ATOMIC ABSORPTION SPECTROMETRY

If a solution containing a metallic salt (or some other metallic compound ) is

aspirated into a flame (e.g. acetylene burning in air), a vapor contains atoms of the
metal may be formed. Some of these gaseous metal atoms may be raised to an
energy level which is sufficiently high to permit emission of radiation characteristic
of the metal, e.g. the characteristic yellow colour imparted to flames by compounds
of sodium.
However, a much larger number of the gaseous metal atoms will normally remain in
the unexited state or the ground state. These ground state atoms are capable of
absorbing radiant energy of their own specific resonance wavelength, which in
general is the wavelength of radiation that the atoms would emit if excited from the
ground state. Hence, if light of the resonance wavelength is passed through a flame
containing the atoms in question, then part of the light will be absorbed , and the
extent of absorption will be proportional to the number of ground state atoms
present in the flame. This is the underlying principle of Atomic Absorption
Spectrometry.
Quantitative measurements in absorption spectrometry:
Quantitative absorption methods require two power or intensity measurements- one
before a beam has passed through the medium that contains the analyte (I 0) and
the other after (It).
Lamberts Law:
Lamberts law states that, when monochromatic radiation passes through a
transparent medium, the rate of decrease in intensity with the thickness of the
medium is proportional to the intensity of the radiation.
So,

-(dI/db) = k I

where, I= intensity of the radiation

b = thickness of the

medium
k = proportionality factor

Integrating and putting I = I0 when b=0 and I= It when b = b,

ln (I 0 /It) = kb
the ratio (It /I0) is the fraction of the incident radiation transmitted by a thickness b
of the medium and is called the Transmittance T. The absorbance A of the
medium is given by

A = log ( I 0/ It)

Beers Law:
Beer studied the effect of concentration of the coloured constituent in solution upon
the light transmission or absorption. He found the same relation between the
transmission and concentration as Lambert had discovered.
As per Beers law, the rate of decrease of intensity of monochromatic radiation with
concentration is proportional to the intensity of radiation.
So,

ln ( I0/ It ) = k c

where, c = concentration
k = proportionality factor

Combined Lambert-Beer Law:

ln ( I0/ It ) = k b

so,

ln ( I 0/ It ) b

and ln ( I0/ It ) = k c

so,

ln ( I 0/ It ) c

hence, if the two laws are combined together,

Then,

ln ( I 0 /It) bc
So,

ln ( I0/ It ) = kb c

or,

log

or,

10

( I0/ It ) = abc

A = abc

where, a = constant
A = absorbance of the medium

Components of Atomic Absorption Spectrometer:

Source
lamp
or heated

Sample
holder/
atomizer

Wavelengt
h
selector

Photoelectric
transducer

Signal
Processor/
Read-out

Resonance line souces:

Hollow cathode lamp:
The most common source for atomic absorption measurements is the hollow
cathode lamp as shown in the fig. This type of lamp consists of a tungsten anode
and a cylindrical cathode sealed in a glass tube that is filled with neon or argon at a
pressure of 1-5 torr. The cathode is constructed of a metal whose spectrum is
desired or serves to support a layer of that metal.

Tungsten anode

Quartz /pyrex window

Glass shield

Hollow cathode

Ionization of the inert gas (Ar/ Ne) occurs when a potential of the order of 300 V is
applied across the electrodes, which generates a current of 5-15 mA as argon ions
and electrons migrate to the electrodes. If the potential is sufficiently large, the
gaseous cations acquire enough kinetic energy to dislodge some of the metal atoms
from the cathode surface and produce an atomic cloud in a process called
sputtering. A portion of the sputtered metal atoms are in excited states and thus
emit their characteristic radiations as they return to the ground states. Eventually,
the metal atoms diffuse back to the cathode surface or to the glass walls of the tube
and are redeposited.
The cylindrical configuration of the cathode tends to concentrate the radiation in a
limited region of the metal tube; this design also enhances the probability of redeposition at the cathode rather than in the glass walls. The cathode may consist of
a mixture of several metals ; such lamps permit the determination of more than a
single element.

Sample Atomization Techniques:

Two most common methods of sample atomization are, 1) Flame atomization and 2)
Electrothermal atomization.
a) Flame atomization:
In a flame atomization, a solution of the sample is nebulized by a flow of
gaseous oxidant, mixed with a gaseous fuel and carried into a flame where
atomization occurs. A complex set of interconnected processes then occur in
the flame. The first is desolvation, in which the solvent is evaporated to
produce a finely divided solid molecular aerosol. Dissociation of most of these
molecules then leads to an atomic gas. Some of the atoms so formed ionize
to give cations and electrons. A fraction of the molecules, atoms and ions are
excited by the heat of the flame, thus giving atomic, ionic and molecular
spectra. These are unwanted.

Solution of
analyte
Nebulizatio
n
Spray mist
Desolvation
Solid/gas
aerosol
Volatilizatio
n
Gaseous
molecules

Excited
molecules
Dessociation

h
Excited atoms

Gaseous
atoms
Ionization
Gaseous ions

Excited ions

b) Electrothermal Atomization:
In electrothermal atomizer a few microliters of sample are first evaporated at
a low temperature and then ashed at a somewhat higher temperature in an
electrically heated graphite tube. After ashing, the current is rapidly
increased to several hundred amperes which causes the temperature to be
raised to ~20000C to 30000C. atomization of sample occurs in a period of a
few milliseconds to seconds. The absorption of the atomized particles is then
measured in the region immediately above the heated surface.
Instruments:
The instruments for atomic absorption spectrometry may be of two types, a) single
beam instrument and b) double beam instruments.
In the typical atomic absorption spectrometers, it is necessary to eliminate
interferences caused by emission of radiations by the flame. Much of this emitted
radiation is of course removed by the monochromators. Nevertheless, emitted
radiation corresponding in wavelength to the monochromator setting is inevitably
present in the flame due to excitation and emission by the analyte atoms. In order
to eliminate the effects of flame emission , it is necessary to modulate the output of
the source so that its intensity fluctuates at a constant frequency. The detector then
receives two types of signals an alternating one from the source, and a continuous
one from the flame. These signals are converted to the corresponding types of
electrical response. If the power supply for the source can be designed for
intermittent or AC operation so that the source is switched on and off at desired
constant frequency, then the effect of emitted radiations can be eliminated. This is
known as power modulation.
Another type of modulation is mechanical modulation. This is a simple and entirely
satisfactory way of modulating the emission from the source is to interpose a
circular metal disc or chopper in the beam between the source and the flame.
Alternating quadrants of these discs are removed to permit passage of light.
Rotation of the disc at constant known rate provides a beam that is chopped to the
desired frequency.
Hollow cathode
Chopper
Flame
Detecto
lamp
r
IA + S

IA = Absorption signal intensity

S= Intensity of emitted radiation
Here the beam is not blocked by chopper, detector receives the signals from both
the lamp and the fleme.

Here the beam from source is blocked, the signal reaching the detector arises from
the flame emission. The difference between the two signals is the analyte signal.

Lamp+ flame
signal

Signa
l

Analyte
signal
Time

Flame
signal