Atomic Emission Spectroscopy Identification and Analysis

ATOMIC EMISSION SPECTROSCOPY
ATOMIC EMISSION
- Technique is also known as
OPTICAL EMISSION SPECTROSCOPY (OES)
- The study of radiation emitted by excited atoms and

monatomic ions
- Relaxation of atoms in the excited state results in

emission of light
- Produces line spectra in the UV-VIS and the

vacuum UV regions
ATOMIC EMISSION
- Used for qualitative identification of elements present

in the sample
- Also for quantitative analysis from ppm levels to percent
- Multielement technique
- Can be used to determine metals, metalloids, and some

nonmetals simultaneously
Emission wavelength and energy are related by

ΔE = hc/λ
ATOMIC EMISSION
- Does not require light source
- Excited atoms in the flame emit light that reaches the

detector
(luminescence)
Techniques Based on Excitation Source

- Flame Photometry (flame OES)
- Furnace (Electrical Excitation)
- Inductively Coupled Plasma (ICP)
 Arc  Flame
 Higher Temperature
 Simpler, less expensive
 Lower interelement
interference instrumentation
 Single set of excitation  Lower operating costs
conditions can excite
multiple elements
 Greater reproducibility
 Permit low detection limits
for refractory complexes
 Larger linear range
 Can directly measure hard to
measure samples
FLAME ATOMIC EMISSION SPECTROSCOPY
- Known as Flame OES
- Also called flame photometry
- Solutions containing metals (or some nonmetals) are

introduced into a flame
- Very useful for elements in groups 1A and 2A

INSTRUMENTATION OF FLAME OES
- No external lamp is needed
- Flame serves as both the atomization source and the

excitation source
Main Components
- Burner assembly
- Flame
- Wavelength selection device
- Detector
Burner Assembly
- The most commonly used is the Lundegarth or the premix burner
- Is the heart of the emission spectrometer
- Nebulizer introduces sample aerosol into the base of the flame
- Free atoms are formed and excited in flame
- Excited free atoms emit radiant energy
- Only about 5% of the aspirated sample reach the flame

General Process in Flame
- Liquid samples enter nebulizer

- Sample droplets of liquid enter flame
- Fine solid particles form
- Particles decompose to free atoms
- Excited atoms form
- Excited atoms relax and emit radiation
- Oxidation of atoms occur
Wavelength Selection Device
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)
Wavelength Selection Device
Multichannel Flame Photometers

- Two or more filters are used simultaneously
- Each filter transmits its designated radiation
- Detector is PMT
- Permits the use of internal standard calibration

Flame Excitation Source
- Two gases (fuel and oxidant) are used
- Oxidant: air or nitrous oxide
- Fuel: acetylene (commonly used), propane, butane, natural gas
- Increase in flame temperature increases emission intensity

of most elements (exception: Na, K, Li)
- Maxwell-Boltzmann equation applies (see chapter 6)

- Each element emits different characteristic wavelength of light
- Emission lines are characterized by wavelength and intensity
Emission intensity depends on

- Analyte element concentration in sample
- Rate of formation of excited atoms in flame
- Rate of introduction of sample into flame
- Flame composition
- Flame temperature
S = kN
S = intensity
k = proportionality constant
N = number of atoms in the excited state
- Increasing temperature increases N
- Atomic emission spectrometry is very sensitive to temperature
- Temperature must be carefully controlled for quantitative analysis

- Elements with emission lines at shorter wavelengths give weak
emission intensity at low temperature
- High-temperature nitrous oxide-acetylene flame is used for

such elements
- High-energy electrical or plasma excitation sources may

also be used
- Ratio of fuel to oxidant also affects emission intensity
- The highest temperature is achieved when stoichiometric

mixture is used
INTERFERENCE
Two Classes
- Spectral interference
and
- Nonspectral interference
INTERFERENCE
Spectral Interference
Two types
Background Radiation
- Broad band emission by excited molecules and radicals in flame
Overlapping emission lines

