ENGINEERING CHEMISTRY AIST SAGAR

UNIT- 6

Spectroscopy
Spectroscopy means the dispersion of light into component colours. In simple words, it is a method to measure how much
light is absorbed by a chemical substance and at what intensity of light passes through it.

As per analytical science, every element or compound has a unique characteristic spectrum. Each compound absorbs and
disperses light over a certain range of wavelengths.

IR Spectroscopy
IR spectroscopy-

(which is short for infrared spectroscopy) deals with the infrared region of the electromagnetic spectrum, i.e. light having a
longer wavelength and a lower frequency than visible light. Infrared Spectroscopy generally refers to the analysis of the
interaction of a molecule with infrared light.

The IR spectroscopy concept can generally be analyzed in three ways: by measuring reflection, emission, and absorption.
The major use of infrared spectroscopy is to determine the functional groups of molecules, relevant to both organic and
inorganic chemistry.

IR Spectroscopy
An IR spectrum is essentially a graph plotted with the infrared light absorbed on the Y-axis against. frequency or wavelength
on the X-axis. An illustration highlighting the different regions that light can be classified into is given below.

IR Spectroscopy detects frequencies of infrared light that are absorbed by a molecule. Molecules tend to absorb these
specific frequencies of light since they correspond to the frequency of the vibration of bonds in the molecule.

The energy required to excite the bonds belonging to a molecule, and to make them vibrate with more amplitude, occurs in
the Infrared region. A bond will only interact with the electromagnetic infrared radiation, however, if it is polar.

The presence of separate areas of partial positive and negative charge in a molecule allows the electric field component of
the electromagnetic wave to excite the vibrational energy of the molecule.

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 1
ENGINEERING CHEMISTRY AIST SAGAR

The change in the vibrational energy leads to another corresponding change in the dipole moment of the given molecule.
The intensity of the absorption depends on the polarity of the bond. Symmetrical non-polar bonds in N≡N and O=O do not
absorb radiation, as they cannot interact with an electric field.

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

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.

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 mor e
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 and the sample respectively.

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 2
ENGINEERING CHEMISTRY AIST SAGAR

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.

Graph of the IR spectrum

Given below is a sample of typical Infrared Absorption Frequencies.

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 3
ENGINEERING CHEMISTRY AIST SAGAR

Thus, IR spectroscopy involves the collection of absorption information and its analysis in the form of a spectrum.

Ultraviolet Spectrophotometer
Ultraviolet/Visible area (UV-Vis) measurements span wavelengths from around 200 nm to 800 nm. The absorption by a
molecule of ultraviolet or visible radiation results in transitions between the molecule’s electrical energy levels. The optical
and electronic properties of different materials, such as films, powders, monolithic solids, and liquids, are suitable for
characterization.

UV-vis spectroscopy is a cost-effective, simple, versatile, non-destructive, analytical technique suitable for a large spectrum
of organic compounds and some inorganic species. As a function of wavelength, UV-vis spectrophotometers measure the
absorption or transmission of light that passes through a medium.

In order to classify and measure the concentration of substances in liquid streams, high performance liquid chromatography
and ultra-high performance liquid chromatography incorporate UV-vis detectors. It allows the detection of all animals by
integrating these techniques with mass spectrometry.

UV- Spectroscopy Theory

When the interaction between incident radiation and the electron cloud in a chromophore results in an electronic transition
involving the promotion of one or more of the outer shell or the bonding electrons from a ground state into a higher energy
state, ultraviolet-visible (UV-Vis) spectra are derived.

Generally, the UV and visible spectral bands of substances are large. And may not exhibit a high degree of compound
recognition accuracy. Nonetheless, they are sufficient for quantitative assays and are useful as an alternate means of
detection for several substances. The radiation from typical hot solids consists of s everal wavelengths and depends
primarily on the temperature of the solid and is predictable from the principle of chance, the energy released at each given
wavelength.

More recently, using a version of this-the tungsten-halogen lamp-has become standard practice. Radiation is transmitted
deep into the UV zone through the quartz envelope. The most popular source is the deuterium lamp for the UV region itself,
and a UV-Visible spectrometer would normally have all types of lamps to fill the whole wavelength spectrum.

Applications of UV- Spectroscopy

In research, ultraviolet/visible spectroscopy is used more commonly than in detection. Through first reacting the sample to
bring the metal into solution as an ion, the trace metal content of an alloy, such as manganese in steel, can be determined.

A common technique for quantitative analysis of analytes in QA/QC, analytical research, and government regulatory
laboratories is UV-Visible spectrophotometry. The fundamentals of the approach are learned in school, such as Beer’s Law.
UV-Visible Mid-range to Upper-end Spectrophotometers are typically used in research laboratories, including university and
industrial laboratories.

The ion is then complexed or made to react so that it can be measured in a shape, such as manganese as the
manganate(VII) ion. When the spectrum is registered, the absorbance is the most valuable bit of information since the
concentration of the solution can be determined if the absorption coefficient of the chromophore is known and thus the mass
of the metal in the sample.

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 4
ENGINEERING CHEMISTRY AIST SAGAR

Derivation of Beer Lambert Law

Beer-Lambert Law- helps us define the relationship between the intensity of visible UV radiation and
the exact quantity of substance present. The derivation of Beer-Lambert Law has many applications in
modern-day science. Used in modern-day labs for testing of medicines, organic chemistry and tests with
quantification. These are some fields in which this law finds its uses.

Beer-Lambert Law Statement

The Beer-Lambert law states that:
for a given material sample path length and concentration of the sample are directly proportional to the
absorbance of the light.
The Beer-Lambert law is expressed as:
A = εLc
where,

 A is the amount of light absorbed for a particular wavelength by the sample

 ε is the molar extinction coefficient
 L is the distance covered by the light through the solution
 c is the concentration of the absorbing species

Beer-Lambert Law

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 5
ENGINEERING CHEMISTRY AIST SAGAR

Absorption of energy causes the absorption of light as well usually by electrons. Different forms of light such as visible light and
ultraviolet light get absorbed in this process. Therefore, change in the intensity of light due to absorption, interference, and scattering
leads to:

Assistant Professor:Seema malviya , Department of Applied Science and Humanities

Page 6