chemistry app 2/3/06 09:10 Page 166
Atomic Spectroscopy
Atomic Spectroscopy
Atomic spectroscopy is the determination of elemental
composition by its electromagnetic or mass spectrum. The
study of the electromagnetic spectrum of elements is called
Optical Atomic Spectroscopy.
Electrons exist in energy levels within an atom. These levels
have well defined energies, and electrons moving between
them must absorb or emit energy equal to the difference
between levels. In optical spectroscopy, the energy absorbed to
move an electron to a more energetic level and/or the energy
emitted as the electron moves to a less energetic energy level
is in the form of a photon.
The wavelength of the emitted radiant energy is directly related
to the electronic transition which has occurred. Since every
element has a unique electronic structure, the wavelength of
light emitted is a unique property of each individual element. As
the orbital configuration of a large atom may be complex, there
are many electronic transitions which can occur, each transition
Figure 1 - Energy Transitions
resulting in the emission of a characteristic wavelength of light,
as illustrated in Figure 1.
The science of atomic spectroscopy has yielded three
techniques for analytical use:
• Atomic Absorption
• Atomic Emission
• Atomic Fluorescence
The processes of excitation and decay impunges on all three
techniques of atomic spectroscopy. Either the energy absorbed
in the excitation process, or the energy emitted in the decay
process is measured and used for analytical purposes.
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Atomic Absorption
Spectroscopy
If light of just the right wavelength impinges on a free, ground state
atom, the atom may absorb the light as it enters an excited state in
a process known as atomic absorption. This process is illustrated
in Figure 2.
Atomic absorption measures the amount of light at the resonant
wavelength which is absorbed as it passes through a cloud of
atoms. As the number of atoms in the light path increases, the
amount of light absorbed increases in a predictable way. By
measuring the amount of light absorbed, a quantitative
determination of the amount of analyte element present can be
made. The use of special light sources and careful selection of
wavelength allow the specific quantitative determination of
individual elements in the presence of others.
The atom cloud required for atomic absorption measurements is
produced by supplying enough thermal energy to the sample to
dissociate the chemical compounds into free atoms. Aspirating a
solution of the sample into a flame aligned in the light beam
serves this purpose. Under the proper flame conditions, most of
the atoms will remain in the ground state form and are capable of
absorbing light at the analytical wavelength from a source lamp.
The ease and speed at which precise and accurate determinations
can be made with this technique have made atomic absorption
one of the most popular methods for the determination of metals.
Figure 2 - The atomic absorption process
Figure 3 - ICCD Quantum Efficiency relevant to Atomic
spectroscopy
chemistry app 2/3/06 09:11 Page 167

Atomic Spectroscopy

Atomic Emission Spectroscopy

In atomic emission, a sample is subjected to a high energy,
thermal environment in order to produce excited-state atoms,
capable of emitting light. The energy source can be an
electrical arc, a flame, or more recently, a plasma.
The emission spectrum of an element exposed to such an
energy source, consists of a collection of the allowable
emission wavelengths, commonly called emission lines,
because of the discrete nature of the emitted wavelengths. This
emission spectrum can be used as a unique characteristic for
qualitative identification of the element. Atomic emission using
electrical arcs has been widely used for qualitative analysis.
Emission techniques can also be used to determine how much
of an element is present in a sample. For a "quantitative"
analysis, the intensity of light emitted at the wavelength of the
element to be determined is measured. The emission intensity
at this wavelength will be greater as the number of atoms of
Figure 4 - How the three techniques are implemented.
the analyte element increases. The technique of flame
photometry is an application of atomic emission for quantitative
analysis. Detector Requirements for
Atomic Spectroscopy
Atomic Fluorescence Considering the needs of atomic spectroscopy, Andor has
designed its line of products to fully cater to the needs of this
Spectroscopy industry. Traditionally this application has used a combination of
The third field of atomic spectroscopy is atomic fluorescence. a monochromator and a PMT, however the Andor solution
This technique incorporates aspects of both atomic absorption provides consists of a high throughput (F/4 aperture ratio)
and atomic emission. Like atomic absorption, ground state imaging spectrograph (Shamrock SR-303i) coupled to an ICCD
atoms created in a flame are excited by focusing a beam of camera (iStar).
light into the atomic vapor. Instead of looking at the amount of The iStar comes with a variety of photocathode tubes which
light absorbed in the process, however, the emission resulting can be selected depending on the range of wavelength desired
from the decay of the atoms excited by the source light is to be detected. These cameras have a single photon sensitivity
measured. The intensity of this "fluorescence" increases with as found in PMTs and can be gated down to 2ns gate widths.
increasing atom concentration, providing the basis for
The advantage of using this combination of an imaging
quantitative determination. spectrograph and ICCD detector, over the monochromator and
The source lamp for atomic fluorescence is mounted at an PMT, is that a number of wavelengths can be detected in one
angle to the rest of the optical system, so that the light detector shot, this drastically reduces the experiment time while
simultaneously provides for high spatial and spectral resolution.
sees only the fluorescence in the flame and not the light from
Single photon sensitivity is offered by the gain multiplication
the lamp itself. It is advantageous to maximize lamp intensity, ability of the intensifier tube.
since sensitivity is directly related to the number of excited
atoms which inturn is a function of the intensity of the exciting
Chemistry
radiation.

Conclusion
While atomic absorption is the most widely applied of the three
techniques and usually offers several advantages over the other
two, particular benefits may be gained with either emission or
fluorescence in special analytical situations.

SR-303i spectrograph fitted with iStar ICCD camera

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