ATOMIC SPECTRA AND QUALITATIVE SPECTRAL ANALYSIS

1. The aim of the laboratory

The aim of these laboratory is: i) to observe the discrete spectra of two gases
and to compare with the continuous spectrum of the natural light ii) to calibrate a
spectroscope (to establish the relationship that exist between the position of the
neon spectral lines observed on a scale and the wavelength) and iii) to use the
calibration curve for the determination of mercury spectral lines wavelengths.

2. Theoretical approach
The Danish physicist Niels Bohr (1885-1962) studied the problem of the atom.
He tried to unify the nuclear model with Einstein's quantum theory of light. In that
time, 1911, Einstein's revolutionary theory of the photoelectric effect had not yet
been confirmed and was not widely believed. Bohr accepted the planetary
arrangement of electrons but made the hypothesis that the laws of
electromagnetism do not operate inside atoms. He postulated that an electron
into a stable orbit does not radiate energy. Therefore, the electron does not fall
into the nucleus, destroying the atom. Bohr assumed that the light emitted by the
hydrogen atoms accompanied changes in the energy of the electrons. He noted
that the specific wavelengths in an atomic spectrum mean that an atomic
electron cannot absorb or emit just any wavelength of light. According to
Einstein, the energy of a light photon is given by E = hν. Thus, an electron can
emit or absorb only specific amounts of energy. That is, the energy of an electron
in an atom is quantized.
The different amounts of energy that an atomic electron is allowed are
called energy levels. When an electron has the smallest allowed amount of
energy, it occupies the lowest energy level. This level is called the ground state.
If an electron absorbs energy it can undergo a transition to a higher level, called
the excited state. Atomic electrons usually remain excited only a very small
fraction of a second before returning to the ground state and thus emitting
electromagnetic waves.
According to Bohr, the energy of an orbiting electron in an atom is the
sum of the kinetic
energy of the electron
and the potential
energy resulting from
the Coulombian attrac-
tion force between the
electron and nucleus.
Work has to be done to
move an electron from
an orbit near the
nucleus to one farther
Figure 1
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away. Therefore, the energy of an
electron from an orbit near the
nucleus is less than that of an
electron in an orbit farther away. The
electrons into an excited states have
larger orbits and thus higher
energies. Einstein demonastrate that
the light photon has an certan energy.
Bohr postulated that an photon can
be absorbed only if the energy of the
photon is equal with the difference in
the energy of the atomic electron
levels (see also figs. 1 and 2). That is:
hν = E excited − E ground . (1)

When the electron makes the

transition to the ground state, a
Figure. 2
photon is emitted (Fig. 1). The energy
of the photon is equal to the energy
difference between the excited and the ground states (see the Lymann series
from Fig. 2). The molecules also have discrete energy levels. Furthermore,
molecules have many ways to absorb energy. For example, they can rotate and
vibrate along the bonds, which atoms cannot do. As a result, molecules can emit
a much wider variety of light frequencies than atoms. While atomic spectra are
discrete spectra of lines, the molecular spactra consist from many bands.

3. Fluorescence and Phosphorescence

There are three ways to cause the atoms to emit photons: thermal excitation,
electronic excitation and photon excitation (see fig 3). Let us consider a
fluorescent lamp filled with mercury vapour. When a high voltage is applied
across the tube, the electrons collide with the Hg atoms, causing them to emit
ultraviolet photons. These photons strike a material called a phosphor, coated on
the inner surface of the glass tube. The ultraviolet photons are absorbed by the
atoms in the phosphor.
The atoms and the molecules of the coated substance are excited,
emitting photons of visible rather than ultraviolet light. Collision with photons,
then, is another method of exciting atoms, besides the thermal excitation and the
electron collision. Both fluorescent and phosphorescent materials contain atoms
that are easily to be excited. The substances differ by the duration of time
needed for excited atoms to relax to their normal energy levels. When an atom of
a fluorescent material is in the excited state, the atoms return to their normal
energy levels at once. In the higher energy levels the atoms have no stability. A
phosphorescent material contains atoms that, once excited, can remain for some
time in higher energy levels. Thus, a fluorescent reflector on an automobile will

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Figure 3
glow only while it is being irradiated by the photons from the headlights of
another automobile. Thus, the coating of a fluorescent lamp emits light only
when current flows through the tube.
Phosphorescence is somohow simmilar with fluorescence but can be
observed also after the incident light is turned off. The atoms in phosphorescent
materials remain longer in excited energy levels than in the case of fluorescent
substances. There is no sharp border-line between fluorescence and
phosphorescence. Generally, if an atom remains on an excited energy level
longer than 10-3 seconds, then the substance is considered to be
phosphorescent.