- Emission by different elements of the same wavelength as
the analyte element
INTERFERENCE
Nonspectral Interference
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
- Excellent method for qualitative determination of multiple

elements in sample
- Characteristic emission lines of analyte are compared

with literature (appendix 7.1)
- Also used for quantitative analysis (application of Beer’s Law)
- Deviation from linearity is generally observed at

high concentrations
APPLICATIONS OF FLAME OES
- More free atoms are liberated in organic solvents than
in aqueous solutions
- Implies emission intensity is relatively higher in

nonaqueous solutions
- Atomization is exothermic and rapid in organic solvents
- Atomization is endothermic and relatively slow in aqueous

solutions
- External calibrations and standard addition methods are used

ATOMIC OPTICAL EMISSION SPECTROSCOPY
- Excitation and emission with the aid of electrical discharge,
glow discharge, or plasma excitation source
- Higher energy excitation sources than the flame source
- All metals, metalloids, and some nonmetals can be detected

at low concentrations
- Electrical and glow discharge sources are used for solids only
- Plasma source is used for liquids and solids
- Electrical source can be used for gases in a sealed quartz tube

ATOMIC OPTICAL EMISSION SPECTROSCOPY
Two Types of Line Spectra
- Atomic emission spectra from neutral atoms

(designated with I in tables of emission lines)
- Emission lines from ions (ion lines)

(lines from singly charged ions are designated II)
(lines from doubly charged ions are designated III)
FURNACE (ELECTRICAL) EXCITATION
- Produces electrical discharge between two electrodes

(the sample electrode and the counter electrode)
- A piece of metal analyte is the sample electrode
- Counter electrode is an inert electrode (tungsten or graphite)
Examples of Sources
- DC arc
- AC arc
- AC spark
- DC is primarily used for qualitative analysis of solids
- Spark source makes use of a switch, a capacitor, an inductor,

and a resistor
- Temperature is higher in spark than in DC arc
- More complex spectra in spark than in DC but more reproducible
- Spark is better for quantitative analysis
- Spark is used for precision and arc is used for sensitivity

Solid Sample Holders
- High purity carbon electrodes
- Well drilled in one end to hold powdered solid samples
- Powdered sample may be mixed with alumina or silica

(improves precision)
- Metallic samples in the form of rod or wire may be used

directly as one of the electrodes
Liquid Sample Holders
- Liquid samples are analyzed directly using rotating

disk electrodes
- This method is used for the determination of metals in

lubricating and fuel oils
- Spectrometers are multichannel
Three Types
Spectrographs
- Uses photographic film or plate to detect and record
emitted radiation
Polychromators
- Multichannel with PMTs as detectors
Array-Based Systems (Electronic Spectrographs)

- Radiation intensity is measured by PMT or array detectors
INTERFERENCE IN ARC & SPARK
- Limited to analysis of solids of trace elements
Matrix Effect
- Emission intensity of trace elements is greatly affected
by the matrix
- Two types
- Background interference and line overlap
- Background is due to thermal radiation, molecular emission,

and polyatomic species
APPLICATIONS OF ARC & SPARK
- Qualitative identification of elements
- Also used for quantitative analysis

PLASMA EMISSION SPECTROSCOPY
Plasma
- State of matter that contains electrons, ions, neutral species,

and radicals
- Highly energetic ionized gas
- Electrically conductive
- Affected by a magnetic field

Excitation Sources
- Inductively Coupled Plasma (ICP) – operates at radiofrequency
- Direct Current Plasma (DCP)
- Helium Microwave Induced Plasma (MIP)
- Temperature in plasma excitation source is between

6500 K and 10000 K
Dispersion Devices
Sequential spectrometer systems

- One wavelength is measured at a time
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
- 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
- For analysis of environmental samples, geological samples,

clinical samples
- For characterization of metal alloys, glasses, ceramics,

polymers, oils
- For food and nutrition
- Forensics
HYPHENATED METHODS
ICP-MS
HPLC-ICP
GC-MIP
GLOW DISCHRGE EMISSION SPECTROSCOPY
Glow Discharge (GD)

- Reduced-pressure gas discharge generated between
two electrodes
- Tube is filled with inert gas (Ar)
Excitation Source
- DC GD
- RF GD
ATOMIC FLUORESCENCE SPECTROMETRY (AFS)
- Involves emission of a photon from a gas phase atom that has

been excited by the absorption of a photon
- Different from the excitation by thermal or electrical means
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
AAS AES
Operator Skill Lower skill Higher skill
Bkgd.Correction
Prec. &
Accuracy
Interferences
Detection limit
AAS AES
Bkgd.Correction Harder to do Easier to do
Prec. &
Accuracy
Interferences
Detection limit
AAS AES
Prec. & Unskilled better Unskilled worse
Accuracy Same for skilled 
Interferences
Detection limit
AAS AES
Interferences Spectral interferences corrected Chemical interferences
in AES on AE (flame) bad,
plasma eliminated
Detection limit
AAS AES
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
Techniques

