CONTENT

INTRODUCTION
ABSORPTION OF RADIANT ENERGY BY ATOMS
DEGREE OF RADIANT ENERGY ABSORPTION
INSTRUMENTATION
STEPS OF EXPERIMENTATION
THE ATOMIZATION PROCESS
INTERFERENCES IN AAS
ANALYTICAL APPLICATIONS OF AAS
ADVANTAGES AND DISADVANTAGES OF AAS

ATOMIC ABSORPTION SPECTOMETRY (AAS)

almost exclusively use for the quantitative

determination of metal elements in aqueous and solid
samples.
an elemental analysis technique capable of providing
quantitative information on ~70 elements, almost all
of them metal or metalloid elements.
The technique makes use of absorption spectrometry
to assess the concentration of an analyte in a sample.
The technique can measure analyte concentrations in
the range from g/L to % with good precision (i.e.
repeatability) at rates of up to 20 per minute.
As small a quantity as 5 mL is needed for analysis

AAS

The technique was introduced in 1955 by Walsh in Australia

(A.Walsh, Spectrochim. Acta, 1955, 7, 108)

Alan Walsh 1916-1998

The first commercial atomic absorption spectrometer was

introduced in 1959

AAS

AAS is based on the absorption of radiant energy by

ground state, free gas phase atoms.

atomic absorption spectra consist of a few very narrow

absorption lines, in contrast to the wide bands of energy
absorbed by molecules in solution(about 0.002 nm),

If energy DE of exactly the right magnitude is applied to a

free gas phase atom, the energy will be absorbed.

only three or four useful lines are available in the UV/VIS

spectral region for each element

AAS

The fraction of incident light absorbed by atoms at a

particular wavelength is proportional to the number of
atoms

The amount of radiation absorbed is only slightly

dependent on temperature

indirectly affects the atomic absorption signal

Low ionization energies and high temperatures result in

the formation of ions rather than atoms.

AAS

the fraction of incident light absorbed by a species can be

expressed as the absorbance, A.
The relationship between absorbance and the amount of
analyte, in this case, atoms, in the light path is given by

Beers Law:

The oscillator strength f is a dimensionless quantity whose

magnitude expresses the transition probability for a specific
transition.

A schematic block diagram of the instrumentation used for AAS

AAS

RADIATION SOURCES

Two radiation sources are commonly used in commercial

AAS instruments
Hollow cathode lamp (HCL)
Electrodeless discharge lamp (EDL)

RADIATION SOURCES

Hollow cathode lamp (HCL)

The cathode is often formed by hollowing out a cylinder of

pure metal or making an open cylinder from pure metal foil.
The metal used for the cathode is the metal whose spectrum
will be emitted by the lamp.
The cathode and an inert anode are sealed in a glass
cylinder filled with Ar or Ne at low pressure (the filler gas).
A window of quartz or glass is sealed onto the end of the
lamp; a quartz window is used if UV wavelengths must be
transmitted.

RADIATION SOURCES

The HCL emits narrow, intense lines from the element

that forms the cathode.
Each hollow cathode emits the spectrum of metal used in
the cathode
Using this light source, atomic absorption is easily
detected and measured and provide not only high
sensitivity, but also specificity.
HCLs have a limited lifetime, usually due to loss of filler
gas atoms through several processes; eventually the
number of filler gas atoms becomes so low that the lamp
will not light.

RADIATION SOURCES

Electrodeless discharge lamp (EDL)

EDLs are very intense, stable emission sources. They

provide better detection limits than HCLs for those
elements that are intensity-limited either because they
are volatile or because their primary resonance lines are
in the low-UV region.

RADIATION SOURCES

Some elements like As, Se, and Cd suffer from both

problems. For these types of elements, the use of an EDL
can result in a limit of detection that is two to three times
lower than that obtained with an HCL.
EDLs are available for many elements, including
antimony, arsenic, bismuth, cadmium, germanium, lead,
mercury, phosphorus, selenium, thallium, tin, and zinc.
Older EDLs required a separate power supply to operate
the lamp..
EDL lamps cost slightly more than the comparable HCL.

Atomizers

Atomizers

is the sample cell of the AAS system

. The atomizer must produce the
ground state free gas phase atoms
necessary for the AAS process to
occur.
The two most common atomizers
flame atomizers
electrothermal (furnace) atomizers
(ETA).

Atomizers

flame atomizers
To create a flame, we need to mix an oxidant gas and a
fuel gas, and light the mixture.
two types of flames
the airacetylene flame
where air is the oxidant and acetylene is the fuel
nitrous oxideacetylene flame
where nitrous oxide is the oxidant and acetylene is
again the fuel
The fuel and oxidant gases are mixed in a burner system,
called a premix burner

Atomizers

The sample is introduced into the burner in the form of a

solution. The solution is aspirated into the nebulizer, an
aerosol is formed, but the droplets are of different sizes.
As a droplet enters the flame, the solvent (water or
organic solvent) must be vaporized, the residue must
vaporize, and the sample molecules must dissociate into
atoms.
The larger the droplet, the more inefficient this
process is.