4. Atomic Spectra
The puzzle of the electron’s positions and motion around the nucleus in atom
was clarified by studying the light emitted by atoms. The set of wavelengths of
light emitted by an atom is called the emission spectrum of that atom. When a
body is heated it becomes incandescent. Moreover, all incandescent solids emits
the same spectrum. The properties of individual atoms become apparent only
when they are not tightly packed into a solid. Many substances can be vaporized
by heating them into a flame. Then the atoms can emit light which is
characteristic to each elements from the substance. For example, if sodium
chloride is held in a flame, the sodium atoms will emit a bright yellow light.
Similarly, lithium salts emit red light, and barium salts emit green light.
Gas atoms can be made to emit their characteristic colours by a electronic
excitation (shown in fig. 3 middle). A glass tube containing neon gas (Ne) has
metal electrodes at each end. When a high voltage is applied across the tube,
electrons pass through the gas, the electrons collide with the neon atoms,
transferring them the kinetic energy and exciting the Ne atoms. When they
release the suppementary energy, this extra energy it is emitted in the form of
light. The light has a red colour. Nitrogen and argon emit a bluish colour, and
mercury, greenish blue. The emission spectrum of an atom can be studied in

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Figure 4
greater detail using the instrument shown in figure 4. In this spectroscope, the
light passes through a slit (S) and is then dispersed by passing through a prism.
A lens system focus the dispersed light which finaly is observed through a
telescope. Each wavelength of light forms an image of the slit. The spectrum of
an incandescent body is a continuous band of colours from red to violet.
However, the spectrum of a gas is a series of lines of different colours. Each line
corresponds to a particular wavelength of light emitted by the atoms. The
emission spectra of atoms are characteristic features of the atoms of that gas.

5. Applications
Optical spectroscopy (which contain the visible, ultraviolet and infrared domains)
allow the identification of constitutive elements from a material, determination of
chemical structure, the establishment of concentration of a specific component
from a material. The utility of spectroscopy as a measurement tool was
demonstrated and now is applied in almost all domains of activity like: physics,
astrophysics, chemistry, biology, medicine, food industry, etc. Some examples
are the qualitative analysis of drugs, the identification and purity control of
various substances, dosage of substances in mixtures.

6. Experimental Procedure
This experiment will focus on:
1. Observing the emission Ne spectrum, with the prism spectroscope. The
wavelengths of the lines in the Ne spectrum are given in table 2 and the
coordinates of the coloured lines are read on the spectroscope scale. All

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being gathered in table 1. These data are then used to draw the
calibration curve of the spectroscope, λ=λ(div).
2. Observing the emission spectrum of an unknown gas and finding out
the wavelengths in its spectrum, by using the spectroscope for positioning
the lines and the calibration graph to find their wavelengths. For a certain
colour, of wavelength, its frequency is ν = c λ , and the energy of the
photon emitted with this frequency is E = hν (J).
3. The second data table will be completed, considering all these and that
the energy of photons is better to be expressed in eV ( 1eV = 1.6 ⋅ 10−19 J ).
Table 1
The studied bright red light left right
line color orange yellow
substance red orange green green green
wavelength
(Å)
Ne
Line position
(x)

Table 2
The studied
line color
substance
wavelength
(Å)
Hg Line
position
(x)

Table 3 Wavelengths of lines in the neon spectrum

Nr.
line color relative magnitude wavelength [Å]
Crt.
1 bright red 10 6402

2 red orange 10 6143

3 orange 5 5945

4 yellow 20 5852

5 light green, first after yellow line 4 5760

6 left green 8 5400

7 right green 6 5330

green from right of those five equally
8 5 5031
spaced lines
9 blue-green 8 4849

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