Lecture 4 - Atomic Absorption and Emission Spectros
Lecture 4 - Atomic Absorption and Emission Spectros
Lecture 4 - Atomic Absorption and Emission Spectros
and emission
spectroscopy
Belay Haile, MSc (Analytical Chemistry),
PhD Scholar (Postharvest Technology),
Arba Minch University, CNS, Chemistry
Department, Arba Minch Ethiopia
February 2021
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Optical
Spectrometry
Absorption
Emission
Fluorescence
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Cont. …
AAS
Higher number of neutral
atom (ground state)
AES
Higher number of neutral
atom (Excited state)
AFS
Higher number of neutral
atom (Excited state).
Emission measured at 90°
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Principle of AAS
The element being determined must be reduced to the
elemental state, vaporized, and imposed in the beam of the
radiation in the source.
Absorption of EMR (UV-Vis) by neutral atoms in gaseous
state
Same principle as molecular Electronic spectroscopy but
sample holding, equipment and spectra are different
There are two basic types of atomic absorption instruments:
single-beam and double-beam.
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Single-Beam AAS
Single-Beam AAS
The light source must be electronically modulated or mechanically
chopped to differentiate between the light from the source and the emission
from the sample cell.
The monochromator disperses the light, and the specific wavelength of
light isolated passes to the detector, which is usually a photomultiplier tube.
Double-Beam AAS
Double-Beam AAS
The light from the source lamp is divided into a sample beam, which is
focused through the sample cell, and a reference beam, which is directed
around the sample cell.
In a double-beam system, the readout represents the ratio of the sample and
reference beams.
AAS Instrumentation
EDL
The benefits:
Analysing volatile elements
like As, Sb, Bi, Cd, Hg, Rb,
Sn, Te, etc.
Chopper:
It is a rotating wheel interposed between the hollow cathode
lamp and flame.
Gives pulsating current in the photocell
Nebulization
A method of forming small droplets from the liquid sample is called Nebulization
Nebulizer:
formation of suck up liquid samples at controlled rate
create a fine aerosol spray for introduction into flame.
Mix the aerosol and fuel and oxidant thoroughly for introduction into flame.
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Atomizer:
Elements to be analyzed
needs to be in atomic sate.
Atomization is separation
of particles into individual
molecules and breaking
molecules into atoms.
This is done by exposing the
analyte to high temperatures
in a flame or graphite
furnace
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Atomizers
Cont. …
Inthis technique, formerly called flame photometry, the source of excitation energy is a
flame.
The sample is introduced into the flame in the form of a solution, and so the technique is
very easy to quantify.
The mist, oxidant, and fuel flow past baffles that promote further mixing and
block large droplets of liquid.
Excess liquid collects at the bottom of the spray chamber and flows out
to a drain.
Aerosol reaching the flame contains only about 5% of the initial sample.
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Cont. …
The most common fuel-oxidizer combination is acetylene and air, which produces
a flame temperature of 2400–2 700 K
Interferences in AAS:
Spectral Interferences: include
Absorption from other closely absorbing atomic species, usually not
a problem because of the extremely narrow band-width used
Non-spectral Interferences:
Could be specific or non-specific
A) Non-specific interferences:
affect the nebulization by altering the viscosity, surface tension, or
density of the analyte solution and consequently the sample flow
rate
Some contaminants also decrease the desolvation and atomization
efficiency by lowering the atomizer temperature
B) Specific interferences:
are also called chemical interferences because they are more
analyte dependent
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Chemical interferences
Solute volatilization interference: refers to the situation when the contaminant forms
non-volatile species with the analyte.
Ionization interferences: occurs when the presence of an easily ionized element, such
as K, affects the degree of ionization of the analyte which leads to changes in the
analyte signal.
Excitation interferences: occur when the analyte atoms are excited in the atomizer
with a subsequent emission at the absorption wavelength . This is more pronounced at
higher temperatures.
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Calibration Curve
o A calibration curve is used to determine the unknown concentration of an element in a
solution.
o The absorbance of each known solution is measured and then a calibration curve of
concentration vs absorbance is plotted.
o The sample solution is fed into the instrument, and the absorbance of the
element in this solution is measured.
o The unknown concentration of the element is then calculated from the calibration curve.
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Application of AAS
Qualitative and quantitative analysis