Atomic Spectroscopy

Variations of
Atomic
Spectroscopy
 Flame emission
spectroscopy (FES)
 Atomic absorption
spectroscopy (AAS)
 Atomic fluorescence
spectroscopy (AFS)
Advantages of Atomic
Spectroscopy
 High selectivity
 Wide application (scores of
elements)
 High sensitivity (ppm  ppb)
 Typically rapid (a few min per
analysis)
Dispersal of Sample
Flame Atomization
 B—heating by
conduction,
radiation from C
 C—non-equlibrium
zone; many radicals
present
 D—Combustion
products CO, CO2,
H2O, N2, H, O, OH,
etc. present;
thermal equilibrium
established
Satisfactory Flame
 Proper temperature for complete
atomization
 Proper fuel/oxidant ratio
 Optically transparent combustion
products, esp. >210 nm
In the Flame
Flame Types
Choice of Flame type
 Hotter flames required to prevent oxide
formation, esp. for oxophilic elements
 acetylene/air OK for alkali metals
 acetylene/N2O required for alkaline earths
 Reducing flames required for refractory
oxides
 acetylene-rich flame mixture required for Al, Cr
etc.
 High propagation rate flames difficult to
ignite and extinguish
Laminar Flow Burner

 Wasteful (10% of
sample  flame)
 Atomic residence
time and
concentration is
small in flame
 Flicker and
instability  noise;
limits detectability
Atomic Distribution in Flame
 Atomization increases with height
 Oxide formation increases with height
Concentration-Height Profiles
 Ag shows increasing
atomization with
flame height
 Cr shows increasing
oxide formation
with flame height
 Mg shows
intermediate
behavior
Atomic Absorption
 Extremely narrow intrinsic spectral
lines (0.002-0.005 nm)
 Experimentally observed linewidths
0.02-0.05 nm due to
 Doppler broadening
 Collision broadening
Non-linear calibration curves are
common...
…unless narrow
bandwidth
source is used.
Hollow Cathode Lamp

 Typically operated at
300 V, 5-10 mA
 Emitted
wavelength(s)
characteristic of
element(s) composing
cathode
 Single or
multielement
AAS Designs
Spectral Interferences
 Overlapping lines (rare)
 Broad-band absorption and
scattering by combustion products
or matrix
Combating Spectral Interference
 Two-line correction
 use reference beam from lamp near line of
interest to correct for background (neon,
impurity lines)
 Continuous source correction
 use D2 continuous lamp to correct for
background; not useful above 350 nm
 Self-reversal of hollow cathode lamp
 periodic “shutdown” of lamp by operating at
high current  self-absorption
Chemical Interferences
 Low volatility
 Oxide formation
 Excessive ionization
Volatility
 Many oxides, sulfates and phosphates have low
volatility
 e.g., Al forms nonvolatile mixed oxides with some metals
 Releasing agents combine with interferents
 e.g., La, Sr salts combine with phosphates
 Protective Agents combine with analyte to form
volatile species, prevent combination with
interferents
 e.g., EDTA combines with many transition metals
 Hotter flames promote greater dissociation
Oxide Formation

 Oxides can have low volatility (e.g.,

CaO) or be refractory (e.g., TiO)
 Hotter flames encourage dissociation
of oxides
 Richer flames reduce available
oxygen in flame, discourage oxide
formation
Note: Hotter flames are usually oxygen-rich, and
richer flames are usually cooler
Ionization

 M ¾ M+ + e–
 Lowers population of absorbing free
atoms
 Exacerbated by hotter flames
 Ionization suppressors are easily
ionized, supply excess of electrons in
flame to reduce ionization of analyte
 e.g. La, Sr, Cs, K added to analyte at
concentrations > 100 ppm
Ionization of Selected Elements
AAS Techniques
 Sample must be in solution
 wet ashing
 combustion with oxygen
 dry ashing
 fusion with B2O3, Na2CO3, etc.
 Standards
 try to approximate matrix
Choice of Method
 AAS—intrinsically most sensitive
 FES—superior at long wavelength,
esp. for alkali metals and alkaline
earths
 AFS—Trace analysis

But…even though AAS, FES, and AFS are

extensively used...ICP methods are
superior
Plasma Emission Spectroscopy
 A type of atomic emission
spectroscopy
 The source is an Inductively
Coupled Plasma torch
Argon Plasma Torch
 Microwave coil
operates at 30
MHz and 2000 W
 Ar  Ar+ + e–
 Temperatures in
excess of 10,000 K
are achievable
 Advantages of Plasma Source
 More complete atomization of sample
 Ion emission lines are significant and usable (e.g., Ca+,
Ca2+)
 Background emission is low in observation region (Ar,
OH, NO, NH, CN lines)
 Surprisingly, excessive ionization is low, due to excess
e– in plasma
 Oxide formation is nil
 Low level of self-absorption due to high proportion of
excited atomsresponse is linear over many orders of
magnitude
2-D Dispersion in ICP-AES
 Grating disperses wavelengths in X-direction
 Prism disperses grating orders in Y-direction
2-D Dispersion Pattern
 Makes possible rapid,
simultaneous
multielement analysis
 Typically only the
higher orders of the
grating dispersion (n
= 50 - 200) are used
 Photodiode array
detector allows signal
integration
Perkin Elmer Optima 3000