FLAME SPECTROSCOPY
The concentration of an element in a
solution is determined by measuring
the absorption, emission or
fluorescence of electromagnetic by
its monatomic particles in gaseous
state in the flame.
Atomization
- It is the conversion of molecules to their component atoms
in gaseous state ; and it is carried out by introduction
of the molecules solution in the flame in very fine droplet
In Flame Emission
-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 the total number of atoms in the flame
i.e. the sample concentration
Flame Spectra
The spectra of gaseous, atomic particles consist of well defined narrow
discrete lines arising from electronic transition of outermost electrons.
Since there is no bonds, atoms undergo electronic transition only,
no vibrational or rotational transitions.
The energy to which the atoms are subjected must be
less than the ionization potential.
The number of atoms of an element excited by the flame depends on :
1- Flame temperature
2- The energy difference between the excited and ground states.
Accordingly
-The number of excited atoms in the flame is considerably small,
even in the case of alkaline metals which are easily excited.
-Any increase of the flame temperature is accompanied by great
increase in the number of excited atoms
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.
INSTRUMENT FOR FLAME EMISSION
1-Flame atomizer.
2- Monochromator
3- Detector.
4- Readout meter.
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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
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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.
In case of potassium, sodium, lithium and calcium, they are atomized and
excited below 20000 k above 25000 k ionization occurs.
The flame temperature must be :
Regular : an increase by 100 c is accompanied by increase of 4% in the excited atoms.
It must be sufficient to cause atomization only and not ionization.
2- Monochromator
Either grating or interference filters which allow the resonance wavelength
to pass to the detector
.
Working:
Fuel gas is fed to burner at steady rate of flow and air/oxygen is supplied
via air compressor
Sample dissolved in solvent is placed in cup of automiser –burner and it is
allowed to sprayed in the flame
The radiation emitted in flame is collected via lens, slit and appropriate filter
which then focused on phtodetector
First adjust the galvanometer reading to zero and then keep highest
concentration of sample and make reading to 100 and then keep
intermediate concentrations and from calibration curve the unknown
concentration of sample is determined
.
Applications:
Widely used in various industries like chemical, pharmaceutical, soil, cement
agriculture, glass and ceramic
1. Determination of Na, K, Ca, Mg in bilogical fluids like serum, plasma, urine
2. Analysis of industrial water for determination of elements responsible for hard
water
3. Analysis of soil samples for Na, K, Ca and Mg.
4. In glass industry, for determination of Li and B
5. In cement industry, for estimation of Na2O, K2O, MgO, MnO2, Li2O
6. Estimation of alkali alkaline earth metals
7. Determination of some other imp metals like Al, Ba, Cr, Fe, Pb, Zn
8. Determination of lead mangnese in petroleum products like gasoline and
lubricating oils
ATOMIC ABSORPTION SPECTROSCOPY
atoms in the vapor state are subjected to external source of
radiation which produces one line or beam of
monochromatic light with single wavelength.
This wavelength is a resonance one for the atoms and that
will be absorbed by them.
All elements can be determined by this technique.
INSTRUMENT FOR ATOMIC ABSORPTION
3- Atomizer
1- Source of radiation 2- Chopper
6- Read out meter
4-Monochromator 5- Detector
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1- Source of radiation ; Hollow cathode lamp:
is a tube with a front quartz window contains an anode of tungsten
and a cylindrical cathode , the material of which is the same
element of the sample to be determined.
The glass tube is filled with neon or argon at a pressure of 1 to 5 tore.
When a low potential is applied between the two electrodes
ionization of the gas occurs
ions move rapidly to the cathode
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2-The chopper
its function is to fluctuate the source output.
It is a circular disc divided into four quarters two are mirrored and two are opened.
The disc rotates at high constant speed, when the mirrored quarter in front of
the lamp, it reflects the radiation
the second moment the open in front of the lamp and the radiation passes
to the sample being absorbed by it and reaches the detector in pulses.
The detector converts the radiation to alternating current signal and amplified it.
The radiation coming from the flame itself and from atoms excited by the
flame will reach the detector continuously and converted to direct current
signal which can be suppressed and eliminated.
This process is known by modulation of the source output.
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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.
4- Monochromator:
Grating to eliminate other resonance lines from the source
or other radiation from the flame or sample
Schematic of an atomic-absorption experiment
Applications:
Qualitative analysis
Quantitative analysis
Determination of metallic elements in biological materials
Determination of elements in food industry as Cu, Zn, Ni,
are the most toxic elements of interest in food analysis
Determination of Ca, Mg Na, K in blood serum
Determination of lead in petrol
