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ATOMIC EMISSION
- Technique is also known as
OPTICAL EMISSION SPECTROSCOPY (OES)
- Multielement technique
Main Components
- Burner assembly
- Flame
- Wavelength selection device
- Detector
INSTRUMENTATION OF FLAME OES
Burner Assembly
Monochromators
- Diffraction grating is used as the dispersion element
Filters
- Good for detection of alkali metals due to simple spectrum
- Material is transparent over a narrow spectral range
- Desired radiation passes through filter and others are absorbed
- One element is determined at a time (single channel)
INSTRUMENTATION OF FLAME OES
Wavelength Selection Device
- Detector is PMT
S = intensity
k = proportionality constant
N = number of atoms in the excited state
Two Classes
- Spectral interference
and
- Nonspectral interference
INTERFERENCE
Spectral Interference
Two types
Background Radiation
- Broad band emission by excited molecules and radicals in flame
Chemical Interference
- Occurs if anions that combine strongly with analyte element
are present in sample
Excitation Interference
- Result of collisions between unexcited atoms of an element with
excited atoms of a different element in sample
Ionization Interference
- Occurs when atoms ionize in flame and cannot emit atomic λs
APPLICATIONS OF FLAME OES
- For measurement of alkali metals in clinical samples such as
serum and urine
- Electrical and glow discharge sources are used for solids only
Examples of Sources
- DC arc
- AC arc
- AC spark
FURNACE (ELECTRICAL) EXCITATION
- DC is primarily used for qualitative analysis of solids
Three Types
Spectrographs
- Uses photographic film or plate to detect and record
emitted radiation
Polychromators
- Multichannel with PMTs as detectors
Matrix Effect
- Emission intensity of trace elements is greatly affected
by the matrix
Spectral Interference
- Two types
- Background interference and line overlap
Plasma
- Electrically conductive
Excitation Sources
Dispersion Devices
Simultaneous systems
- Contains either a polychromator or an Echelle spectrometer
- Measures multiple wavelengths at the same time
Combination systems
- Consists of both polychromators and monochromators
INTERFERENCE IN PLASMA EMISSION
Spectral Interference
- Much more common in plasma than in flame
Nonspectral Interference
Chemical Interference
- Rare in plasma emission due to efficiency of atomization
Ionization Interference
- Results in suppression and enhancement of signals from
easily ionized elements (EIE: alkali metals)
APPLICATIONS OF PLASMA EMISSION
- Forensics
HYPHENATED METHODS
ICP-MS
HPLC-ICP
GC-MIP
GLOW DISCHRGE EMISSION SPECTROSCOPY
Excitation Source
- DC GD
- RF GD
ATOMIC FLUORESCENCE SPECTROMETRY (AFS)
Interferences
- Chemical interference
- Spectral interference
Comparison of Plasma to Flame
Emission Sources
Plasma sources offer significantly better quantitative
data than do other flame emission sources
- High stability
- Low noise
- Low background
- Freedom from interferences
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill
Bkgd.Correction
Prec. &
Accuracy
Interferences
Detection limit
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill Lower skill Higher skill
Bkgd.Correction
Prec. &
Accuracy
Interferences
Detection limit
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill Lower skill Higher skill
Bkgd.Correction Harder to do Easier to do
Prec. &
Accuracy
Interferences
Detection limit
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill Lower skill Higher skill
Bkgd.Correction Harder to do Easier to do
Prec. & Unskilled better Unskilled worse
Accuracy Same for skilled
Interferences
Detection limit
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill Lower skill Higher skill
Bkgd.Correction Harder to do Easier to do
Prec. & Unskilled better Unskilled worse
Accuracy Same for skilled
Interferences Spectral interferences corrected Chemical interferences
in AES on AE (flame) bad,
plasma eliminated
Detection limit
Comparison between Atomic Absorption
& Emission Techniques
AAS AES
Instruments Requires HC lamp for each Flame/ sample is source
element Requires high quality MC
No high quality MC required
Operator Skill Lower skill Higher skill
Bkgd.Correction Harder to do Easier to do
Prec. & Unskilled better Unskilled worse
Accuracy Same for skilled
Interferences Spectral interferences corrected Chemical interferences
in AES on AE (flame) bad,
plasma eliminated
Detection limit Flame some metals better on Plasma comparable to
AA than AES flame for some metals,
other metals plasma
better
Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Qualitative
analysis
Elemental
range
Trace
analysis
Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Elemental
range
Trace
analysis
Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Trace
analysis
Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Costs
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Matrix high high high low low
interfernces
Spectral low low low moderate high
Interferences
Precision &
Accuracy
Costs
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Matrix high high high low low
interfernces
Spectral low low low moderate high
Interferences
Precision & Better Worse
Accuracy for for
unskilled unskilled
Same same
skilled skilled
Costs
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Matrix high high high low low
interfernces
Spectral low low low moderate high
Interferences
Precision & Better Worse
Accuracy for for
unskilled unskilled
Same same
skilled skilled
Costs $$ $$$ $ $$$ $$$$
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Costs
Instrumentat low low low moderate high
ion
Maintenance
Sample
Preparation
Operator
skill
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Costs
Instrumentat low low low moderate high
ion
Maintenance low low low moderate high
Sample
Preparation
Operator
skill
Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Costs
Instrumentat low low low moderate high
ion
Maintenance low low low moderate high