range
Qualitative poor poor excellent excellent excellent

analysis
Elemental
range
Trace
analysis
Techniques

range

analysis
Elemental excellent excellent excellent excellent excellent

range
Trace
analysis
Techniques

range

analysis

range
Trace excellent excellent excellent excellent excellent

analysis
Techniques

range

analysis

range
Trace excellent excellent excellent excellent excellent

analysis
Techniques continued
Matrix high high high low low
interfernces
Spectral
Interferences
Precision &
Accuracy
Costs
interfernces
Spectral low low low moderate high
Interferences
Precision &
Accuracy
Costs
interfernces
Interferences
Precision & Better Worse
Accuracy for for
unskilled unskilled
Same same
skilled skilled
Costs
interfernces
Interferences
Precision & Better Worse
Accuracy for for
unskilled unskilled
Same same
skilled skilled
Costs $$ $$$ $ $$$ $$$$
Costs
Instrumentat low low low moderate high
ion
Maintenance
Sample
Preparation
Operator
skill
Costs
ion
Maintenance low low low moderate high
Sample
Preparation
Operator
skill
Costs
ion
Sample moderate moderate low moderate moderate

Preparation
Operator
skill
Costs
ion
Sample moderate moderate low moderate moderate

Preparation
Operator lower higher higher higher higher
skill

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ATOMIC EMISSION SPECTROSCOPY

- The study of radiation emitted by excited atoms and

- Relaxation of atoms in the excited state results in

- Produces line spectra in the UV-VIS and the

- Used for qualitative identification of elements present

- Also for quantitative analysis from ppm levels to percent

- Can be used to determine metals, metalloids, and some

Emission wavelength and energy are related by

- Excited atoms in the flame emit light that reaches the

Techniques Based on Excitation Source

- Known as Flame OES

- Also called flame photometry

- Solutions containing metals (or some nonmetals) are

- Very useful for elements in groups 1A and 2A

- Flame serves as both the atomization source and the

- The most commonly used is the Lundegarth or the premix burner

- Is the heart of the emission spectrometer

- Nebulizer introduces sample aerosol into the base of the flame

- Free atoms are formed and excited in flame

- Excited free atoms emit radiant energy

- Only about 5% of the aspirated sample reach the flame

- Liquid samples enter nebulizer

Multichannel Flame Photometers

- Each filter transmits its designated radiation

- Permits the use of internal standard calibration

- Two gases (fuel and oxidant) are used

- Oxidant: air or nitrous oxide

- Fuel: acetylene (commonly used), propane, butane, natural gas

- Increase in flame temperature increases emission intensity

- Maxwell-Boltzmann equation applies (see chapter 6)

- Emission lines are characterized by wavelength and intensity

Emission intensity depends on

- Increasing temperature increases N

- Atomic emission spectrometry is very sensitive to temperature

- Temperature must be carefully controlled for quantitative analysis

- High-temperature nitrous oxide-acetylene flame is used for

- High-energy electrical or plasma excitation sources may

- Ratio of fuel to oxidant also affects emission intensity

- The highest temperature is achieved when stoichiometric

Overlapping emission lines

- Excellent method for qualitative determination of multiple

- Characteristic emission lines of analyte are compared

- Also used for quantitative analysis (application of Beer’s Law)

- Deviation from linearity is generally observed at

- Implies emission intensity is relatively higher in

- Atomization is exothermic and rapid in organic solvents

- Atomization is endothermic and relatively slow in aqueous

- External calibrations and standard addition methods are used

- Higher energy excitation sources than the flame source

- All metals, metalloids, and some nonmetals can be detected

- Plasma source is used for liquids and solids

- Electrical source can be used for gases in a sealed quartz tube

Two Types of Line Spectra

- Atomic emission spectra from neutral atoms

- Emission lines from ions (ion lines)

- Produces electrical discharge between two electrodes

- A piece of metal analyte is the sample electrode

- Counter electrode is an inert electrode (tungsten or graphite)

- Spark source makes use of a switch, a capacitor, an inductor,

- Temperature is higher in spark than in DC arc

- More complex spectra in spark than in DC but more reproducible

- Spark is better for quantitative analysis

- Spark is used for precision and arc is used for sensitivity