ATOMIC ABSORPTION

SPECTROSCOPY

• Rashmi Mishra
• PhD Scholer
• National Institute of Technology Raipur
Introduction
principle
instrumentation
interferences
Application
Conclusion
 Introduction

Atomic Absorption Spectrophotometry,

which are standard instruments for
the determination of metal elements,
are widely applied of samples, such as
agriculture chemical, clinical and
biochemistry, minerals, food and
drugs, environmental and other.
The original 1954 AAS instrument

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Basic Principle
• The technique of (AAS) requires a liquid sample to be aspirated,
aerosolized, and mixed with combustible gases, such as
acetylene and air or acetylene and nitrous oxide.

• The mixture is ignited in a flame whose temperature ranges

from 2100 to 2800 oC.

• During combustion, atoms of the element of interest in the

sample are reduced to free, unexcited ground state atoms,
which absorb light at characteristic wavelengths.
Basic Principle … Continue

• The characteristic wavelengths are element specific and

accurate to 0.01-0.1nm.

• To provide element specific wavelengths, a light beam from a

lamp whose cathode is made of the element being
determined is passed through the flame.

• A device such as photomultiplier can detect the amount of

reduction of the light intensity due to absorption by the
analyte, and this can be directly related to the amount of the
element in the sample.
Atomic absorption spectrometer
“block diagram”
 PARTS OF ATOMIC ABSOPTION
SPECTROMETER
• RADIATION SOURCE
• CHOPPER
• ATOMISERS
• NEBULIZATION OF LIQUID SAMPLE
• MONOCHROMATORS
• DETECTORS
• AMPLIFIER
• READ OUT DEVICE
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 RADIATION SOURCE

• HOLLOW CATHOD LAMP

• ELECTRODELESS DISHCHARGE LAMP

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 Hallow cathode lamp
• 300 V applied between anode (+) and metal
cathode (-)

• Ar ions bombard cathode and sputter cathode

atoms

• Fraction of sputtered atoms excited, then

fluoresce

• Cathode made of metal of interest (Na, Ca, K,

Fe...)

• Different lamp for each element

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• The cathode consists of a hollow cup. In the
cup is the element which is determined.

• The anode is tungsten wire. The two

electrodes keep in a tube containing an inert
gas.

• The lamp window is constructed of quartz,

silica, or glass. 12
• When a potential is applied between the two
electrodes, the inert gas is charged at the anode,
and the charged gas is to the cathode. The impact
with the cathode vapourizes some of the sodium
atoms and give rise to the sodium emission spectrum

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 The neon or helium gas in the hollow cathode
lamp performs three functions

• It dislodges atoms from the surface of the

cathode

• responsible for excitation of the ground state

metal atoms

• It is main source of current carrying capacity

in the HCL.
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• The pressure maintained in the lamp is 1 to 5
torr.
• The spectral lines produced by the HCL are so
narrow that they are completely absorbed by the
atoms.
• Each hollow cathode lamp emits the spectrum
of the metal which is used in the cathode, for
example copper cathode emits copper spectrum
which is absorbed by copper atoms.
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 ELECTRODELESS DISHCHARGE 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.
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 CHOPPER

• A rotating wheel is interposed between the HCL

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.
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 ATOMISERS

• 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
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 FLAME ATOMISERS

• 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
vapour.

• There two types of burners

• Total consumption burner

• Premixed burner.
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Flame atomizer

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TOTAL CONSUMPTION BURNER

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• In this burner, the sample solution, the fuel, and
oxidizing gases are passed through separate
passages to meet at the opening of the base of
flame. Sample in liquid form then the flame
breaks into the droplets which are evaporated
and burns. Leaving the residue which is reduced
to atoms.
• Total consumption burners do use oxygen with
hydrogen or acetylene, gives very hot flames.
• Disadvantage is there it is noisy and hard to use.
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 PREMIXED BURNER

• IN this burner, the sample is aspirated into a

large chamber by means of fuel gas and
oxidant under pressure.

• The fine droplets get carried out along with

the fuel gas at outlet, the large drops of
sample get collected in chamber and are
drained out.
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 NEBULIZATION:

• Before the liquid sample enters the burner ,it

is converted into droplets this method a
formation of small droplets its called
nebulization

• Common method of nebulization is by use of s

gas moving at high velocity, called pneumatic
nebulization.
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 MONOCHROMATORS

• This is a very important part in an AA spectrometer. It

is used to separate out all of the thousands of lines.

• Without a good monochromator, detection limits are

severely compromised.

