Atomic Spectroscopy
• Atomic spectroscopy refers to the absorption and emission of ultraviolet–visible (UV-
Vis) light by atoms and monoatomic ions.
• Three forms of atomic spectroscopy are based on absorption, emission, and fluorescence
• Atomic absorption - atoms in gas phase absorb part of the light from the source and the
remainder of the light reaches the detector.
• Atomic emission - gas phase atoms or monoatomic ions in excited states because of the
high thermal energy of the flame emit light as they return to the ground state.
• Atomic fluorescence - atoms are excited by an external lamp or laser. An excited atom
can fall to a lower state and emit radiation.
ATOMIZATION PROCESS
The first step in all atomic spectroscopic procedures is atomization, a process in which a sample
is volatilized and decomposed in such a way as to produce gas-phase atoms and ions.
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Basic steps:
a) nebulization – solution sample, get into fine droplets by spraying thru thin nozzle or
passing over vibrating crystal.
b) desolvation - heat droplets to evaporate off solvent just leaving analyte and other matrix
compounds
c) volatilization – convert solid analyte/matrix particles into gas phase
d) dissociation – break-up molecules in gas phase into atoms.
e) ionization – cause the atoms to become charged
f) excitation – with light, heat, etc. for spectra measurement.
Flame Atomizers - In flame atomization the sample is first converted into a fine mist consisting
of small droplets of solution. This is accomplished using a nebulizer assembly.
• The sample is aspirated into a spray chamber by passing a high-pressure stream
consisting of one or more combustion gases, past the end of a capillary tube immersed in
the sample.
• The impact of the sample with the glass impact bead produces an aerosol mist. The
aerosol mist mixes with the combustion gases in the spray chamber before passing to the
burner where the flame’s thermal energy desolvates the aerosol mist to a dry aerosol of
small, solid particles.
• Thermal energy volatilizes the particles, producing a vapor consisting of molecular
species, ionic species, and free atoms.
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• The most common means for introducing
samples into a flame atomizer is continuous
aspiration, in which the sample is
continuously passed through the burner while
monitoring the absorbance.
• A significant disadvantage to flame atomizers
is that the efficiency of atomization may be
quite poor. As much as 95% of the sample
never reaches the flame.
• A second reason for poor atomization
efficiency is that the large volume of
combustion gases significantly dilutes the
sample. This reduces sensitivity.
Electrothermal Atomizers: A significant improvement in sensitivity is achieved by using
resistive heating in place of a flame. A typical electrothermal atomizer, also known as a graphite
furnace, consists of a cylindrical graphite tube. The assembly also allows for the passage of a
continuous stream of inert gas, protecting the graphite tube from oxidation, and removing the
gaseous products produced during atomization. A power supply is used to pass a current through
the graphite tube, resulting in resistive heating.
Miscellaneous Atomization Methods: A few elements may be atomized by a chemical reaction
that produces a volatile product. Elements such as As, Se, Sb, Bi, Ge, Sn, Te,
Sequence
of events in
FES, AAS,
AFS
