.ijpharm.2004.07.004

Wei, Z., Jiao, D., & Xu, J. (2015). Using Fourier Transform Infrared Spectroscopy to Study
Effects of Magnetic Field Treatment on Wheat ( Triticum aestivum L.) Seedlings.
Journal of Spectroscopy, 2015, 1–6. https://doi.org/10.1155/2015/570190