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Chapter 5 - AAS - 2019
Chapter 5 - AAS - 2019
Line source
Monochromator
:
Nebulizer
Sample
Compartment
Atomic spectrum
Mg is more
complicated
N∗ g∗
= ( ) × e −(E/kT)
𝐍𝐨 𝐠𝐨
N0 P0 equation
between no of
-23 -1
excited and 1.38 X 10 JK
Flame profile:
• Is a contour plot that reveals region of the flame that has similar values for variables
of interest (temperature, chemical composition, absorbance etc). This provides useful
information that goes into the flame.
• According to temperature profile maximum temperature (for natural gas air) lies
about 1cm above the primary combustion zone.
• According to absorbance profile,
Species forming oxides only at high
temperature, (like Mg): exhibits maximum
absorbance at about middle of the flame.
Species which donot get oxidized readily (Ag):
shows continuous increase in absorbance, due
to increase in number of atoms from base to
the periphery.
Species forming stable oxides (Cr): shows
continuous decrease in absorbance as the
distance from base is increased.
Thus depending on type of analyte different part of the flame should be used to have
maximum sensitivity, i.e. flame must be moved up and down until maximum
absorbance get observed.
Mr. Prakash Lamichhane/ Apr 2019 16
Instrumental analysis for Undergraduate level
Kathmandu University 8/23/2019
(A) Flame atomizer
i. Laminar flow burner (premixed burner):
Laminar flow burner provides quiet
flame and long path length usually 5-
10 cm which enhances sensitivity and
reproducibility.
Has concentric tube nebulizer /control sample uptake 1-5 cm2/min/produces aerosols/
It is premixed burner: sample is mixed with oxidant and fuel and passes a series of
baffles that permits only finest droplets. Big drop sample is collected at the bottom of
mixing chamber, where it drains to the waste container.
i. Electro
thermal
atomization:
(HCL) (ETAAS
or
GFAAS)
GF Design
Graphite cap Graphite holder
Sample
Cooling block inlet
Aperture
plate socket Seal
シール Graphite tube
Absorption
Cell
Burner Head
Peristal of AAS
tic Manifold
Pump Gas
Reactio Liquid
n Coil Separat
Draior
n
HClNaBH
SamplCarrier
4 Gas
e Ar Structural Diagram of Hydride
Vapor Generator
Mr. Prakash Lamichhane/ Apr 2019 23
Instrumental analysis for Undergraduate level
Kathmandu University 8/23/2019
SnCl2
5%KMnO4
5%H2SO4
Radiation source:
Atomic absorbance lines are remarkably
narrow 0.002-0.005nm and unique for each
element.
Thus the bandwidth of the source must be
narrow relative to the absorption peak, to
minimize the interferences by impurity.
Monochromators (give effective bandwidth >
Absorbance-band)
•Non linear calibration curves
•Slope of calibration curve will be less
The peak may be broadened up to 0.02-0.05 Ao
by different phenomenon:
Uncertainty effect, Doppler Effect, Pressure
effect, Electric and magnetic field effect.
with a metal
Ionization of inert gas occurs at anode, which are accelerated to cathode. This
generates current of (5-15mA).
The highly energetic ions strike the surface of cathode and dislodge some M-atoms
from the surface, producing metallic cloud in the atmosphere (sputtering).
A portion of sputtered atom in excited state emits radiation with a very narrow
wavelength, which is a characteristic of the M-element. Finally metal diffuse back
to metal or glass, are then re-deposited).
The cylindrical configuration of the cathode concentrates the radiation
source and also enhances the probability of re deposition on the M-surface.
Multi-element lamps are available in which cathode is made from such element.
synchronized
• Chemical Interferences
Analyte species will be atomized in the mantle of the flame. The
atomized analyte species may undergo different extent of combination or
ionization reaction so the measured concentration may be varied at
different condition which is termed as the chemical interference.
(a) Formation of compounds of low volatility
– The most common type of interference is by anions that form compounds
of low volatility with the analyte and thus reduce the rate at which the
analyte is atomized. Interference by cations is also feasible.
