Infrared Spectroscopy

Introduction:
Infrared (IR) spectroscopy is one of the most common and widely used spectroscopic
techniques. Absorbing groups in the infrared region absorb within a certain wavelength
region. The absorption peaks within this region are usually sharper when compared
with absorption peaks from the ultraviolet and visible regions. In this way, IR
spectroscopy can be very sensitive to determination of functional groups within a
sample since different functional group absorbs different particular frequency of IR
radiation. Also, each molecule has a characteristic spectrum often referred to as the
fingerprint. A molecule can be identified by comparing its absorption peak to a data
bank of spectra. IR spectroscopy is very useful in the identification and structure
analysis of a variety of substances, including both organic and inorganic compounds. It
can also be used for both qualitative and quantitative analysis of complex mixtures of
similar compounds.

The use of infrared spectroscopy began in the 1950's by Wilbur Kaye. He had designed
a machine that tested the near-infrared spectrum and provided the theory to describe
the results. Karl Norris started using IR Spectroscopy in the analytical world in the
1960's and as a result IR Spectroscopy became an accepted technique. There have
been many advances in the field of IR Spec, the most notable was the application of
Fourier Transformations to this technique thus creating an IR method that had higher
resolution and a decrease in noise. The year this method became accepted in the field
was in the late 1960's.

Advantages of IR
 High Scan Speed: Infrared spectroscopy can get information for the whole
range of frequency simultaneously, within one second. Therefore, IR can be used
to analyze a substance that is not very stable and finish the scan before it start
to decompose.
 High Resolution: The resolution of general prism spectrometer is only about 3
cm-1, but the resolution of infrared spectrometer is much higher. For example,
the resolution of Grating infrared spectrometer could be 0.2 cm -1, the resolution
of FT infrared spectrometer could be 0.1-0.005 cm-1.
 High Sensitivity: With Fourier Transform, the infrared spectrometer doesn't
need to use the slit and monochromator. In this way, the reflection specularity
will be increased and the loss of energy in the analysis process will be decreased.
Therefore the energy that reaches the detector is large enough and even very
small amount of analytes could be detected. Nowadays, the infrared
spectroscopy could detect the sample as small as 1-10 grams.
  Wide Range of Application: Infrared spectroscopy could be used to analyze
almost all organic compounds and some inorganic compounds. It has a wide
range of application in both qualitative analysis and quantitative analysis. Also,
the sample of Infrared spectroscopy doesn't have phase constraints. It could be
gas, liquid or solid, which has enlarged the range of analytes a lot.
 Large Amount of Information: Infrared Spectra could give us lots of
structural information of the analytes, such as the type of compound, the
functional group of compound, the stereoscopic structure of compound, the
number and position of substituent group and so on. Depending on the available
information form the functional part and the fingerprint part, infrared
spectroscopy has become a great method to identify different kinds of
compounds.
 Non-Destructive: Infrared Spectroscopy is non-destructive to the sample.

Disadvantages of IR
 Sample Constraint: Infrared spectroscopy is not applicable to the sample that
contains water since this solvent strongly absorb IR light.
 Spectrum Complication: The IR spectrum is very complicated and the
interpretation depends on lots of experience. Sometimes, we cannot definitely
clarify the structure of the compound just based on one single IR spectrum.
Other spectroscopy methods, such as ( Mass Spectrometry) MS and ( Nuclear
Magnetic Resonance) NMR, are still needed to further interpret the specific
structure.
 Quantification: Infrared spectroscopy works well for the qualitative analysis of
a large variety of samples, but quantitative analysis may be limited under certain
conditions such as very high and low concentrations.

