ATOMIC ABSORPTION

SPECTROSCOPY
Atomic Absorption Spectroscopy (AAS)
 most widely used of all atomic methods
because of its simplicity, effectiveness, and
low cost
 Atomic absorption methods were not used
before this because of problems due to very
narrow widths of atomic absorption lines
Line Width Effects in Atomic Absorption

 The width of atomic absorption lines are very

narrow (0.002 – 0.005 nm)
 Even good – quality monochromators have
effective bandwidths greater than the width of
atomic absorption lines
 This results to instrumental departures from
Beer’s law

non linear calibration curves are produced

 Only a small fraction of the radiation from the
monochromator slit is absorbed by the
sample

- obtain small slopes of calibration curves

- poor sensitivity
 Solution :
Use of line sources with bandwidths narrower
than the absorption band widths
Example: use sodium vapor lamp
Sodium atoms are excited by an electrical
discharge to produce a line
Other sodium lines produced are filtered
by a monochromator
Source temperature and pressure are
kept below that of the atomizer so that the
Doppler broadening of the emitted lines is
less than the broadening which occurs in
the flame/atomizer
Hollow Cathode lamp
 Application of about 300 V across the
electrodes causes ionization of inert gas and
generation of a current of 5 – 10 mA
 Sputtering – gaseous cations acquire enough
kinetic energy to dislodge some of the metal
atoms from the cathode surface and produce an
atomic cloud
 Some of the sputtered metal atoms are in
excited states and thus emit radiation as they
return to their ground states
 Metal atoms diffuse back to the cathode suface
or glass walls of tube and are redeposited
 Cylindrical configuration
concentrates the radiation in a limited region of
the metal tube
Enhances the probability that redeposition will
occur at the cathode rather than glass walls
 Efficiency depends on operating voltage
 high voltages and thus high currents lead to
greater intensities
BUT: greater currents produce an increased
number of unexcited atoms in the cloud which are
capable of self absorption and leads to lowered
intensities
Electrodeless Discharge Lamp
 The inert gas ionizes in this field
 The ions are accelerated by the high –
frequency component of the field until they
gain sufficient energy to excite atoms of
the metal whose spectrum is sought
 Performance is not as reliable as hollow
cathode lamps
 Has better detection limits for Se, As, Cd,
and Sb
Source Modulation
 In atomic absorption measurement, it is
necessary to eliminate interferences
caused by emission of radiation by the
flame
 Much of this emitted radiation is removed
by the monochromator
 However, emitted radiation corresponding
in wavelength to the monochromator
setting is present in the flame because of
excitation and emission of analyte atoms
 The source is then modulated so that its
intensity fluctuates at a constant frequency
 The detector receives two types of signals:
Source: alternating
Flame: continuous
 These signals are converted into the
corresponding types of current and an
electronic system eliminates the unmodulated
dc signal produced by the flame
 The ac signal is passed from the source to
the amplifier and to the readout device
 Modulation can be accomplished by
interposing a motor – driven circular chopper
between the source and the flame
 Rotation of the disk at a constant speed
provides a beam that is chopped to the
desired frequency
 As an alternative, the power supply for the
source can be designed to pulse the hollow –
cathode lamps in an alternating manner
Spectrophotometers
 Most AAS instruments are equipped with
ultraviolet – visible monochromators,
which are capable of achieving a very
narrow bandwidth
 Atomic absorption instruments use
photomultiplier tubes as transducers
Single - Beam
Double - Beam
Atomic Absorption Analytical Techniques
nebulizers
Nebulization – to convert a liquid into a fine
spray or mist

Aerosol – suspension of finely divided liquid or

solid particles in a gas

Nebulizer functions because the high

velocity of the combustion gases of the
fuel and oxidant rushing past a small
orifice draws the liquid into the flow as
small droplets.
Types of nebulizers
Pneumatic Nebulizer

- liquid sample is introduced to a high velocity

jet of the oxidant gas, and the mist produced is
mixed with the fuel gas and passed via a mixing /
expansion chamber to the burner