The linear decrease in calcium absorbance that is observed with
increasing concentrations of sulfate or phosphate, until anion-cation ratio
is 0.5. Here abs will droped by 30-50% of initial value and then become
independent of anion concentration.
Aluminum is found to cause low results in the determination of
magnesium, apparently as a result of the formation of a heat-stable
aluminum/magnesium compound.
Experimental procedures
ATOMIC ABSORPTION ANALYTICAL TECHNIQUES
Sample Preparation:
• A disadvantage of flame spectroscopic methods is the requirement that the
sample be introduced into the excitation source in the form of a solution, most
commonly an aqueous one.
• Unfortunately, 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.
• Indeed, the decomposition and solution steps are often more time consuming
and introduce more error than the spectroscopic measurement itself.
• Some of the common methods used for decomposing and dissolving samples for
atomic absorption methods include
• treatment with hot mineral acids;
• oxidation with liquid reagents, such as sulfuric, nitric, or perchloric acids;
• combustion in an oxygen bomb or other closed container to avoid loss of analyte.
Calibration Curves:
• Atomic absorption should follow Beer’s law with absorbance being
directly proportional to concentration.
• In fact, however, departures from linearity are often encountered, and it
is foolhardy to perform an atomic absorption analysis without
experimentally determining whether or not a linear relationship does
exist.
• A calibration curve that covers the range of concentrations found in the
sample should be prepared.
• Standard Addition Method: It is widely used in atomic absorption
spectroscopy in order to partially or wholly counteract the chemical and
spectral interferences introduced by the sample matrix.
• The resonance lines for the nonmetallic elements are generally located
below 200 nm, thus preventing their determination by convenient,
nonvacuum spectrophotometers.
Common application of AAS
• Mostly used in: mines, food industries, environmental control, petroleum
products as they: detect deficiencies / excessive amounts of certain
metals in our body fluids such as: our blood and urine
• Tracks harmful metals in our food/drinks;
• analyze metal ions that are polluting the soil, air and water.
• Investigating different locations to test for different elements present and
how much of these elements are present.
• Analyze metals present in engine oils.
Mr. Prakash Lamichhane/ Apr 2019 45
Instrumental analysis for Undergraduate level
Kathmandu University 8/23/2019
• Moderately expensive
• Can only process one element
at a time.
• Slower than ICP-AES
• Can only identify limited types
of elements
Amplifier
Filter
Gas
inlet
Nebulizer
Drain -
U tube
Air
Theory (FES):
• Flame photometry is based on the fact that compounds of alkali and alkaline
earth metals can be thermally excited in a low temperature flame.
• When the atoms return to the ground state they emit radiation which lies
mainly in the visible region of the spectrum.
• Each element emits radiation at a wavelength specific to that element. e. g.
Na 589nm, K 766nm, Ca 622nm, Li 670.8nm, etc.
• Over a certain range of concentration the intensity of the emitted radiation is
directly proportional to the number of atoms returning to the ground state.
This in turn is proportional to the absolute quantity of the species volatized in
the flame i.e. light emitted is proportional to the sample concentration.
• The light emitted by the element at its characteristics wavelength is isolated
by an optical filter and the intensity of that light is measured by photo
detector which provides a signal proportional to the sample concentration.
Such an electrical signal is processed with the help of analog to digital
converter and the microprocessor.
Procedure:
• Prepare standard solutions of sodium chloride/ potassium
chloride (1 and 100 ppm respectively)
• Turn on the instrument and compressor. Adjust the
pressure of the compressor.
• Check the gas circuit, ignite and adjust the flame.
• From menu and option calibrate the instrument with
standard solutions.
• Determine the concentration of sodium from the
instrument.
• Atoms in gaseous state in the flame absorb thermal
energy from the flame itself ,some of the atoms get
excited & as they return back to the ground state they
emit radiation having energy
• equal to that absorbed. The emission is proportional to
the number of excited atoms, which is proportional to
- total number of atoms in the flame i.e. the sample
the
concentration
References
• www.anachem.umu.se/cgi/jumpstation.exe?AtomicSpectroscopy
• http://www.agsci.ubc.ca/fnh/courses/food302/atomic/aatomic03.htm#electr
o
• http://www.scpscience.com/products/AA/hollowlamps.asp