ATOMIC ABSORBTION

ABHAY ML VERMA SPECTROSCOPY

Definition: Atomic absorption spectroscopy is a type of quantitative analysis where in a specific wave length of light
absorbed by atoms in neutral state is detected or recorded.

The more the number of the atoms, the more is the intensity of absorption and vice-verse.

This can also be called as metal analysis spectrometer as it mainly used for metal analysis.

Atomic absorption Spectroscopy theory:

The method relies on absorption method of spectroscopy.

The method involves, the spraying of sample in solution state over a burner. This leads to evaporation of solvent and
leave fine dry residue behind which is nothing but neutral atoms in ground state. To these atoms, a light of specific wave
length is passed and the un-absorbed light is recorded over a detector.

THE ATOM AND ATOMIC SPECTROSCOPY

The science of atomic spectroscopy has yielded three techniques for analytical use: atomic emission, atomic
absorption, and atomic fluorescence. In order to un- derstand the relationship of these techniques to each other, it is
necessary to have an understanding of the atom itself and of the atomic process involved in each technique.

The atom is made up of a nucleus surrounded by electrons. Every element has a specific number of electrons which are
associated with the atomic nucleus in an orbital structure which is unique to each element. The electrons occupy orbital
po- sitions in an orderly and predictable way. The lowest energy, most stable electronic configuration of an atom, known
as the ground state, is the normal orbital con- figuration for an atom. If energy of the right magnitude is applied to an
atom, the energy will be absorbed by the atom, and an outer electron will be promoted to a less stable configuration or
excited state. As this state is unstable, the atom will immediately and spontaneously return to its ground state
configuration. The elec- tron will return to its initial, stable orbital position, and radiant energy equivalent to the amount
of energy initially absorbed in the excitation process will be emitted. The process is illustrated in Figure 1-1. Note that in
Step 1 of the process, the ex- citation is forced by supplying energy. The decay process in Step 2, involving the
emission of light, occurs spontaneously.

Figure 1-1. Excitation and decay processes.

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The wavelength of the emitted radiant energy is directly related to the electronic transition which has occurred. Since
every element has a unique electronic struc- ture, the wavelength of light emitted is a unique property of each
individual ele- ment. As the orbital configuration of a large atom may be complex, there are many electronic transitions
which can occur, each transition resulting in the emission of a characteristic wavelength of light, as illustrated in Figure
1-2.

Figure 1-2. Energy transitions.

The process of excitation and decay to the ground state is involved in all three fields 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
pur- poses. In atomic emission, a sample is subjected to a high energy, thermal envi- ronment 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 in qualitative analysis.

Emission techniques can also be used to determine how much of an element is pre- sent 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 the analyte element increases. The technique of
flame photometry is an application of atomic emission for quantitative analysis.

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 ab-
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Figure 1-3. The atomic absorption process.

sorption. This process is illustrated in Figure 1-3. Note the similarity between this illustration and the one in Step 1 of
Figure 1-1. The light which is the source of atom excitation in Figure 1-3 is simply a specific form of energy. The
capability of an atom to absorb very specific wavelengths of light is utilized in atomic ab- sorption spectrophotometry.

ATOMIC ABSORPTION PROCESS

The quantity of interest in atomic absorption measurements is the amount of light at the resonant wavelength which is
absorbed as the light 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 ab- sorbed, a quantitative
determination of the amount of analyte element present can be made. The use of special light sources and careful
selection of wavelength al- low the specific quantitative determination of individual elements in the presence of others.

The atom cloud required for atomic absorption measurements is produced by sup- plying 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 ana- lytical wavelength from a source lamp. The ease and speed at which
precise and accurate determinations can be made with this technique have made atomic ab- sorption one of the most
popular methods for the determination of metals.

A third field in atomic spectroscopy is atomic fluorescence. This technique incor- porates aspects of both atomic
absorption and atomic emission. Like atomic ab- sorption, ground state atoms created in a flame are excited by
focusing a beam of light into the atomic vapor. Instead of looking at the amount of light absorbed in the process,
however, the emission resulting from the decay of the atoms excited by the source light is measured. The intensity of
this fluorescence increases with increasing atom concentration, providing the basis for quantitative determi- nation.
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The source lamp for atomic fluorescence is mounted at an angle to the rest of the optical system, so that the light
detector sees only the fluorescence in the flame and not the light from the lamp itself. It is advantageous to maximize
lamp inten- sity with atomic fluorescence since sensitivity is directly related to the number of excited atoms which is a
function of the intensity of the exciting radiation.

Figure 1-4. Atomic spectroscopy systems.

Figure 1-4 illustrates how the three techniques just described are implemented. 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.

Atomic absorption Spectroscopy Instrumentation:

Atomic absorption spectroscopy unlike other spectroscopy methods has two additional requirements like a specially
designed lamp to produce light of desired wave and a burner to prepare the sample for absorption of light.

The instrumentation includes:

1. The burner to dry the sample and produce atoms.

2. Sample container.

3. Fuel and oxidant to burn the sample by heat.

4. Hallow cathode lamp to produce light of desired wave length.

5. Detector to detect the absorption intensity.

6. Amplifier and data recorder.

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The burner: Here sample from the capillary rises to the tip of burner where it is burned with flame produced by the fuel
and oxidant combination. The sample after evaporation leaves a fine residue of neutral atoms.

Sample container: This is a beaker like container of sample which is placed below the burner preferably. A capillary tube
drains the sample to the tip of burner.

Fuel and oxidant: This is a very important part of entire process to be remembered. If the heat produced is not sufficient
then the sample doesnt form neutral atoms. If the heat of burner is more, the sample molecules may ionize instead of
forming atoms. So both are undesirable for experimentation.Hence a proper combination of fuels and oxidant are to be
used to produce recommended temperatures. Commonly used flues include propane, Hydrogen and acetylene ad
oxidants are mostly air or oxygen.

Hallow cathode lamp: This is another primary requirement in the entire process. If the element to be analyzed is
magnesium, the cathode lamp made of magnesium is used and so for all the other metal elements analyzed like Na, Ca, K,
Zn etc.

Detector: The used can be a simple photo multiplier tube or photo cell. The current or potential recorded for the sample
absorption is recorded in a computer software and then analyzed.

Atomic Absorption Spectroscopy applications:

1. Atomic spectroscopy is used for quantitative analysis of metal elements in any sample.

2. It is specially useful to analyze trace metal elements in plasma and other body fluids.

3. To determine metal elements in food industry.

4.To estimate Lead in petroleum products.

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