Atomizers

ELECTROTHERMAL (FURNACE) ATOMIZERS

(ETA).

In order to measure ppb concentrations of metals, a

different type of atomizer is needed.
A furnace or electrothermal atomizer (ETA) was
developed less than 10 years after the technique of AAS
was developed.
In 1961 B.V. Lvov built a heated carbon tube atomizer
The most common atomizer of this type uses a tube of
graphite coated with pyrolytic graphite and heated by
electrical resistance; therefore, this commercial ETA is
called a graphite furnace atomizer.
The acronym GFAAS tells the reader that the atomizer
used is a graphite furnace, as opposed to a flame.

Spectrometer Optics

SPECTROMETER OPTICS

Monochromator
A monochromator is required to separate the
absorption line of interest from other spectral
lines emitted from the HCL and from other
elements in the atomizer that are also emitting
their spectra

Spectrometer Optics

1.

2.

designed for the measurement of one wavelength at a

time; they are single-element instruments.
The monochromator in the aas spectrometer is placed
between the flame/graphite furnace and the detector in
order:
To allow monitoring one line in the spectrum of the
analyte ( remember that atomic spectra consist of many
lines)
To minimize the emission from the flame itself
( remember that the detector (photomultiplier) detects
photons over a wide wavelength range)

Spectrometer Optics

The most common dispersion

element used in AAS is a diffraction
grating
The grating can be rotated to
select the wavelength that will
pass through the exit slit to the
detector. All other wavelengths
are blocked from reaching the
detector.
The more lines/mm on the grating, the higher is the dispersion.
Higher dispersion means greater separation between adjacent
lines.
Large high-quality gratings with high dispersion are expensive,
but they offer better energy throughput than cheaper lowdispersion gratings.

Detectors
The detector takes the light signal after
modification by the sample and converts it
into a useable electrical signal which will
subsequently be shown as an absorbance
reading.

The common detector for AAS is the PMT

(Photomultiplier Tube)-the principle of operation
is the emission of electrons upon exposure to
radiation.

The analyte is prepared in aqueous solution

The solution is aspirated into flame, using the
nebulizer
The solvent evaporates
The gaseous analyte decomposes, and some of it
is converted to gaseous atoms
The gaseous atoms absorb radiation from HCL
The absorbance of the sample is determined by
comparing Io (when no analyte is present in the
flame) and Itrans.

AAS

Most samples we want to examine by AAS are solid or

liquid materials.
For flame AAS (FAAS) and most GFAAS determinations, the
sample must be in the form of a solution.
There are many differences in the atomization process in a
flame and in a graphite furnace.
One very important difference to keep in mind is that in
FAAS, the sample solution is aspirated into the flame
continuously for as long as it takes to make the
absorbance measurement.This is usually not longabout
30 s once the flame has stabilized after introducingthe
sample solution, but it is a continuous process.
GFAAS is not a continuous process, aswill be seen; the
atomization step produces a transient signal that must be
measured in less than 1 s.

AAS

Interferences are physical or chemical processes that cause

the signal from the analyte in the sample to be higher or
lower than the signal from an equivalent standard.
Interferences can therefore cause positive or negative errors
in quantitative analysis.
There are two major classes of interferences in AAS:
1. spectral interferences
Spectral interferences cause the amount of light absorbed
to be erroneously high due to absorption by a species
other than the analyte atom.
2. Nonspectral interferences
Nonspectral interferences are those that affect the
formation of analyte free atoms

AAS

AAS is used for the determination of all metal and metalloid elements
Nonmetals cannot be determined directly because their most sensitive
resonance lines are located in the vacuum UV region of the spectrum.

QUALITATIVE ANALYSIS
The radiation source used in AAS is an HCL or an EDL, and a different
lamp is needed for each element to be determined. Because it is
essentially a single-element technique, AAS is not well suited for
qualitative analysis of unknowns.
To look for more than one element requires a significant amount of sample and
is a time-consuming PROCESS.

QUANTITATIVE ANALYSIS
Quantitative measurement is one of the ultimate objectives of
analytical chemistry. AAS is an excellent quantitative method. It is
deceptively easy to use, particularly when flame atomizers are
utilized.

AAS

a given element can be determined in

the presence of other elements, which
do not interfere by absorption of the
analyte wavelength.
Easy to use
High precision

AAS

no information is obtained on the chemical

form of the analyte ( there is no
speciation)
often only one element can be determined
at a time
Useful for metallic elements, not for non
metals

THANK YOU...
END.