History of spectroscopy

In the year of 1666, Sir Isaac Newton accomplished the first spectroscopic experiment by collecting sunlight through a hole after which, a prism broke the light up into a continuous band of colors. Newton called this band a spectrum. Nearly one hundred years later, color bands with dark spaces between, i.e., a discontinuous spectrum, were observed for the first time by Thomas Melvill . He used the Newton prism method for the study of bright light of salt burning in a flame. The Newton method was improved for the first time in 1802 when Wollaston replaced the round hole by a slit resulting in a purer and clearer spectrum. Thereby, he saw not a continuous sun spectrum as Newton had thought to see but dark lines in the solar spectrum. However, the explanation of this observation was first given by Joseph Fraunhofer a decade later. He examined the sun spectrum through a telescope allowing the observation of brighter spectra in more detail. The pioneer work of Fraunhofer was not only based on the discovery and mapping of hundreds of the dark sun lines, but also on finding them in the spectra of the planets and on observing similar lines in the spectra of a few of the brighter stars. A further step in the history of spectroscopy was the discovery of the missing of entire bands in the spectrum when Sir John Herschel observed light shining through certain colored glasses. Ten years later, a material was finally assigned to an absorption spectrum for the first time. Brewster studied light passing through certain types of gases and he found out in the comparison of the solar spectrum that the atmosphere of the sun contained among other things "nitrous acid gas". A significant improvement of the spectrum clarity dates from 1839. A lens, i.e. a collimator, was introduced into the spectroscope independently by Swan and Simms. The collimator arranged the incoming light in such a way that all rays felt on the prism with the same orientation ensuring an identical refraction of the different colors. After this

upgrade, the spectroscope, however, found its use not in the investigation of the origin of absorption or emission lines but as an ideal monochromatic light source for experiments like microscopic observations without chromatic aberration. It was not until the late 1850s, when Robert Bunsen and Gustav Kirchoff stated together the general principle that the line positions in a spectrum are characteristic for a specific substance. The science of optical spectroscopy was born. Unfortunately, there was no theory before the 20th century that could satisfactorily explain the origin of the spectra of the elements or the reason why different elements have different spectra. It was Johann J. Balmer who found a simple numerical pattern following the frequency spectrum of hydro gen. Johannes R. Rydberg revised the pattern and smoothed the way for a first theoretical model presented by the Danish physicist Niels Bohr. The model predicting quantized energy levels was in good quantitative agreement with a measured hydrogen spectrum. In 1925, a new revolutionary theory, the so-called quantum mechanics explaining the discrete, quantum nature of the spectra, was developed by the physicists Werner Heisenberg and Erwin Schrdinger. Finally, the quantum mechanics has been extended to the quan tum electrodynamics by Dirac, Heisenberg, and Pauli. It describes the inter action of radiation with matter completely

Spectroscopic Analysis
Today, a very wide application area is covered by spectroscopic techniques analyzing all kinds of samples qualitatively and / or quantitatively. The qualitative analysis implies the identification of a single unknown sample or of different components in an unknown mixture. Thereby, the characteristic energy transitions of an atom or molecule, i.e. the characteristic absorption lines or its characteristic fingerprint, provide the explicit sample identification. The quantitative analysis determines the concentration of a known substance or component and is achieved in consideration of the absorbed or transmitted

intensity of the incident light or by the determination of the intensity of light emitted by the sample. Figure 1.1 summarizes the two types of spectroscopic analyses.

Spectroscopic analysis

Qualitative analysis

Quantitative analysis

Characteristic wavelength (finger print) of a given sample

Intensity of emission or absorption

Identification

Concentration of a sample

Fig 1: Spectroscopic analysis