Atomic Absorption Spectroscopy

Atoms have a number of excited energy levels

accessible by visible-UV optical methods

Must have atoms (break up molecules)

Optically transparent sample of neutral atoms
(flames, electrical discharges, plasmas)
Metals accessible by UV-Vis, non-metals
generally less than 200nm where vacuum UV
needed)
Atomic spectra

Outer shell electrons excited to higher energy

levels
Many lines per atom (50 for small metals over
5000 for larger metals)
Lines very sharp (inherent line width of 0.00001
nm)
Collisional and Doppler broadening (0.003 nm)
Strong characteristic transitions
 Atomic spectroscopy for analysis
Flame emission - heated atoms emit
characteristic light
Electrical or discharge emission -
higher energy sources with more lines
Atomic absorption - light absorbed by
neutral atoms
Atomic fluorescence - light used to
excite atom then similar to FES
 INSTRUMENT FOR FLAME EMISSION

1-Flame atomizer.
2- Monochromator
3- Detector.
4- Readout meter
 In the burner

The combustion of fuel occurs producing the necessary heat for atomization
and excitation but not ionization .

The temperature of the flame produced depends on fuel-oxidant ratio and kind.
1-Flame Atomizer

a-Atomization of the sample.

b- Source of thermal energy to excite the atoms.

The atomizer is composed of : Nebulizer, and burner

Nebulizer:
is a device by which sample solution is divided into very fine
droplets which are aspirated into fine spray or aerosol.
As the oxidant flows it withdraws the sample from the capillary in
very fine droplets
Then mixed in the premixing chamber with the fuel gas .

The fuel-oxidant-sample aerosol mixture passes to the burner producing

the necessary heat for atomization and excitation r
Limitation of Flame Emission
Photometry

1-The number of excited atoms in flame is very small. It is the alkaline

and alkaline earth metals that can be practically determined.

2-It needs perfect control of flame temperature.

3- Interference by other elements is not easy to be eliminated.

4-Heavy and transition metals , the number of absorption

and emission lines is enormous and the spectra are complex.
Atomic Absorption spectrophotometer
AA Instrument Schematic
Double Beam AAS Instruments account for instability in the
source. Other techniques are added to account for
scattering if light in the sample and the absorption of light by
non-atomic species in the sample. In the example shown
here, P/Po is alternatively recorded by the instrument to
cancel out short-term lamp fluctuations.
Deuterium Background Correction: A D2 lamp (continuum lamp) alternately
passes light through the sample with the HCL. Analytes don’t absorb much
D2 radiation since it is a continuum source. The light absorbed with the
HCL light passes through the sample minus the light absorbed when the D2
radiation passes through is the signal that is measured
AA instrumentation
Radiation source (hollow cathode lamps)
Optics (get light through ground state atoms
and into monochromator)
Ground state reservoir (flame or
electrothermal)
Monochromator
Detector , signal manipulation and readout
device
Hollow Cathode Lamp

Emission is from elements in cathode that

have been sputtered off into gas phase
 Light Source
Hollow Cathode Lamp - seldom used,
expensive, low intensity
Electrodeless Discharge Lamp - most used
source, but hard to produce, so its use has declined
Xenon Arc Lamp - used in multielement analysis
Lasers - high intensity, narrow spectral bandwidth,
less scatter, can excite down to 220 nm wavelengths,
but expensive
Atomizers

Flame Atomizers - rate at which sample

is introduced into flame and where the
sample is introduced are important
 3- Atomizer:
a- Flame atomizer

b- Flameless or non flame atomizer

It is a graphite furnace heated electrically up to 6000oC and

contains a ribbon or boat in which one can inject the sample.

Upon heating the furnace

the sample is ashen, then atomized by action of heat.

Advantages of non flame atomizer

-The sample volume is small . - No need for fuel -oxidant mixture.

- Unusual high sensitivity - No flame noise.
-Solid sample can be used directly.

