Topic 2: Radiations by atoms

2.1 Atomic spectra

▪ As we learnt previously about the structure of an atom, the electrons surrounding the atomic
nucleus are arranged in a series of levels of increasing energy.

▪ Also, from Bohr model we learnt that when an electron gets excited and transition (jump)
from one energy level to another, it either emits (if going from a higher level to a lower one)
or absorbs (if going from a lower level to a higher) energy in the form of light (photon) with
a discrete and specific wavelength.

▪ The collection of all these specific wavelengths of the atom in a given set of conditions like
pressure, temperature, etc. is the atomic spectra of atoms.

▪ Definition: Thus, atomic spectra are defined as the spectrum of the electromagnetic radiation
emitted or absorbed by an electron during transitions between different energy levels within
an atom.

▪ The study of atomic spectra is scientifically referred to as atomic spectroscopy.

2.2 Atomic spectroscopy

Atomic spectroscopy is the study of the electromagnetic radiation absorbed or emitted by atoms
when electrons transition from one energy level to another.

There are three types of atomic spectroscopy, and they are:

• Atomic emission spectroscopy: This involves the transfer of energy from the ground
state to an excited state. The electronic transition can be explained in atomic emission.
• Atomic absorption spectroscopy: For absorption to take place there should be identical
energy differences between the lower and higher energy levels. The atomic absorption
spectroscopy principle uses the fact that the free electrons generated in an atomizer can
absorb radiation at a specific frequency. It quantifies the absorption of ground-state atoms
in the gaseous state.
• Atomic fluorescence spectroscopy: This is a combination of atomic emission and
atomic absorption as it involves radiation of both excitation and de-excitation.

2.2.1 Uses of atomic spectroscopy

• It is used in pharmaceutical industries to find the traces of materials used.
• It can be used to study multidimensional elements.
• Also, it is useful as a tool to study the structure of atoms and molecules.
• It gives an accurate analytical method for finding components in a material that has an
unknown chemical composition.
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 • It is applicable for identification of the spectral lines of materials used in metallurgy.
• Atomic spectroscopy is also useful for occupational and environmental monitoring.

2.3 Types of spectra

A spectrum may be continuous, or may comprise bright lines (an emission spectrum), or dark
lines (an absorption spectrum) superimposed on a background. The main difference between
continuous spectrum and line spectrum is that continuous spectrum contains no gaps whereas
line spectrum contains many gaps.

2.3.1 Continuous spectra or blackbody spectra

Continuous spectra, also called thermal or blackbody spectra arises from hot dense gases or
solid objects which emit radiation over a broad range of wavelengths without any gaps, skips, or
breaks, thus, the spectra appear smooth and continuous.

A continuous spectrum literally results when the gas pressures are higher, so that the absorption
and emission spectral lines are broadened by collisions between the atoms until they are smeared
into a continuum.

In other words, a continuous spectrum can be viewed as an emission spectrum in which the lines
overlap with each other and can no longer be distinguished as individual emission lines.

Examples of continuous spectra

▪ Rainbow: The rainbow contains seven colors of the visible portion of the electromagnetic
spectrum which fade into each other without leaving any gap.
▪ White (visible) light: When visible light is dispersed by a diffracting grating or a prism, it
produces a continuous spectrum of all the colors of the rainbow. When this light passes
through an object or medium, the wave with the shortest wavelength (violet) deviates the most
than the one with the longest wavelength (red).

▪ Stars: Hot, dense light sources like stars, for example, emit a nearly continuous spectrum of
light, which travels out in all directions and interacts with other materials in space. The broad
range of colors that a star emits depends on its temperature.
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▪ Blackbody: When a black object is heated to glow, it emits radiation in a continuous
spectrum.

2.3.2 Line spectra

Line spectra can be produced using the same source of light which produces a continuous
spectrum. Under high pressure, a gas produces a continuous spectrum. However, under low
pressure, the same gas can give rise to either an absorption or an emission spectrum. Thus, line
spectra are composed of only certain wavelengths and frequencies that are characteristic for each
element (characteristic spectrum); occurring at specified frequencies and not continuously
distributed.

Line spectrum of any element is specific (essential characteristic), because its wavelength and
frequency differ from element to another. Thus, line spectra can be used to identify the elements
present in a source. There are no two elements with the same spectral lines. It is like the finger
print in human, which can be used to distinguish one person from another.

2.3.3 Types of line spectra

Line spectra are generated only in either absorption spectrum or emission spectrum. It shows
separate isolated lines in a given spectrum. These can be absorption lines which appear as dark
lines in a bright background or bright emission lines that appear on a dark background.