Symmetry & IR Spectroscopy

One of the most importance applications of IR spectroscopy is structural assignment of
the molecule depending on the relationship between the molecule and observed IR
absorption bands. Every molecule is corresponding to one particular symmetry point
group. Then we can predict which point group the molecule is belonging to if we know
its IR vibrational bands. Vice versa, we can also find out the IR active bands from the
spectrum of the molecule if we know its symmetry.
Uses & Application
Infrared spectroscopy is a simple and reliable technique widely used in both organic and inorganic
chemistry, in research and industry. It is used in quality control, dynamic measurement, and
monitoring applications such as the long-term unattended measurement of CO 2 concentrations in
greenhouses and growth chambers by infrared gas analyzers.
It is also used in forensic analysis in both criminal and civil cases, for example in identifying polymer
degradation. It can be used in determining the blood alcohol content of a suspected drunk driver.
IR-spectroscopy has been successfully used in analysis and identification
of pigments in paintings[22] and other art objects[23] such as illuminated manuscripts.[24]
A useful way of analyzing solid samples without the need for cutting samples uses ATR
or attenuated total reflectance spectroscopy. Using this approach, samples are pressed against the
face of a single crystal. The infrared radiation passes through the crystal and only interacts with the
sample at the interface between the two materials.
With increasing technology in computer filtering and manipulation of the results, samples in solution
can now be measured accurately (water produces a broad absorbance across the range of interest,
and thus renders the spectra unreadable without this computer treatment).
Some instruments also automatically identify the substance being measured from a store of
thousands of reference spectra held in storage.
Infrared spectroscopy is also useful in measuring the degree of polymerization
in polymer manufacture. Changes in the character or quantity of a particular bond are assessed by
measuring at a specific frequency over time. Modern research instruments can take infrared
measurements across the range of interest as frequently as 32 times a second. This can be done
whilst simultaneous measurements are made using other techniques. This makes the observations
of chemical reactions and processes quicker and more accurate.
Infrared spectroscopy has also been successfully utilized in the field of semiconductor
microelectronics:[25] for example, infrared spectroscopy can be applied to semiconductors
like silicon, gallium arsenide, gallium nitride, zinc selenide, amorphous silicon, silicon nitride, etc.
Another important application of Infrared Spectroscopy is in the food industry to measure
the concentration of various compounds in different food products[26][27]
The instruments are now small, and can be transported, even for use in field trials.
Infrared Spectroscopy is also used in gas leak detection devices such as the DP-IR and EyeCGAs.
[28]
These devices detect hydrocarbon gas leaks in the transportation of natural gas and crude oil.
In February 2014, NASA announced a greatly upgraded database,[29] based on IR spectroscopy, for
tracking polycyclic aromatic hydrocarbons (PAHs) in the universe. According to scientists, more than
20% of the carbon in the universe may be associated with PAHs, possible starting materials for
the formation of life. PAHs seem to have been formed shortly after the Big Bang, are widespread
throughout the universe, and are associated with new stars and exoplanets.[30] Infrared spectroscopy
is an important analysis method in the recycling process of household waste plastics, and a
convenient stand-off method to sort plastic of different polymers (PET, HDPE, ...).[31]
Recent developments include a miniature IR-spectrometer that's linked to a cloud based database
and suitable for personal everyday use,[32] and NIR-spectroscopic chips[33] that can be embedded in
smartphones and various gadgets.
Infrared spectroscopy, an analytical technique that takes advantage of the
vibrational transitions of a molecule, has been of great significance to scientific
researchers in many fields such as protein characterization, nanoscale
semiconductor analysis and space exploration.

Principle Of Infrared Spectroscopy

The IR spectroscopy theory utilizes the concept that molecules tend to absorb specific frequencies
of light that are characteristic of the corresponding structure of the molecules. The energies are
reliant on the shape of the molecular surfaces, the associated vibronic coupling, and the mass
corresponding to the atoms.
For instance, the molecule can absorb the energy contained in the incident light and the result is a
faster rotation or a more pronounced vibration.

IR Spectroscopy Instrumentation
The instrumentation of infrared spectroscopy is illustrated below. First, a beam of IR light from the
source is split into two and passed through the reference ant the sample respectively.

Now, both of these beams are reflected to pass through a splitter and then through a detector.
Finally, the required reading is printed out after the processor deciphers the data passed through the
detector.

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-1. These bands are only used to compare the spectra of one compound to
another.

Samples in Infrared Spectroscopy

The samples used in IR spectroscopy can be either in the solid, liquid, or gaseous state.

 Solid samples can be prepared by crushing the sample with a mulling agent which has an
oily texture. A thin layer of this mull can now be applied on a salt plate to be measured.
 Liquid samples are generally kept between two salt plates and measured since the plates
are transparent to IR light. Salt plates can be made up of sodium chloride, calcium fluoride,
or even potassium bromide.
 Since the concentration of gaseous samples can be in parts per million, the sample cell must
have a relatively long pathlength, i.e. light must travel for a relatively long distance in the
sample cell.
Thus, samples of multiple physical states can be used in Infrared Spectroscopy.