- Heat distribution is uniform and temperature is steady.

AA - Flame atomization

Use liquids and nebulizer

Slot burners to get large optical path
Flame temperatures varied by gas
composition
Molecular emission background
(correction devices )
Sources of error
solvent viscosity
temperature and solvent evaporation
formation of refractory compounds
chemical (ionization, vaporization)
salts scatter light
molecular absorption
spectral lines overlap
background emission
Atomizers
Flame Atomizers - rate at which sample is introduced
into flame and where the sample is introduced is
important
Graphite Furnace Atomizers - used if sample is too
small for atomization, provides reducing environment
for oxidizing agents - small volume of sample is
evaporated at low temperature and then ashed at
higher temperature in an electrically heated graphite
cup. After ashing, the current is increased and the
sample is atomized
Electrothermal atomization
Graphite furnace (rod or tube)
Small volumes measured, solvent evaporated, ash,
sample flash volatilized into flowing gas
Pyrolitic graphite to reduce memory effect
Hydride generator
Graphite Furnace AA
Closeup of graphite furnace
Controls for graphite furnace
Detector

Photomultiplier Tube
has an active surface which is capable of
absorbing radiation
absorbed energy causes emission of
electrons and development of a
photocurrent
encased in glass which absorbs light
Charge Coupled Device
made up of semiconductor capacitors on a
silicon chip, expensive
Background corrections

Two lines (for flame)

Deuterium lamp
Smith-Hieftje (increase current to
broaden line)
Zeeman effect (splitting of lines in
a strong magnetic field)
Problems with Technique

Precision and accuracy are highly

dependent on the atomization step
Light source
molecules, atoms, and ions are all in
heated medium thus producing three
different atomic emission spectra
 Problems continued
Line broadening occurs due to the uncertainty
principle
limit to measurement of exact lifetime and
frequency, or exact position and momentum
Temperature
increases the efficiency and the total number of
atoms in the vapor
but also increases line broadening since the
atomic particles move faster.
increases the total amount of ions in the gas and
thus changes the concentration of the unionized
atom
 Interferences
If the matrix emission overlaps or lies too close
to the emission of the sample, problems occur
(decrease in resolution)
This type of matrix effect is rare in hollow
cathode sources since the intensity is so low
Oxides exhibit broad band absorptions and can
scatter radiation thus interfering with signal
detection
If the sample contains organic solvents,
scattering occurs due to the carbonaceous
particles left from the organic matrix
 Interferences in Atomic
Absorption Spectroscopy
Spectral interferences
Chemical interferences
1 Spectral Interferences

Spectral interferences arise when the

absorption or emission of an
interfering species either overlaps or
lies so close to the analyte absorption
or emission that resolution by the
monochromater becomes impossible.
2 Chemical Interferences

Chemical interferences are more

common than spectral ones. Their
effects can frequently be minimized
by a suitable choice of operating
conditions.
Interferences continued
 Sample Preparation

Many materials of interest, such as

soils, animal tissues, plants,
petroleum products, and minerals are
not directly soluble in common
solvents, and extensive preliminary
treatment is often required to obtain a
solution of the analyte in a form ready
for atomization.
Organic Solvents

Leaner fuel/oxidant ratios must be

employed with organic solvents in
order to offset the presence of the
added organic material.
Calibration Curves

In theory, atomic absorption should

follow beer’s law with absorbance
being directly proportional to
concentration.
Standard Addition Method

The standard addition method is

widely used in atomic absorption
spectroscopy in order to partially or
wholly counteract the chemical and
spectral interferences introduced by
the sample matrix.
 Applications of Atomic
Absorption Spectrometry
Atomic absorption spectrometry is a
sensitive means for the quantitative
determination of more than 60 metals or
metalloid elements. The resonance lines
for the nonmetallic elements are
generally located below 200 nm, thus
preventing their determination by
convenient,nonvacuum
spectrophotometers.