- fabricated from inert material, usually

platinum-iridium alloy for capillary and tantalum or
titanium or platinum for the nosepiece and
annulus.
Ultrasonic Nebulizer
Babington and V-groove
Sample Preparation
 Flame Spectroscopic methods
Disadvantages
○ The sample must be introduced in the form of
a solution .
○ Decomposition of materials may lead to loss
of analyte.
○ The reagents used can also introduce
chemical and spectral interferences.
○ Moreover, the decomposition and solution
steps are time-consuming and error-prone.
Sample Preparation
 Treatment with hot mineral acids
 Oxidation with liquid reagents
 Combustion in an oxygen bomb
 Ashing at a high temperature
 High-temperature fusion
Sample Introduction by Flow Injection
 Flow injection analysis (FIA)
An excellent method of sample introduction
especially when sample conservation is
important
The carrier system of the FIA system
(deionized water or dilute electrolyte)
provides continuous flushing of the flame
atomizer.
advantageous for samples with high level
of salts or suspended solids.
Organic Solvents
 Enhanced absorbances due to
increased nebulizer efficiency .
Lower surface tension results in smaller drop
sizes which eventually leads to an increase in
the amount that reaches the flame.
 Rapid solvent evaporation contributes to
the enhanced absorbance.
 The added organic material may be
offset by leaner fuel-oxidant ratios.
Organic Solvents
 Methyl butyl ketone
To extract chelates of metallic ions
The sensitivity of the method is enhanced
and interferences are reduced.
Calibration Curve
 A calibration curve that covers the range of
concentrations found in the sample should be
prepared periodically.
 In addition, the number of uncontrolled variables in
atomization and absorbance measurements is
large to allow measurement of one standard
solution each time an analysis is performed.
Standard Addition Method
 Applied only when calib. Curve is linear
over region of interest and background
correction is made
 Advantage: Matrix matching is achieved
automatically
Accuracy

the relative error is of the order of I% to 2%. With

special precautions, this can be lowered to a few
tenths of a percent.
Errors encountered with electrothermal
atomization usuallv exceed those for flame
atomization by a factor of 5 to 10
Detection Limits
Sample Atomization Techniques
 Atomization – process in which a
sample is converted into gas – phase
atoms or elementary ions

Flame Atomization

Electrothermal Atomization

Special Atomization Techniques

Flame Atomization
 Analyte  Dissociation

 Nebulization  Ionization

 Desolvation  Excitation

 Volatilization
Types of Flames

 Temperature of 1700 °C to 2400 °C when air

is the oxidant.

 Temperature of 2500 °C to 3100 °C when

oxygen or nitrous oxide is used as oxidant.
Flame Atomizers
Flame Atomizers
 Aerosol  Most of the sample
solution
 Mixes with fuel
 Mixing chamber
 Runs through a
series of baffles  Waste container

 Collects the finest

solution droplets
Performance Characteristics of Flame
Atomizers
 Flame atomization – most reproducible
 Low sampling efficiency
A large portion of the sample flows down the
drain.
Residence time of individual atoms in the
optical path of the flame is brief.
Electrothermal Atomization
 Enhanced sensitivity because the entire
sample is atomized in a short period of
time.
 Long residence of atoms in the optical
path
 Used in atomic absorption or atomic
fluorescence but not for atomic
emission.
Electrothermal Atomization
 A small volume of  Current is rapidly
sample (in μL) increased.

 Evaporation  Temperature is
consequently
 Ashing in an increased.
electrically heated
graphite tube
Electrothermal Atomizers
Electrothermal Atomizers
 Graphite Tube
Where atomization occurs
Open at both ends and has a central hole
for sample introduction
Fits into a pair of cylindrical graphite
contacts which are held in a water-cooled
metal housing
Electrothermal Atomizers
 Two inert gas streams
External stream prevents outside air from
entering and incinerating the tube.
Internal stream excludes air and carries
away the vapors generated from the sample
matrix during the initial heating stages.
Electrothermal Atomizers
 L’vov Platform
Made of graphite and located below the
sample entrance.
Where the sample is evaporated and ashed
Improves reproducibility of analytical signals
○ The sample is not in contact with the furnace
wall so atomization occurs in an environment
where the temperature is not rapidly changing.
Electrothermal Atomizers
 Two ways of heating
Longitudinal mode continuously
varying temperature profile
Transverse mode uniform temperature
profile
optimum condition for the formation
of free atoms
Performance Characteristics of
Electrothermal Atomizers
 Advantages  Disadvatages

