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.
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.

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

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.
Commented [t1]: Solar irradiance is the power per unit
area received from the Sun in the form of electromagnetic
radiation, in the wavelength range of the measuring
instrument. Irradiance may be measured in space or at
the Earth's surface after atmospheric absorption
and scattering. It is measured perpendicular to the incoming
sunlight. It depends on the height of the Sun above the
horizon and the cloud cover.

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.