• A monochromator is used to select the specific

wavelength of light which is absorbed by the sample,
and to exclude other wavelengths. The selection of the
specific light allows the determination of the selected
element in the presence of others. 25
DETECTORS

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• As soon as photon strikes the photocathode an
electrons is dislodged and photon is accelerated
to dynode I., resulting in the liberation of two or
more electrons from this dynode. Similarly, the
electrons from this dynode I are accelerated to
dynode 2, resulting in the liberation of move
electrons. Thus, the current multiplied at each
dynode and the resultant electron current is
received by the anode which goes to external
amplifier and read-out system.
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AMPLIFIER

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 READ OUT DEVICE

• In the most of AAS measurement, chart recorders are

used as read out device. A chart recorder is a
potentiometer.

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 INTERFERENCE
Interference is a phenomenon in which two waves superimpose
to form a resultant wave of greater or lower amplitude.
Interference decrease the intensity of absorption of light .
Interference usually refers to the interaction of waves that are
correlated or coherent with each other, either because they come
from the same source or because they have the same or nearly
the same frequency.
Types of interferences
1) Spectral interference
2) Chemical interference
3) Physical interference
Spectral interferences
 Spectral interferences arise when the absorption or emission of
an interfering species either overlaps or lies so close to the
analyte absorption or emission that resolution by the
monochromator becomes impossible. ex:-Manganese triplet
(4031,4033,4035Å) overlapped by gallium line(4033Å).
 This interference can be corrected by amplitude modulation of
the source.
Chemical interference
 Occurs due to incomplete dissociation of compounds in the
flame when the concentration of compound is more.
 Removed by use of higher flame temperature.
 Chemically –by addition of more thermally stable compound.
ex-addition of lanthanum to the aluminium and magnesium for
detection of magnesium
Physical interference :-viscosity
-solvent
-ionization
1) Viscosity – viscosity is invertionaly proportional to the
intensity of absorption.
2) Solvent – organic solvent increases the intensity and aqueous
solvent decreases the intensity of absorption.
3) Ionization – occurs due to high flame temperature. A number
of vaporized atoms become ionized by the flame. Resulting
ions absorb at a different wavelength than the vaporized
atoms the new wavelength will not be selected by the
monochromator and low results occurs.
Na  Na+ + e-
Overcome by addition of more easily ionizable element
Ex- ionization interference of Na is corrected by the addition
of Potassium to the Sodium .
APPLICATIONS OF AAS
 Qualitative analysis of elements.
 Quantitative analysis of elements.
 Simultaneous elemental analysis.
 Clinical analysis of biological fluids such as urine and blood
 Environmental analysis – analysis of river water, industrial wastes,
seawater, drinking water, air etc….
 Pharmaceutical analysis
 Determination of metallic elements( Cu,Zn,Ni) in food industry.
 Determination of lead in petrol (diethyl lead and tetraethyl lead)
 application

• QUALITATIVE ANALYSIS : in atomic absorption

spectroscopy, a different HCL is to be used for
each element to be tested. It means that an
element which Is used in in the construction
of cathode of HCL, can be detected only. As
QUALITATIVE ANALYSIS involves the checking
of one element at a time, it means that the
process is very laborious. There for , AAS is the
seldom used in practice for the purpose.
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• QUANTITATIVE ANALYSIS: it is used
determination of the amt of radiation
absorbed by the sample if the value of
radiation absorbed is substituted in equation.

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• Simultaneous malticomponent analysis is
available, such determination using
multicomponent HCL
• Determination of metallic elements in biological
materials:
• Determination of metallic elements in food
industry: copper, zinc, and nickel are the most
common toxic elements of interests to food
analysis
• Determination of calcium, magnesium, sodium
and potassium in blood serum
• Determination of lead in petrol. 36
 CONCLUSION

• One of the most important technique in

quantitative analysis
• It is based on the absorption of radiation
• Measurements could be done at ppb levels
• It’s widely used method
• The preparation of the sample is usually
simple and rapid
 CONCLUSION

• There are many adventages

High sensitivity
[10-10 g (flame), 10-14 g (non-flame)]
 Good accuracy
(Relative error 0.1 ~ 0.5 % )
 High selectivity
 REFERENCES
• SKOOG, Instrumental analysis , Indian Edition ,
CENGAGE Learning,2007.
• B.K. SHARMA , Instrumental methods of
chemical analysis, third edition,GOEL
publishing house,2004.
• http://www.shsu.edu/~chm_tgc/sounds/soun
d.html
• www.bing.com.
• www.googleimagesearch.com
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