A. Emission line spectra

Emission spectra are produced when a beam of electromagnetic radiation (electrical or thermal
energy) is sent through a sample of atoms or molecules and the electrons in the sample absorb
energy, get excited, and transfer themselves to higher energy states. They cannot stay at the
higher level for very long and they fall back to the ground state, releasing energy equivalent to
the difference between the energies of the two levels. When the released energy is plotted against
the wavelength it forms the emission line spectrum in form of one or several thin bright colored
lines with dark background. Thus, emission lines correspond to photons of discrete energies that
are emitted when excited atomic states in the gas make transitions back to lower-lying levels.

B. Absorption line spectra

An absorption spectrum is produced when bright light of all wavelengths is passed through a
cold material and some characteristic wavelengths are absorbed by the elements in the
material. However, the re-emitted photons are not re-emitted in the same direction. Due to the
absence of this absorbed electromagnetic radiation, dark lines (absence of light) appear
superimposed on the continuous spectrum. Absorption spectra are used in various analysis
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techniques such as atomic absorption spectroscopy and UV-absorption spectroscopy. These
techniques are used in identifying a certain species in a given mixture or confirming
the identity of a particular species.

NB: It is interesting to note that the positions or the wavelengths of lines appearing in both
emission and absorption spectra are exactly the same. In emission spectrum, these lines appear
bright because the corresponding wavelengths are being emitted by the element, whereas they
appear dark in absorption spectrum because the wavelengths are being absorbed by the element.

2.4 Differences between emission and absorption spectra

Emission spectra Absorption spectra

▪ Produced when atoms release energy ▪ Produced when atoms absorb energy
▪ Comprise of colored lines in the spectrum ▪ Comprise of dark lines or gaps in the spectrum
▪ Helpful in determining composition of ▪ Helpful to determine the ability of certain objects to
matter absorb and retain energy e.g., heat energy
▪ Can emit all the colors in an ▪ Can have a few colors missing due to the
electromagnetic spectrum redirection of absorbed photons

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2.5 Application of atomic spectra
1. Identification of elements in salts by flame test
2. Street advertisement light
3. Fireworks: The colors of fireworks are due to atomic emission spectra. As shown in part
(a), a typical shell used in a fireworks display contains gunpowder to propel the shell into
the air and a fuse to initiate a variety of redox reactions that produce heat and small
explosions. Thermal energy excites the atoms to higher energy states; as they decay to
lower energy states, the atoms emit light that gives the familiar colors. When
oxidant/reductant mixtures are ignited, a flash of white or yellow light is produced along
with a loud bang. Achieving the colors shown in part (b) requires adding a small amount of
a substance that has an emission spectrum in the desired portion of the visible spectrum.

For example, sodium is used for yellow because of its 589 nm emission lines. Strontium salts,
which are also used in highway flares, emit red light, whereas barium gives a green color. Blue is
one of the most difficult colors to achieve. Copper salts emit a pale blue light, but copper is
dangerous to use because it forms highly unstable explosive compounds with anions such as
chlorate. As you might guess, preparing fireworks with the desired properties is a complex,
challenging, and potentially hazardous process.

4. Lasers
Laser beams are generated by the same general phenomenon that gives rise to emission spectra,
with one difference: only a single excited state is produced, which in principle results in only a
single frequency of emitted light.

The schematic diagram in (a) shows the ruby rod, the flash lamp used to excite the Cr3+ ions in
the ruby, and the totally and partially reflective mirrors. (b) This schematic drawing illustrates
how light from the flash lamp excites the Cr3+ ions to a short-lived excited state, which is
followed by decay to a longer-lived excited state that is responsible for the stimulated in-phase
emission of light by the laser.
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2.6 Hydrogen line spectra
Hydrogen atom has the simplest line spectrum of all elements. Interpretation of spectra from multi-
electron atoms (heavier atoms) becomes more and more complex, even by today’s standards. Thus,
understanding of atomic spectra must begin with the simplest atom of all — atomic hydrogen
(an atom with only one electron) as adequately explained by the Bohr model.

According to Bohr, electron in hydrogen atom may revolve in any orbit depending upon its energy.
When hydrogen gas is heated or subjected to an electric discharge, its electron moves from one of
the lower to higher orbit, absorbing particular wavelength of energy. Subsequently, when it comes
back, the same energy is released. This energy is observed as radiation of particular wavelengths in
the form of bright lines seen in the certain region of the emission spectrum of hydrogen gas.

