Infrared Spectroscopy

‫رقيه عماد جمال حسنين‬:‫االسم‬

‫الكمياء التطبيقيه‬:‫الشعبة‬
20211133:‫الكود‬

DECEMBER 5, 2023
APPLIED CHEMISTRY
HELWAN UNIVERSITY
 Contents:
-Basic Principles
-Instrumentation
-Sampling Technique
-Applications
Basic Principles
Infrared spectroscopy (IR spectroscopy) deals with the infrared region of the
electromagnetic spectrum, i.e. light having a longer wavelength and a lower
frequency than visible light. Infrared Spectroscopy generally refers to the analysis
of the interaction of a molecule with infrared light.
The IR spectroscopy concept can generally be analyzed in three ways: by measuring
reflection, emission, and absorption. The major use of infrared spectroscopy is to
determine the functional groups of molecules, relevant to both organic and inorganic
chemistry.
IR Spectroscopy detects frequencies of infrared light that are absorbed by a molecule.
Molecules tend to absorb these specific frequencies of light since they correspond to
the frequency of the vibration of bonds in the molecule.

1.1. Regions of the Infrared spectrum

Most of the bands that indicate what functional group is present are found in the
region from 4000 cm-1 to 1300 cm-1. Their bands can be identified and used to
determine the functional group of an unknown compound.

Bands that are unique to each molecule, similar to a fingerprint, are found in the
fingerprint region, from 1300 cm-1 to 400 cm These bands are only used to compare the
spectra of one compound to another.
1.2. Theory of IR-spectroscopy:
IR Spectroscopy measures the vibrations of atoms, and based on this it is possible to
determine the functional groups. Generally, stronger bonds and light atoms will vibrate
at a high stretching frequency (wavenumber).

In order for a vibrational mode in a molecule to be "IR Active ", it must be associated
with changes in the permanent dipole. A molecule can vibrate in many ways, and each
way is called a vibrational mode.

Linear molecules have 3N - 5 degrees of vibrational modes whereas nonlinear

molecules have 3N - 6 degrees of vibrational modes (also called vibrational degrees of
freedom. As an example H2O, a non-linear molecule, will have 3 × 3 - 6 = 3 degrees of
vibrational freedom, or modes.

Molecular vibrations to Infrared radiations

There are six types of vibration usually encountered in IR spectroscopy:
(1) Asymmetrical stretching
(2) Symmetrical stretching
(3) Bending and scissoring
(4) Rocking or in-plane bending
(5) Twisting
(6) Wagging
1.3. IR Spectroscopy Instrumentation
The main parts of the IR spectrometer are as follows:
1. Radiation source
IR instruments require a source of radiant energy which emits IR radiation which must be
steady, intense enough for detection, and extend over the desired wave length .Various
radiation sources are known, such as Nernst glower, Mercury arc, Tungsten lamp, etc.
2. Sample cells and sampling of substances
IR spectroscopy has been used for the characterization of solid, liquid, or gas samples.
1- Solid – Various techniques are used for preparing solid samples such as pressed pellet
technique, solid run in solution, solid films, mull technique, etc.
2-Liquid – Samples can be held using a liquid sample cell made of alkali halides. Aqueous
solvents cannot be used as they will dissolve alkali halides. Only organic solvents like
chloroform can be used.
3- Gas– Sampling of gas is similar to the sampling of liquids.
3. Monochromators
Various types of monochromators are can be used, such as prism, gratings and filters.
4. Detectors
Detectors are used to measure the intensity of unabsorbed infrared radiation. Detectors
like thermocouples, Bolometers, thermistors, Golay cell, and pyro-electric detectors are
used.
5. Recorder
Recorders are used to record the IR spectrum.
1.4. IR Chart or spectrum
An IR spectrum is essentially a graph plotted with the infrared light absorbed on the Y-
axis against frequency or wavelength on the X-axis. Given below is a sample of
typical IR spectrum.

1.5. Sampling Technique

IR spectroscopy is used for the characterization of solid, liquid or gas samples. Material
containing sample must be transparent to the IR radiation. So, the salts like NaCl , KBr
are only used.
1. Sampling of solids
Various techniques used for preparing solid samples are as follows:
a) Mull technique: In this technique, the finely crushed sample is mixed with Nujol
(mulling agent) in n a marble or agate mortar, with a pestle to make a thick paste. A
thin film is applied onto the salt plates. This is then mounted in a path of IR beam and
the spectrum is recorded.
b) Solid run in Solution – In this technique, solid sample may be dissolved in a non-
aqueous solvent provided that there is no chemical interaction with the solvent and the
solvent is not absorbed in the range to be studied. A drop of solution is placed on the
surface of alkali metal disc and solvent is evaporated to dryness leaving a thin film of
the solute.
c) Case film technique – If the solid is amorphous in nature then the sample is
deposited on the surface of a KBr or NaCl cell by evaporation of a solution of the solid
and ensured that the film is not too thick to pass the radiation.
d) Pressed pellet technique – In this technique, a small amount of finely ground solid
sample is mixed with 100 times its weight of potassium bromide and compressed into a
thin transparent pellet using a hydraulic press. These pellets are transparent to IR
radiation and it is used for analysis.
2. Sampling of liquids
Liquid sample cells can be sandwiched using liquid sample cells of highly purified alkali
halides, normally NaCl. Other salts such as KBr and CaF2 can also be used. Aqueous
solvents cannot be used because they cannot dissolve alkali halides. Organic solvents
like chloroform can be used. The sample thickness should be selected so that the
transmittance lies between 15-20%. For most liquids, the sample cell thickness is 0.01-
0.05 mm. Some salt plates are highly soluble in water, so the sample and washing
reagents must be anhydrous.
3. Sampling of gases
The sample cell is made up of NaCl, KBr etc. and it is similar to the liquid sample cell.
A sample cell with a long path length (5 – 10 cm) is needed because the gases show
relatively weak absorbance.

1.6. Applications of IR Spectroscopy

IR spectroscopy is a widely used analytical technique in a variety of fields, including
chemistry, materials science, and biochemistry. Moreover, it is applied as follows:

Identification of an organic Compound : Functional groups, for example, two

compounds with similar overlay able spectra must have the same functional groups.
Interestingly, an FT-IR spectrophotometer is used at airports to detect drug addicts.

Purity of chemical compound: Although thorough FTIR is not commonly used as a

quantitative analysis, it is useful for determining the purity of chemical compounds.

Reaction progress: Organic chemical reactions are slow, so their progress is to be

measured after time intervals through IR spectroscopy of the mixture.
References
1. Zeitler JA, Taday PF, Newnham DA, Pepper M, Gordon KC, Rades T (February
2007). "Terahertz pulsed spectroscopy and imaging in the pharmaceutical setting-
-a review".
2. Atkins P, de Paula J (2002). Physical Chemistry (7th ed.). New York: W.H. Freeman
3. Schrader B (1995). Infrared and Raman Spectroscopy: Methods and Applications.
New York.
4. Jump up to: a b Harwood LM, Moody CJ (1989). Experimental organic chemistry:
Principles and Practice (Illustrated ed.