Spectroscopy/Spectrometry

Spectroscopy is the study of the interaction between matter and electromagnetic radiation.
Historically, spectroscopy originated through the study of visible light dispersed according to
its wavelength, by a prism. Later the concept was expanded greatly to include any interaction with
radiative energy as a function of its wavelength or frequency. Spectroscopic data are often represented
by an emission spectrum, a plot of the response of interest as a function of wavelength or frequency.

Information:
 Composition of Material
 Type of elements
 Detection of drug interaction
 Analysis of space object

Types of Spectrometry/ Spectroscopy

i) Adsorption Spectroscopy/Spectrometry : It refers to spectroscopic techniques that measure
the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a
sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the
absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption
spectroscopy is performed across the electromagnetic spectrum.
Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a
particular substance in a sample and, in many cases, to quantify the amount of the substance
present. Infrared and ultraviolet-visible spectroscopy are particularly common in analytical
applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics,
astronomical spectroscopy and remote sensing.
There are a wide range of experimental approaches for measuring absorption spectra. The most
common arrangement is to direct a generated beam of radiation at a sample and detect the intensity of
the radiation that passes through it. The transmitted energy can be used to calculate the absorption. The
source, sample arrangement and detection technique vary significantly depending on the frequency
range and the purpose of the experiment.
ii) Mass Spectroscopy:
Mass spectrometry (MS) is an analytical technique that ionizes chemical species and sorts
the ions based on their mass-to-charge ratio. In simpler terms, a mass spectrum measures the masses
within a sample. Mass spectrometry is used in many different fields and is applied to pure samples as
well as complex mixtures.
A mass spectrum is a plot of the ion signal as a function of the mass-to-charge ratio. These spectra are
used to determine the elemental or isotopic signature of a sample, the masses of particles and
of molecules, and to elucidate the chemical structures of molecules and other chemical compounds.
In a typical MS procedure, a sample, which may be solid, liquid, or gas, is ionized, for example by
bombarding it with electrons. This may cause some of the sample's molecules to break into charged
fragments. These ions are then separated according to their mass-to-charge ratio, typically by
accelerating them and subjecting them to an electric or magnetic field: ions of the same mass-to-charge
ratio will undergo the same amount of deflection. The ions are detected by a mechanism capable of
detecting charged particles, such as an electron multiplier. Results are displayed as spectra of the
relative abundance of detected ions as a function of the mass-to-charge ratio. The atoms or molecules
in the sample can be identified by correlating known masses (e.g. an entire molecule) to the identified
masses or through a characteristic fragmentation pattern.

1
Fig: Sample spectrum produced by mass spectrometer. Simplified mass spectrum of pentane.
iii) Energy Dispersive Spectroscopy:
Energy-dispersive X-ray spectroscopy (EDS, EDX, EDXS or XEDS), sometimes called energy
dispersive X-ray analysis (EDXA) or energy dispersive X-ray microanalysis (EDXMA), is an
analytical technique used for the elemental analysis or chemical characterization of a sample. It relies
on an interaction of some source of X-ray excitation and a sample. Its characterization capabilities are
due in large part to the fundamental principle that each element has a unique atomic structure allowing
a unique set of peaks on its electromagnetic emission spectrum[2] (which is the main principle
of spectroscopy).
To stimulate the emission of characteristic X-rays from a specimen, a high-energy beam of charged
particles such as electrons or protons (see PIXE), or a beam of X-rays, is focused into the sample being
studied. At rest, an atom within the sample contains ground state (or unexcited) electrons in discrete
energy levels or electron shells bound to the nucleus. The incident beam may excite an electron in an
inner shell, ejecting it from the shell while creating an electron hole where the electron was. An electron
from an outer, higher-energy shell then fills the hole, and the difference in energy between the higher-
energy shell and the lower energy shell may be released in the form of an X-ray. The number and
energy of the X-rays emitted from a specimen can be measured by an energy-dispersive spectrometer.
As the energies of the X-rays are characteristic of the difference in energy between the two shells and
of the atomic structure of the emitting element, EDS allows the elemental composition of the specimen
to be measured.

EDS spectrum of the mineral crust of the vent shrimp Rimicaris exoculata Most of these peaks are X-
rays given off as electrons return to the K electron shell.(K-alpha and K-beta lines) One peak is from
the L shell of iron.

2
iv) Biomedical Spectroscopy:
Biomedical spectroscopy is a multidisciplinary research field involving spectroscopic tools for
applications in the field of biomedical science. Vibrational spectroscopy such as Raman or infrared
spectroscopy is used to determine the chemical composition of a material based on detection of
vibrational modes of constituent molecules. Some spectroscopic methods are routinely used in clinical
settings for diagnosis of disease; an example is Magnetic resonance imaging (MRI). Fourier transform
infrared (FTIR) spectroscopic imaging is a form of chemical imaging for which the contrast is provided
by composition of the material.
v) Astronomical Spectroscopy:
Astronomical spectroscopy is the study of astronomy using the techniques of spectroscopy to measure
the spectrum of electromagnetic radiation, including visible light and radio,
which radiates from stars and other celestial objects. A stellar spectrum can reveal many properties of
stars, such as their chemical composition, temperature, density, mass, distance, luminosity, and relative
motion using Doppler shift measurements. Spectroscopy is also used to study the physical properties
of many other types of celestial objects such as planets, nebulae, galaxies, and active galactic nuclei.

Interaction of Electromagnetic Radiation with matter

(EMR), i.e., light from an appropriate source, and the amount absorbed is related to the concentration
of the analyte in the solution.
EMR is absorbed by solution/solid sample, amount of radiation absorbed is equal to concentration of
sample.

AαC
A = Absorbance, C= concentration of sample
A Solution containing copper ions is blue because it absorbs the complementary color yellow from
white light and transmits the remaining blue light (see Table). The more concentrated the copper
solution, the more yellow light is absorbed and the deeper the resulting blue color of the solution. In a
spectrometric method, the amount of this yellow light absorbed would be measured and related to the
concentration. We can obtain a better understanding of absorption spectrometry from a consideration
of the electromagnetic spectrum and how molecules absorb radiation. Absorption of light can also
result in the emission of light; light can also be scattered in a characteristic manner by molecules; all
of these phenomena have analytical utility.

3
The Electromagnetic Spectrum

For our purposes, electromagnetic radiation can be considered any form of radiant energy that is
propagated as a transverse wave. It vibrates perpendicular to the direction of propagation, and this
imparts a wave motion to the radiation, as illustrated in Figure The wave is described either in terms
of its wavelength, the distance of one complete cycle, or in terms of the frequency, the number of cycles
passing a fixed point per unit time. The reciprocal of the wavelength is called the wavenumber and is
the number of waves in a unit length or distance per cycle.

The wavelength of electromagnetic radiation varies from a few angstroms to several meters. The
units used to describe the wavelength are as follows:

Electromagnetic radiation possesses a certain amount of energy. The energy of ultimately indivisible
unit of radiation, called the photon, is related to the frequency or wavelength by