When an electric discharge is passed through gaseous hydrogen, the H2 molecules dissociate and
the energetically excited hydrogen atoms emit spectra of electromagnetic radiation of discrete
frequencies as they lose the excitation energy and return to their stable states.

The spectra of atomic hydrogen consist of a set of characteristic isolated sharp spectral lines; one
set in the ultraviolet region of the electromagnetic spectrum, one set in the visible region, and
several sets in the infrared region.

These spectral lines can be classified into five groups called spectral series. These series are named
after their discoverers as:
(i) Lyman series (UV region)
(ii) Balmer series (visible region)
(iii) Paschen series (IR region)
(iv) Brackett series (IR region)
(v) Pfund series (IR region)

When the lines corresponding to a particular series are examined, they are seen that they all fit in
the general Rydberg formula;

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 where and

RH is called the Rydberg constant for hydrogen, and has a value of 109,677 cm–1. The first five
series of lines that correspond to n = 1, 2, 3, 4, 5 are known as Lyman, Balmer, Paschen, Bracket
and Pfund series, respectively.

Series n m Spectral region

Lyman 1 2, 3, … Ultraviolet
Balmer 2 3, 4, … Visible
Paschen 3 4, 5, … Infrared
Bracket 4 5, 6, … Infrared
Pfund 5 6, 7, … Infrared

2.3.1 Ultraviolet spectral series for hydrogen – Lyman series

Discovered by Lyman in 1906. This occurs when electron moves from higher levels n= 2, 3, 4 …
down to the 1st level K (n = 1). By applying the above equation, Lyman discovered that these
series have wavelengths that lie in the ultraviolet range (short wavelengths and high frequency).

Lyman series of hydrogen spectrum has the largest energy and highest frequencies than other
seriates. Because it occurs due to transfer of electron from higher energy levels to the 1st energy
level (K), so the difference in energy (∆E) between the higher levels and the 1st level (K) (n=1) is
very large. So, it has highest frequencies because ∆E = h → h is Planck's constant → ∆E  .
The wavelengths for Lyman series calculated from the general equation are tabulated below.

2.3.2 The visible spectra for hydrogen – Balmer series

Discovered by Balmer in 1885. This occurs when an electron moves from higher levels down to
the 2nd level L (n = 2). By applying the general equation, Balmer found the series spectra lines
have wavelengths that lie in the visible range of the electromagnetic spectrum. The longest
wavelength in this series occurs when electron transmitted from 3rd level to 2nd level.

The four visible hydrogen emission spectrum lines in the Balmer series have wavelengths
656.21 nm (red), 486.07 nm (blue/green), 434.01 nm (blue/violet) and 410.12 nm (violet).

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2.3.3 The infrared spectral series for hydrogen
▪ Paschen series: The electron moves from higher levels down to level M (n = 3).
▪ Brackett series: Electron moves down to level N (n = 4) from higher levels.
▪ Pfund series: Electron moves down to level O (n = 5) from higher levels. This series has the
longest wavelengths and lowest frequencies among the line spectrum of hydrogen. Because it
occurs due to transferee of electron from higher energy level to 5th energy level (O) where (n
= 5) → so the difference in energy between the higher levels and the energy level (O) (∆E) is
small.

Energy level diagram for hydrogen

2.4 Calculation of the energy loss by electron during atomic transition

The emission line spectrum results from electrons dropping from higher energy level to lower
energy levels. Each time an electron drops, a light is released whose energy corresponds to the
difference in energy between the two levels. The energy difference between one energy level to
another can simply be expressed as;
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 ΔE = (Ei – Ef) eV.
= (Ei – Ef) x 1.6 x 10-19 (electron charge) joule.
ΔE = h  = h C/

▪ Wavelength of the emitted radiation is given by;

▪ Frequency of the emitted radiation is given by;

where,  = h C/

Worked examples

1. If the shortest wavelength in one series of hydrogen spectrum atom is (8212 A). What are
the series and the longest wavelength in it?

Given: shortest = 8212 A. Wanted: name of series; longest.

Solution:

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2. Calculate the shortest wavelength in Paschen series if the energy of the 3rd level (E = - 1.51)
eV.

Solution
▪ Given: E3 = - 1.51 eV. Wanted: 
▪ The shortest wavelength is obtained when electron returns from infinity (E) to certain
energy level (M), thus:

∆E = E  - E 3 = 0 – (- 1.51) = 1.51 eV.

= 1.51 x 1.6 x 10-19 Joule = 2.416 x 10-19 Joule

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