 High sensitivity for  The method is slow.

small volumes of
sample.
 Detection limits lie in
the range of 10-10 to
10-13 g of the analyte.
 The analytical range
is narrow, less than
two orders of
magnitude.
Specialized Atomization Techniques
 Glow-Discharge Atomization

 Hydride Atomization

 Cold Vapor Atomization

Interferences
 Chemical Interferences
 from chemical processses during atomization,
altering absorption characteristics of analyte
 Physical Interferences
Any influence of present materials in the
sample
 Spectral Interferences
 occur when absorption/emission of interfering
species overlaps or lies close to analyte
absorption
Dissociation Equilibria
 Dissociation and association reactions lead
to conversion of metallic constituents to the
elemental state.

 Dissociation reactions play an important part

in determining the nature of the emission or
absorption spectra for an element
Dissociation Equilibria
 Dissociation equilibria that involve
anions other than oxygen may also
influence flame emission and
absorption.
 For example, the line intensity for
sodium is markedly decreased by the
presence of HCl.
Ionization Equilibria
 Ionization is important in higher
temperature flames where oxygen or
nitrous oxide serves as the oxidant.
 There is a significant concentration of
free electrons produced by the
equilibrium
Ionization Equilibria
 Increased temperatures cause an increase
in the population of excited atoms,
according to the Boltzmann relationship .
 Counteracting this effect, is a decrease in
concentration of atoms
 A decrease in emission or absorption may
be observed in hotter flames. Thus lower
excitation temperatures are usually
specified for the determination of alkali
metals.
Ionization Equilibria
 The effects of shifts in ionization
equilibria can be eliminated by addition
of an ionization suppressor
 Higher temperature with nitrous oxide
enhances the degree of decomposition
and volatilization of the compounds
Spectral Interferences
 From combustion products which exhibit
broadband absorption of particulate
products that scatter radiation
 Often occur with aspirated concentrated
solutions with : Ti, Zr and W
 Caused by scattering – due to
carbonaceous particles from incomplete
combustion of organic matrix.
 Interferences due to overlapping lines are rare
Spectral Interferences
 Avoided by varying analytical variables
such as flame temp. And fuel-to-oxidant
ratio
 If source of interference is known, an
excess of the interfering substance can
be added to both sample and standards.
The added substance is sometimes called a
radiation buffer.
Methods of Correction
 Two-line Correction Method
 Continuum-Source Correction Method
 Background Correction Based on the
Zeeman Effect
Two-Line Correction Method
 Uses a line from the source as a
reference,
This line should lie as close as possible to the
analyte line but must not be absorbed
 Any decrease in power of the reference
line observed during calibration arises
from absorption or scattering by the matrix
products of the sample
 This decrease in power is then used to
correct the absorbance of the analyte line
Continuum-Source Correction Method

A background corrector compensates for the background

absorption
Background Correction Based on the
Zeeman Effect
 Zeeman Background correction
An applied magnetic field to the source or
atomizer is used to split the resonance line
into its Zeeman components (π and ±σ).
The background is monitored by the
polarizers
The analyte and signal background are
monitored with the central component
Background Correction Based on the
Zeeman Effect
 Application
based on the differing response of the two
types of absorption lines to polarized
radiation.
The π line absorbs only that radiation that is
plane polarized in a direction parallel to the
external magnetic field
the σ lines, absorb only radiation polarized
at 90° to the field
Background Correction Based on the
Zeeman Effect
Background Correction Based on the
Zeeman Effect
 A more accurate correction for
background
 Particularly useful for electrothermal
atomizers and permit the direct
determination of elements in samples
such as urine and blood
 The decomposition of organic material in
these samples leads to large background
corrections (background A > I)
Sources
[1] Skoog, et al. Principles of Instrumental
Analysis 6th edition. Thomson Brooks/Cole.
USA. 2007.
[2] Verma, A. CRC Handbook of Atomic Absorption
Analysis Vol. 1. CRC Press Inc. USA.1987.
[3] Skoog, et al. Fundamentals of Analytical
Chemistry 8th edition. Thomson Brooks/Cole. USA.
2004.
[4]http://weather.nmsu.edu/Teaching_Material/soil
698/Student_Reports/Spectroscopy/report.htm