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Department of Chemical and

Environmental Engineering
J12ANM Analytical Measurement
Lecture 1: Part II
Atomic Absorption
Spectroscopy
How are atoms are ions produced?
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Keywords:
Atomisation
Nebulisation
Aerosol
Light Source: Hollow Cathode Lamp
The hollow cathode lamp is an excellent, bright-line source which is available for
most of the elements determinable by atomic absorption.
The cathode of the lamp is a hollowed-out cylinder of the metal whose
spectrum is to be produced.
The anode and cathode are sealed in a glass cylinder normally filled with either
argon or neon at low pressure.
A window transparent to the emitted radiation is fused to the end of the
cylinder.
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The emission process
When an electrical potential is applied between anode and cathode, some of
the fill gas atoms are ionised.
The positively charged fill gas ions accelerate through the electrical field to
collide with the negatively charged cathode and dislodge individual metal atoms
in a process called 'sputtering'.
Sputtered metal atoms are then excited to an emission state through the kinetic
energy transfer by impact with fill gas ions.
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Nebuliser and Spray Chamber
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Nebulisers and Burner Heads
Nebulisers are constructed from a corrosion resistant material,
such as:
Plastic, or,
platinum-Iridium.
Burner heads are constructed of titanium to provide extreme
resistance to heat and corrosion.
An alternative way to increase the linear working range is to rotate
the burner through a fixed amount.
This, in effect, decreases the path length that the analytical beam interacts with the
atom cloud and thus desensitises the analysis.
This approach to extending the linear working range will almost always have a
detrimental affect on the detection limit.
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Nebuliser Detail
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The flame process
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M
+
+ A
-
(Solution)
1) Nebulisation
M
+
+ A
-
(Aerosol)
2) Desolvation
MA (Solid)
3) Liquefaction
MA (Liquid)
4) Vaporisation
MA (Gas)
5) Atomisation
M
o
+ A
o
(Gas)
6) Excitation
M* (Gas)
7) Ionisation
M
+
+ e
-
(Gas)
Atomic absorption process
In order to get the atomic absorption process to occur, we must produce
individual atoms from our sample which starts out as a solution of ions.
1. First, by the process of nebulisation, we aspirate the sample into the burner
chamber, where it mixes as a fine aerosol with the fuel and oxidant gases.
At this point, the metals are still in solution in the fine aerosol droplets.
2. As these minute droplets pass into the flame, the process of evaporation or
desolvation removes the solvent and leaves tiny solid particles of sample
material.
3. As more heat is applied, liquefaction takes place, and additional heat will
vaporise the sample.
4. At this point the metal of interest (analyte), is still bound up with some anion to
form a molecule which does not exhibit the atomic absorption phenomenon we
wish to measure.
5. By applying still more heat energy, this molecule is dissociated into individual
atoms which make it up.
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Since the thermal energy from the flame is responsible for producing the
absorbing species, flame temperature is an important parameter governing the
flame process.
Two premixed flames are now used almost exclusively for atomic absorption:
air-acetylene (2125-2400
o
C), and
nitrous oxide-acetylene (2600-2800
o
C).
The number of ground state metal atoms formed in step 5 of the flame process
will determine the amount of light absorbed.
Concentration is determined by comparing the absorbance of the sample to
that of known standard concentrations.
The relationship between the number of atoms in the flame and the
concentration of analyte in solution is governed by the flame process.
If any constituent of the sample alters one or more steps of this process from
the performance observed for the standard, an interference will exist, and an
erroneous concentration measurement will result if the interference is not
recognised and corrected or compensated for.
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Flame: Burner
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Wavelength Selectors
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Prism
Incident
radiation
Monochromatic
radiation
Monochromators
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Light from the source must be
focused on the sample cell and
directly to the monochromator:
wavelengths of light are dispersed,
and the analytical line of interest is
focused onto the detector.
Wavelength dispersion is
accomplished with a grating:
i.e. a reflective surface ruled with
many fine parallel lines very close
together.
Reflection from this ruled surface
generates an interference
phenomenon known as
diffraction, in which wavelengths
of light diverge from the grating
at different angles.
Light from the source enters the
monochromator at the entrance
slit and is directed to the grating
where diffraction takes place.
The diverging wavelengths of
light are directed toward the exit
slit.
By adjusting the angle of the
grating, a selected emission line
from the source can be allowed
to pass through the exit slit and
fall onto the detector.
All other lines are blocked from
exiting.
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Detector: Photomultiplier Tube
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Mad as a Hatter!!
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