SPECTROSCOPY

Spectroscopy is the science of study the Interaction between radiation and matter.
The absorption of light, as it passes through a medium, varies linearly with the distance
the light travels and with concentration of the absorbing medium. Where a is the
absorbance, the Greek lower-case letter epsilon is a characteristic constant for each
material at a given wavelength (known as the extinction coefficient or absorption
coefficient), c is concentration, and l is the length of the light path, the absorption of light
may be expressed by the simple equation a= epsilon times c times l.

FTIR

Fourier Transform Infrared Spectroscopy (FTIR) is a technique which is used to obtain

an infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer
simultaneously collects high spectral resolution data over a wide spectral range. The
term Fourier transform infrared spectroscopy originates from the fact that a Fourier transform (a
mathematical process) is required to convert the raw data into the actual spectrum. The goal of
any absorption spectroscopy (FTIR) is to measure how well a sample absorbs light at each
wavelength.
FT-IR analysis of evolved products has advantages over mass spectroscopy in allowing analysis
of very heavy products in speed.
FTIR Spectroscopy is a molecular spectroscopy which is used to characterize both
organic and inorganic evidence.
A method of obtaining an Infrared spectrum by measuring the interferogram of a sample
using an interferometer, then performing a Fourier Transform upon the interferogram to
obtain the spectrum.
The sample is bombarded with infrared radiation.

When the frequency of the infrared radiation matches the natural frequency of the bond,
the amplitude of the vibration increases, and the infrared is absorbed.
The resulting spectrum represents the molecular absorption and transmission, creating a
molecular fingerprint of the sample.
Like a fingerprint no two unique molecular structures produce the same infrared
spectrum. This makes infrared spectroscopy useful for several types of analysis.
 The output of an infrared spectrophotometer is a chart.

Vibrational / Rotational
No. Region Range cm-1
Information

1 Near IR 14000 - 4000 Changes in Vibrational and rotational levels,

electron transitions

2 Mid-IR 4000 - 400 Changes in fundamental Vibrational levels of

most molecules

3 Far-IR 400 - 20 Rotational energy level changes

The INFRARED spectrum is divided into three region, which can be distinguished each other by
the Wavelength |ranging from 14000 cm-1 to 20 cm-1.
Instrumentation
Source
Laser
Interferometer
Detector
Source
Electronically Temperature Controlled (ETC) EverGlo.
The ETC EverGlo source is an efficient ceramic, refractory composite that rapidly rises
to operating temperature and is also thermally insulated to maintain a constant operating
temperature.
Provide energy for the spectral region from 7400 50 cm-1.
The source temperature is constantly monitored and controlled at 1140C by the ETC.
Infrared energy is emitted from a glowing black-body source. This beam passes through
an aperture which controls the amount of energy presented to the sample (and, ultimately,
to the detector).
Laser
A Heliumneon laser or He-Ne laser, is a type of gas laser whose gain medium consists
of a mixture of helium and neon (10:1) inside of a small bore capillary tube, usually
excited by a DC electrical discharge.
Laser create the drive volt for the moving mirror.

The He-Ne laser is used as an internal reference.

Interferometer
The beam enters the interferometer where the spectral encoding takes place. The
resulting interferogram signal then exits the interferometer.
Sample
The beam enters the sample compartment where it is transmitted through or reflected off
of the surface of the sample, depending on the type of analysis being accomplished. This
is where specific frequencies of energy, which are uniquely characteristic of the sample,
are absorbed.
Detector
The beam finally passes to the detector for final measurement. The detectors used are
specially designed to measure the special interferogram signal.
Principle
Radiation emitted from the source is split into two with a beam splitter in the interferometer. The
fixed and moving mirrors reflect each of the beam back to the beam splitter, where the two
beams recombine into one and falls on the detector. The two beams combine constructively or
destructively, varying as the optical path difference, when the moving mirror is moved. When the
combined beam is transmitted through the sample, it is detected as an interferogram and contains
all infrared information on the sample. The infrared spectrum is obtained from the interferogram
by the mathematical process of Fourier transformation.

Fourier Transform Infrared (FT-IR) spectrometry was developed in order to overcome the
limitations encountered with dispersive instruments. The main difficulty was the slow scanning
process. A method for measuring all of the infrared frequencies simultaneously, rather than
individually, was needed. A solution was developed which employed a very simple optical
device called an interferometer. The interferometer produces a unique type of signal which has
all of the infrared frequencies encoded into it. The signal can be measured very quickly,
usually on the order of one second or so. Thus, the time element per sample is reduced to a
matter of a few seconds rather than several minutes.

Most interferometers employ a beam splitter which takes the incoming infrared beam and divides
it into two optical beams. One beam reflects off of a flat mirror which is fixed in place. The other
beam reflects off of a flat mirror which is on a mechanism which allows this mirror to move a
very short distance (typically a few millimeters) away from the beam splitter. The two beams
reflect off of their respective mirrors and are recombined when they meet back at the beam
splitter. Because the path that one beam travels is a fixed length and the other is constantly
changing as its mirror moves, the signal which exits the interferometer is the result of these two
beams interfering with each other. The resulting signal is called an interferogram which has the
unique property that every data point (a function of the moving mirror position) which makes up
the signal has information about every infrared frequency which comes from the source.

This means that as the interferogram is measured, all frequencies are being measured
simultaneously. Thus, the use of the interferometer results in extremely fast measurements. A
means of decoding the individual frequencies is required. This can be accomplished via a well-
known mathematical technique called the Fourier transformation. This transformation is
performed by the computer which then presents the user with the desired spectral information for
analysis.
 Advantages of FT-IR compared to dispersive IR
Short measurement time; all of the frequencies are measured simultaneously, most
measurements by FT-IR are made in a matter of seconds rather than several minutes. This is
sometimes referred to as the Felgett Advantage.

Throughput advantage (Jacquinot Advantage); advantage of FTIR is 100 times

better than a dispersive IR.

Measuring dark samples; Samples with high carbon content (such as black
rubber) can be measured.

Internally Calibrated; FTIR employ a He-Ne laser as an internal wavelength

calibration standard. He-Ne laser has a very stable frequency. Therefore, FTIR will have
excellent long term stability and repeatability in the spectrum. These instruments Provides a
precise measurement method which requires no external calibration.

Mechanical Simplicity: The moving mirror in the interferometer is the only

continuously moving part in the instrument. Thus, there is very little possibility of mechanical
breakdown.

Sensitivity; is dramatically improved with FT-IR for many reasons. The detectors
employed are much more sensitive, the optical throughput is much higher. Sensitivity from very
low parts per million to high percent levels.

Simultaneous analysis of multiple gaseous compounds.

Measures a wide variety of volatile compounds (Inorganic and Organic).

Advantages-
FTIR is a simple and sensitive analytical tool.
Provide fast data acquisition & Simple to operate.
Most useful for analytical process.
To determine the composition of organic materials
To identify IR transparent or semi-transparent inorganic films
Provides quantitative determination of compounds in mixtures

Disadvantages-
Interpretation of the data requires some experience.
Carbon di-oxide & Water Sensitive.
Applications of FTIR
Identification of inorganic compounds and organic compounds.

Identification of components of an unknown mixture.

Analysis of solids, liquids, and gasses.

In measurement and analysis of Atmospheric Spectra.

Solar irradiance at any point on earth.

Can also be used on satellites to probe the space.

Opaque or cloudy samples.

Energy limiting accessories such as diffuse reflectance or FT-IR microscopes.

High resolution experiments (as high as 0.001 cm-1 resolution).

Trace analysis of raw materials or finished products.

Depth profiling and microscopic mapping of samples.