Region of IR
The IR region of the electromagnetic spectrum ranges in wavelength from 2 -15 µm.
Conventionally the IR region is subdivided into three regions, near IR, mid IR and far
IR. Most of the IR used originates from the mid IR region. The table below indicates the
IR spectral regions

Wavenumbers
Region Wavelength Frequencies (v), HZ
(V), cm-1
Near 0.78 -2.5 12800 - 4000 3.8 x 1014 - 1.2 x 1014

Middle 2.5 - 50 4000 - 200 3.8 x 1014 - 1.2 x 1014

Far 50 -100 200 -10 3.8 x 1014 - 1.2 x 1014

Most
2.5 -15 4000 -670 3.8 x 1014 - 1.2 x 1014
Used

IR deals with the interaction between a molecule and radiation from the
electromagnetic region ranging (4000- 40 cm-1). The cm-1 is the wave number scale and
it can also be defined as 1/wavelength in cm. A linear wavenumber is often used due to
its direct relationship with both frequency and energy. The frequency of the absorbed
radiation causes the molecular vibrational frequency for the absorption process. The
relationship is given below

v¯(cm−1)=1λ(μm)×104(μmcm)=v(Hz)c(cm/s)(24)
(24)v¯(cm−1)=1λ(μm)×104(μmcm)=v(Hz)c(cm/s)
 Near InfraRed Spectroscopy: Absorption bands in the near infrared (NIR)
region (750 - 2500 nm) are weak because they arise from vibrational overtones
and combination bands. Combination bands occur when two molecular vibrations
are excited simultaneously. The intensity of overtone bands reduces by one
order of overtone for each successive overtone. When a molecule is excited from
the ground vibrational state to a higher vibrational state and the vibrational
quantum number v is greater than or equal to 2 then an overtone absorption
results. The first overtone results from v = 0 to v = 2. The second overtone
occurs when v =0 transitions to v = 3. Transitions arising from the near ir
absorption are weak, hence they are referred to as forbidden transitions but
these transitions are relevant when non-destructive measurements are required
such as a solid sample. Near IR spectra though have low absorption they have a
high signal to noise ratio owing to intense radiation sources and NIR is able to
penetrate undiluted samples and use longer path lengths; it becomes very useful
for rapid measurement of more representative samples.
 Far InfraRed Spectroscopy: The far IR region is particularly useful for
inorganic studies due to stretching and bending vibrations of bonds between the
metal atoms and ligands. The frequencies, which these vibrations are observed,
are usually lower than 650 cm-1. Pure rotational absorption of gases is observed
in the far IR region when there is a permanent dipole moment present. Examples
include H2O, O3, HCl.

Working:
Infrared (IR) spectroscopy uses infrared radiation to excite the
molecules of a compound and generates an infrared spectrum of the
energy absorbed by a molecule as a function of the frequency or
wavelength of light.
Different types of bonds respond to the IR radiation differently. For
example, triple and double bonds are shorter and stiffer than single
bonds, and therefore will vibrate at higher frequencies. The types of
atoms involved in the bonds are also relevant. For example, O-H bonds
are stronger than C-H bonds, so O-H bonds vibrate at higher
frequencies. IR spectroscopy therefore allows us to identify the
various functional groups present in a compound.
It is worth noting that a dipole moment is required for a molecule to
absorb IR radiation. In general, if a bond has a dipole moment, its
stretching frequency causes an absorption in the IR spectrum. If a
bond is symmetrically substituted and has zero dipole moment, its
stretching vibration is weak or entirely absent in the spectrum (IR-
active vs. IR-inactive vibrations). However, bonds with zero dipole
moments sometimes produce weak absorptions because molecular
collisions, rotations, and vibrations make them unsymmetrical part of
the time.
Here is an example of an IR spectrum for formaldehyde.

Diagram:

Importance:
Infrared Spectroscopy is the analysis of infrared light interacting with a molecule.
This can be analyzed in three ways by measuring absorption, emission and
reflection. The main use of this technique is in organic and inorganic chemistry. It is
used by chemists to determine functional groups in molecules. IR Spectroscopy
measures the vibrations of atoms, and based on this it is possible to determine the
functional groups.5 Generally, stronger bonds and light atoms will vibrate at a high
stretching frequency (wavenumber).