ATOMIC

ABSORPTION
SPECTROSCOPY

Dr. Shital Patel

Introduction
• Atomic Absorption Spectroscopy is a very common technique for detecting
metals and metalloids in samples.
• It is very reliable and simple to use.
• It can analyze over 62 elements.
• It also measures the concentration of metals in the sample.
• Atomic absorption spectroscopy is an analytical technique that measure the
concentration of an element by measuring the amount of light that is
absorbed at a characteristic wavelength when it passes through cloud of
atoms.
• As the number of atoms in the light path increases, the amount of light
absorbed increases.
 Principle
• When a solution containing metallic species is introduced into a flame,
the vapor of metallic species will be obtained.
• These ground state atoms of a particular element are receive of light
radiation of their own wavelength. Since the electronic structure of
every element is unique, the radiation absorbed represents a unique
property of each individual element and it can be measured.
• Part of that light will be absorbed by the particular element and the
absorption will be proportional to the density of atoms in the flame.
• Thus, in AAS, one determines the amount of light absorbed. Once this
value of absorption is known, the concentration of the metallic element
can be known from a calibration curve.
• Mathematically the amount of energy of light absorbed by atoms can be
given by the expression :
• A = (xe2/mc)N f
Where m & e are the mass and charge of the electron
N is the number of atoms per cm3 capable of absorbing radiation of
frequency v ( ie., ground state atoms )
f is the oscillator strength ( defined as the number of electrons per atom
capable of being excited by the incident radiation )
Hence , for transitions from the ground state , integrated absorption is
proportional to N ,which approximates to the concentration (c) of the
element in the sample
INSTRUMENTATION:
1) Radiation Source
2) Nebulization of liquid sample
3) Atomizers
4) Monochromator
5) Detectors
6) Amplifier
7) Read-out meter
Radiation Source
• Hollow cathode lamp: are the most common radiation source in AAS.
• It contains a tungsten anode and a hollow cylindrical cathode (made
up of element which is to be determined).
• These are sealed in a glass tube filled with an inert gas (mainly neon
or argon) at low pressure.
• Each elements has its own unique lamp which must be used for that
analysis.
• When a voltage of 300-500 volt is put across anode and cathode.
Atoms of filler gas (neon and argon) undergoes ionization and are
attracted towards anode and cathode. The fast moving ions of filler
gas will strike the surface of cathode and displace metal atoms. This
metal atom emits the characteristics spectrum of radiation.
Electrodeless Discharge Lamp
• It is difficult to make stable hollow cathode lamp from certain
elements particularly those that are volatile, such as arsenic,
germanium.
• An alternative light has been developed in the EDL. It consists of an
evacuated tube in which the metal of interest is placed. The tube is
filled with argon at low pressure and sealed off. The sealed tube is
then placed in microwave discharge cavity.
• Under these conditions the argon becomes a plasma and cause
excitation of the metal sealed inside the tube. The emission from the
metal is that of its spectrum.
Chopper
• A rotating wheel is interposed between the radiation source and the
flame. This rotating wheel is known as chopper
• It is interposed to break the steady light from the lamp into a
pulsating light. This gives pulsating current in photocell.
• There is also steady current caused by light which is emitted by flame.
But only pulsating current is amplified and recorded.
Atomizer
• Atomization is separation of particles into individual molecules and
breaking molecules into atoms .This is done by exposing the analyte
to high temperatures in a flame or graphite furnace.
• FLAME ATOMISERS
• NON FLAME ATOMISERS
Flame Atomizer
• A most common way is to use a flame which is used for converting
liquid into gaseous state and also converting the molecular form into
atomic vapor.
• There two types of burners
• Total consumption burner
• Premixed burner
Flame AAS
• Advantages
Short analysis time possible
Good precision
Easy to use
Cheap
• Limitation
Sensitivity
Dynamic range
Requires flammable gases
Unattended operation is not possible because of flammable gases
Must not contain excessive amounts of dissolved solids
 Non flame atomizer (Electro Thermal
Atomizer)
• The graphite furnace is an electro thermal atomizer system that can produce
temperatures as high as 3,000°C using a high current power supply .
• Graphite furnace technique uses a graphite coated furnace to vaporize the
sample.
• Samples are deposited in a small graphite coated tube which can then be
heated to vaporize and atomize the analytes.
• The heated graphite furnace provides the thermal energy to break chemical
bonds within the sample held in a graphite tube, and produce free ground
state atoms.
• The ground-state atoms are capable of absorbing energy, in the form of light,
and are elevated to an excited state.
 Graphite Furnace AAS
• Advantages
Small sample sizes ( as low as 0.5 uL)
Very little or no sample preparation is needed
High sensitivity due to entire sample is atomized at one time and free atoms remain in
the optical path longer
Ultra trace analysis possible
• Limitation
Very slow
Poorer precision
More chemical interferences
Method development requires skill
Standard additions calibration required more frequently
Expensive consumables (graphite tubes)
• Monochromator
• Detector
• Amplifier
• Read out meter
Interferences
• Spectral interferences
• Ionised interferences
• Chemical interferences
• Solvent interferences
Application
• Determination of metal elements in biological samples
• Determination of metallic element in food industry