Chapter 9

Atomic Absorption and Atomic

Fluorescence Spectrometry

Atomic Spectroscopy
Atomization is by
far the most
critical step in
atomic
spectroscopy.
In AAS and AFS
there are two
factors
involved.
The intensity of
light source.
The probability
of transition.

Flame Atomization

Flame Structure

Flame Atomizer

Flame Atomizer

Electrothermal Atomizers
Graphite furnace atomic absorption spectrometry (GFAAS) is also
known by various other acronyms, including electrothermal
atomic absorption spectrometry (ETAAS).
An ideal graphite furnace should fulfill the following requirements:
A constant temperature in time and space during the interval in
which free atoms are produced
Quantitative atom formation regardless of the sample
composition
Separate control of the volatilization and atomization processes
High sensitivity and good detection limits
A minimum of spectral interferences

Specialized Atomization
Techniques
Glow

Discharge Atomization
Hydride Atomization
Cold-Vapor Atomization

Flame Atomic Absorption

Spectroscopy

Radiation Sources
Doppler

Broadening
Pressure Broadening
Electrodeless Discharge Lamps
Source Modulation
Hollow Cathode Lamps:

Spectrophotometers
In general, the instrument must contain:
Narrow bandwidth to isolate the line chosen for measurement
Sufficient glass filter
Interchangeable interference filters
Good-quality ultraviolet/visible monochromators
Photomultiplier tubes

Spectrophotometers
Single-Beam
Double-Beam

Spectral Interferences
The

Two-Line Correction Method

The Continuum-Source Correction
Method
Background Correction Based on the
Zeeman Effect
Background Correction Based on the
Source Self-Reversal

Chemical Interference
The equilibria of principle interest include:
Formation of Compounds of Low
Volatility
Dissociation Reactions
Ionization

Calibration Curves
Should

follow Beers Law

Standard Addition Method

Instrumentation
Sources:
Hollow Cathode Lamp- only
observed the fluorescent signal
during pulses
Electrodeless Discharge Lampproduced intensities that
exceed those of hollow cathode
lamps
Lasers- ideal source with high
intensities and narrow
bandwidths

Instrumentation
Dispersive Instruments- They are made up of a modulated
source, an atomizer, a monochromator or an interference
filter system, a detector, and a signal processor and
readout.
Nondispersive Instruments- They ideally are made up of a
source, an atomizer, and a detector.
Advantages:
Simplicity and low-cost instrumentation
Ready adaptability to multi-element analysis
High-energy throughput and thus high sensitivity
Simultaneous collection of energy from multiple lines,
enhancing sensitivity

References

www.anachemumu.se.htm
www.aurora-instr.com/right.htm
www.anachem.umu.se/jumpstation.htm
www.anachem.umu.se/cgi/jumpstation.exe?AtomicSpectroscopy
www.anachem.umu.se/cgi/jumpstation.exe?OpticalMolecularSpectroscopy
www.minyos.its.rmit.edu.au/~rcmfa/mstheory.html
http://science.widener.edu/sub/ftir/intro_it.html
http://www.s-a-s.org/
http://www.chemsw.com
http://www.scimedia.com/chem-ed/spec/atomic/aa.htm
http://nercdg.org
http://www.analyticon.com
www.lcgmag.com/
www.lcms.com/

References

www.dq.fct.unl.pt/QOF/Chroma.html
www-ssg.chem.utas.edu.au/
www.yahoo.com/science/chemistry/chromatography/
www.onlinegc.com
http://www.scimedia.com/chem-ed/analytic/ac-meth.htm
http://www.scimedia.com/chem-ed/spec/atomic/aa.htm
http://www.scimedia.com/chem-ed/spec/atomic/afs.htm
http://www.cee.vt.edu/program_areas/environmental/teach/smprimer/aa/aa.
html#Features
http://www.anachem.umu.se/aas/gfaas.htm
http://www.agsci.ubc.ca/fnh/courses/food302/atomic/aatomic03.htm#electro
http://www.scpscience.com/products/AA/hollowlamps.asp
http://las.perkinelmer.com/catalog/Product.aspx?ProductId=N3050691
http://elchem.kaist.ac.kr/vt/chem-ed/spec/atomic/aa.htm