2.3.3 Evidence for the quantized* Electronic Energy Levels: Atomic spectra

The speed of light depends upon the nature of the medium through which it passes. As a result, the beam of light is deviated or refracted from its original path as it passes from one medium to another. It is observed that when a ray of white light is passed through a prism, the wave with shorter wavelength bends more than the one with a longer wavelength.

Since ordinary white light consists of waves with all the wavelengths in the visible range, a ray of white light is spread out into a series of coloured bands called spectrum. The light of red colour which has longest wavelength is deviated the least while the violet light, which has shortest wavelength is deviated the most.

The spectrum of white light, that we can see, ranges from violet at 7.50 × 1014 Hz to red at 4×1014 Hz. Such a spectrum is called continuous spectrum. Continuous because violet merges into blue, blue into green and so on. A similar spectrum is produced when a rainbow forms in the sky.

Remember that visible light is just a small portion of the electromagnetic radiation (Fig.2.7). When electromagnetic radiation interacts with matter, atoms and molecules may absorb energy and reach to a higher energy state. With higher energy, these are in an unstable state.

For returning to their normal (more stable, lower energy states) energy state, the atoms and molecules emit radiations in various regions of the electromagnetic spectrum.

 

Emission and Absorption Spectra

The spectrum of radiation emitted by a substance that has absorbed energy is called an emission spectrum. Atoms, molecules or ions that have absorbed radiation are said to be “excited”.

To produce an emission spectrum, energy is supplied to a sample by heating it or irradiating it and the wavelength (or frequency) of the radiation emitted, as the sample gives up the absorbed energy, is recorded. An absorption spectrum is like the photographic negative of an emission spectrum.

A continuum of radiation is passed through a sample which absorbs radiation of certain wavelengths. The missing wavelength which corresponds to the radiation absorbed by the matter, leave dark spaces in the bright continuous spectrum. The study of emission or absorption spectra is referred to as spectroscopy.

The spectrum of the visible light, as discussed above, was continuous as all wavelengths (red to violet) of the visible light are represented in the spectra. The emission spectra of atoms in the gas phase, on the other hand, do not show a continuous spread of wavelength from red to violet, rather they emit light only at specific wavelengths with dark spaces between them.

Such spectra are called line spectra or atomic spectra because the emitted radiation is identified by the appearance of bright lines in the spectra (Fig. 2.10 page 45). Line emission spectra are of great interest in the study of electronic structure. Each element has a unique line emission spectrum.

The characteristic lines in atomic spectra can be used in chemical analysis to identify unknown atoms in the same way as fingerprints are used to identify people.

The exact matching of lines of the emission spectrum of the atoms of a known element with the lines from an unknown sample quickly establishes the identity of the latter, German chemist, Robert Bunsen (1811-1899) was one of the first investigators to use line spectra to identify elements.

Elements like rubidium (Rb), caesium (Cs) thallium (Tl), indium (In), gallium (Ga) and scandium (Sc) were discovered when their minerals were analysed by spectroscopic methods. The element helium (He) was discovered in the sun by spectroscopic method.

 

Line Spectrum of Hydrogen

When an electric discharge is passed through gaseous hydrogen, the H2 molecules dissociate and the energetically excited hydrogen atoms produced emit electromagnetic radiation of discrete frequencies. The hydrogen spectrum consists of several series of lines named after their discoverers.

Balmer showed in 1885 on the basis of experimental observations that if spectral lines are expressed in terms of wavenumber, then the visible lines of the hydrogen spectrum obey the following formula:

where n is an integer equal to or greater than 3 (i.e., n = 3,4,5,....)

The series of lines described by this formula are called the Balmer series. The Balmer series of lines are the only lines in the hydrogen spectrum which appear in the visible region of the electromagnetic spectrum. The Swedish spectroscopist, Johannes Rydberg, noted that all series of lines in the hydrogen spectrum could be described by the following expression:

where n1 =1,2........

n2 = n1 + 1, n1 + 2......

The value 109,677  is called the Rydberg constant for hydrogen. The first five series of lines that correspond to n1 = 1, 2, 3, 4, 5 are known as Lyman, Balmer, Paschen, Bracket and Pfund series, respectively, Table 2.3 shows these series of transitions in the hydrogen spectrum. Fig 2.11 shows the Lyman, Balmer and Paschen series of transitions for hydrogen atom. Of all the elements, hydrogen atom has the simplest line spectrum. Line spectrum becomes more and more complex for heavier atom.

There are, however, certain features which are common to all line spectra, i.e.,

  • line spectrum of element is unique and
  • there is regularity in the line spectrum of each element. The questions which arise are: What are the reasons for these similarities? Is it something to do with the electronic structure of atoms? These are the questions need to be answered. We shall find later that the answers to these questions provide the key in understanding electronic structure of these elements.

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