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Infrared spectroscopy is certainly one of the most important analytical techniques

available to today’s scientists. One of the great advantages of infrared spectroscopy is that
virtually any sample in virtually any state may be studied. Infrared spectrometers have been
commercially available since the 1940s. At that time, the instruments relied on prisms to act as
dispersive elements, but by the mid 1950s, diffraction gratings had been introduced into
dispersive machines. The most significant advances in infrared spectroscopy have come about
as a result of the introduction of Fourier-transform spectrometers.

Infrared spectroscopy is a technique based on the vibrations of the atoms of a molecule.


An infrared spectrum is commonly obtained by passing infrared radiation through a sample and
determining what fraction of the incident radiation is absorbed at a particular energy. The energy
at which any peak in an absorption spectrum appears corresponds to the frequency of a
vibration of a part of a sample molecule (Stuart, 2004).

IR Frequency Range and Spectrum Presentation


I nfrared radiation spans a section of the electromagnetic spectrum having wavenumbers
from roughly 13,000 to 10 cm–1, or wavelengths from 0.78 to 1000 μm. It is bound by the red
end of the visible region at high frequencies and the microwave region at low frequencies. IR
absorption positions are generally presented as either wavenumbers ( ) or wavelengths (l).
Wavenumber defines the number of waves per unit length. Thus, wavenumbers are directly
proportional to frequency, as well as the energy of the IR absorption. The wavenumber unit
(cm–1, reciprocal centimeter) is more commonly used in modern IR instruments that are linear
in the cm–1 scale. In the contrast, wavelengths are inversely proportional to frequencies and
their associated energy. At present, the recommended unit of wavelength is μm (micrometers),
but μ (micron) is used in some older literature. Wavenumbers and wavelengths can be
interconverted using the following equation:

IR absorption information is generally presented in the form of a spectrum with


wavelength or wavenumber as the x-axis and absorption intensity or percent transmittance as
the y-axis.
The far IR requires the use of specialized optical materials and sources. It is used for
analysisof organic, inorganic, and organometallic compounds involving heavy atoms (mass
number over 19). It provides useful information to structural studies such as conformation and
lattice dynamics of samples. Near IR spectroscopy needs minimal or no sample preparation. It
offers high-speed quantitative analysis without consumption or destruction of the sample. Its
instruments can often be combined with UV-visible spectrometer and coupled with fiberoptic
devices for remote analysis. Near IR spectroscopy has gained increased interest, especially in
process control applications.

Theory of Infrared Absorption


At temperatures above absolute zero, all the atoms in molecules are in continuous vibration with
respect to each other. When the frequency of a specific vibration is equal to the frequency of the
IR radiation directed on the molecule, the molecule absorbs the radiation. Each atom has three
degrees of freedom, corresponding to motions along any of the three Cartesian coordinate axes
(x, y, z). A polyatomic molecule of n atoms has 3n total degrees of freedom. However, 3
degrees of freedom are required to describe translation, the motion of the entire molecule
through space. Additionally, 3 degrees of freedom correspond to rotation of the entire molecule.
Therefore, the remaining 3n – 6 degrees of freedom are true, fundamental vibrations for
nonlinear molecules. Linear molecules possess 3n – 5 fundamental vibrational modes because
only 2 degrees of freedom are sufficient to describe rotation. Among the 3n – 6 or 3n – 5
fundamental vibrations (also known as normal modes of vibration), those that produce a net
change in the dipole moment may result in an IR activity and those that give polarizability
changes may give rise to Raman activity. Naturally, some vibrations can be both IR- and
Raman-active. The total number of observed absorption bands is generally different from the
total number of fundamental vibrations. It is reduced because some modes are not IR active
and a single frequency can cause more than one mode of motion to occur. Conversely,
additional bands are generated by the appearance of overtones (integral multiples of the
fundamental absorption frequencies), combinations of fundamental frequencies, differences of
fundamental frequencies, coupling interactions of two fundamental
absorption frequencies, and coupling interactions between fundamental vibrations and
overtones or combination bands (Fermi resonance). The intensities of overtone, combination,
and difference bands are less than those of the fundamental bands. The combination and
blending of all the factors thus create a unique IR spectrum for each compound.
The major types of molecular vibrations are stretching and bending. The various types of
vibrations are illustrated in Fig. 15.2. Infrared radiation is absorbed and the associated energy is
converted into these type of motions. The absorption involves discrete, quantized energy levels.
However, the individual vibrational motion is usually accompanied by other rotational motions.
These combinations lead to the absorption bands, not the discrete lines, commonly observed in
the mid IR region.

Figure 15.2 Major vibrational modes for a nonlinear group, CH2. (+ indicates motion from the plane of page toward
reader; – indicates motion from the plane of page away from reader.) (Reprinted from R. M. Silverstein,
G. C. Bassler, and T. C. Morrill, Spectrometric Identification of Organic Compounds, 4th edition. New York: JohnWiley & Sons, 1981, p. 166, by permission of John
Wiley & Sons, Inc., copyright © 1981.)
Principles of IR Spectroscopy
The IR region of the EM spectrum
Infrared radiation is electromagnetic energy with wavelengths longer than visible light but
shorter than microwaves. Generally, wavelengths from 0.8 to 100 micrometers can be used for
IR spectroscopy and are divided into the near-IR (0.8-2.5 μm), the mid-IR (2.5-15 μm) and the
far-IR (15-100 μm) regions. The near and mid IR regions are most useful for quantitative and
qualititative analysis of foods.
IR radiation also can be measured in terms of its frequency, which is useful because
frequency is directly related to the energy of the radiation by the following relationship: E=hv
Where E=energy of the system h=Planck’s constant v=frequency in hertz
Molecular vibrations
A molecule can absorb IR radiation if it vibrates in such a way that its charge distribution
and therefore its electric dipole moment changes during the vibration. The most important
vibrations that produce a change in dipole moment are stretching and bending (scissoring,
rocking, twisting, wagging motions). Stretching motions vibrate at higher frequencies than
scissoring motions. Also, asymmetric stretches are more likely to result in a change in dipole
moment, with corresponding absorption of IR radiation than asymmetric stretches.

(oops, forgot to leave the references, sorry)