Scribd
Upload
613 views

Infrared Spectros

1. Infrared (IR) spectroscopy involves measuring the absorption of IR radiation by a sample. Different functional groups absorb characteristic frequencies that can be used to determine a sample's structure. 2. IR absorption is generally presented as a spectrum with wavenumber on the x-axis and absorption/transmittance on the y-axis. Each compound has a unique IR spectrum due to the vibrational modes of its bonds and functional groups. 3. IR spectroscopy is used for structural elucidation and compound identification by analyzing the characteristic absorption frequencies of functional groups and complex fingerprint regions between 1500-910 cm-1.

Uploaded by

Ana-Maria Pantazica
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
613 views

Infrared Spectros

1. Infrared (IR) spectroscopy involves measuring the absorption of IR radiation by a sample. Different functional groups absorb characteristic frequencies that can be used to determine a sample's structure. 2. IR absorption is generally presented as a spectrum with wavenumber on the x-axis and absorption/transmittance on the y-axis. Each compound has a unique IR spectrum due to the vibrational modes of its bonds and functional groups. 3. IR spectroscopy is used for structural elucidation and compound identification by analyzing the characteristic absorption frequencies of functional groups and complex fingerprint regions between 1500-910 cm-1.

Uploaded by

Ana-Maria Pantazica
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

Infrared Spectroscopy

Infrared (IR) spectroscopy is one of the most common spectroscopic


techniques used by organic and inorganic chemists. Simply, it is the
absorption measurement of different IR frequencies by a sample positioned in the path of an IR beam. The main goal of IR spectroscopic
analysis is to determine the chemical functional groups in the sample. Different
functional groups absorb characteristic frequencies of IR radiation. Using various
sampling accessories, IR spectrometers can accept a wide range of
sample types such as gases, liquids, and solids. Thus, IR spectroscopy is
an important and popular tool for structural elucidation and compound
identification.
IR Frequency Range and Spectrum Presentation
Infrared radiation spans a section of the electromagnetic spectrum having
wavenumbers from roughly 12500 to 400 cm1, or wavelengths from 0.78 to
1000 m. 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
().
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 (cm1, reciprocal centimeter) is more commonly used
in modern IR instruments that are linear in the cm 1 scale.
In contrast, wavelengths are inversely proportional to frequencies and
their associated energy. At present, the recommended unit of wavelength
is m (micrometers), but (micron) is used in some older literature.
Wavenumbers and wavelengths can be interconverted using the following
equation:

1
104

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

Transmittance, T, is the ratio of radiant power transmitted by the sample


(I) to the radiant power incident on the sample (I0 ). Absorbance (A) is
the logarithm to the base 10 of the reciprocal of the transmittance (T).
= log(

1
) = log /0

The transmittance spectra provide better contrast between intensities of


strong and weak bands because transmittance ranges from 0 to 100% T
whereas absorbance ranges from infinity to zero.
The IR region is commonly divided into three smaller areas: near IR, mid
IR, and far IR.
The most comonly used domain for organic coumpound analysis is the
mid IR, because its energy is high enough to incure vibrations and
deformations within the molecule, without destroying the overall chemical
structure of the compound.
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.

Symetrical vibration

Asymetrical vibration

Stretching vibration
()

Scissoring
Bending vibration ()

Infrared radiation is absorbed and the associated energy is converted into


these types 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.

Analytical Information
The combination of the fundamental vibrations or rotations of various
functional groups and the subtle interactions of these functional groups

with other atoms of the molecule results in the unique, generally complex
IR spectrum for each individual compound.
IR spectroscopy is mainly used in two ways: structural elucidation and
compound identification.
Because of complex interactions of atoms within the molecule, IR
absorption of the functional groups may vary over a wide range.
However, it has been found that many functional groups give
characteristic IR absorption at specific, narrow frequency ranges
regardless of their relationship with the rest of the molecule. Generalized
tables of the positions and relative intensities of absorption bands have
been established and used to determine the functional groups present or
absent in a molecule.
Multiple functional groups may absorb at one particular frequency range,
but a functional group often gives rise to multiple-characteristic
absorption. Thus, the spectral interpretations should not be confined to
one or two bands and the whole spectrum should be examined.
To confirm or better elucidate the structure of an unknown substance,
other analytical information provided by nuclear magnetic resonance
(NMR), mass spectrometry (MS), or other chemical analysis should also
be used where possible.
For systematic evaluation, the IR spectrum is commonly divided into two
large regions.
The Diagnostic Region, from 4000 to 1500 cm-1, in which the absorbtion
bands chracterize the functional groups stretching and bending vibrations.
This helps to identify which funtional groups are or are not present in the
compunds structure. This diagnostic region is further divided into four
regions, in regards to the type of bonding the atoms of the functional
group are engaged in.
The Fingerprint Region, from 1500 to 910 cm1. Absorptions in this
region include the contributions from complex interacting vibrations,
giving rise to the generally unique fingerprint for each compound. A good
match between the IR spectra of two compounds in all frequency ranges,
particularly in the fingerprint region, strongly indicates that they have the
same molecular structures. However, detailed interpretation of the
fingerprint region without overlaying two IR spectra is difficult, and
requires a vast ammount of experience.

You might also like