Emission Spectroscopy Based upon

Plasma, Arc, and Spark Atomization

 Arc  Flame
 Higher Temperature
 Simpler, less
 Lower interelement
interference expensive
 Single set of excitation instrumentation
conditions can excite
multiple elements  Lower operating costs
 Permit low detection limits  Greater reproducibility
for refractory complexes
 Larger linear range
 Can directly measure hard to
measure samples
Emission Spectroscopies Cont.
 Plasma (def.) Electrically conducting
gaseous mixture containing significant
concentrations of cations and electrons

 ICP and DCP

Inductively Coupled Plasma
 Inductively coupled
means that the plasma
is generated due to
differences in the
magnetic field and
currents
 Temp. very hot (4000-
8000K)
 Good & bad
Direct Current Plasma (DCP)
 Plasma forms by
bringing graphite and
W electrodes in
contact with one
another
 Temp @ core 10,000K
in viewing region
5000K
ICP DCP Comparison
 DCP is an order of  Auxillary power less
magnitude less expensive in DCP
sensitive than ICP  Graphite electrode
 Similar must be replaced every
reproducibilities couple of hours
 DCP requires less Ar
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

Dynamic limited limited wide wide Wide

range

Qualitative
analysis

Elemental
range

Trace
analysis
 Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES

Dynamic limited limited wide wide Wide

range

Qualitative poor poor excellent excellent excellent

analysis

Elemental
range

Trace
analysis
 Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES

Dynamic limited limited wide wide Wide

range

Qualitative poor poor excellent excellent excellent

analysis

Elemental excellent excellent excellent excellent excellent

range

Trace
analysis
 Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES

Dynamic limited limited wide wide Wide

range

Qualitative poor poor excellent excellent excellent

analysis

Elemental excellent excellent excellent excellent excellent

range

Trace excellent excellent excellent excellent excellent

analysis
 Comparison of Metal Spectroscopic
Techniques
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES

Dynamic limited limited wide wide Wide

range

Qualitative poor poor excellent excellent excellent

analysis

Elemental excellent excellent excellent excellent excellent

range

Trace excellent excellent excellent excellent excellent

analysis
 Comparison of Metal Spectroscopic
Techniques continued
Performance Flame Electrothermal Flame DCP ICP
Criteria AA Sampling AES
Matrix high high high low low
interfernces
Spectral
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 &
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

Sample moderate moderate low moderate moderate

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 moderate moderate low moderate moderate

Preparation
Operator lower higher higher higher higher
skill