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Atomic Spectroscopy
atomic spectroscopy is the determination of elemental
composition by its electromagnetic or mass spectrum.
the study of the electromagnetic spectrum of elements is
called Optical Atomic Spectroscopy.
electrons exist in energy levels within an atom
these levels have well defined energies
electrons moving between them must absorb or emit
energy equal to the difference between them.
Atomic Spectroscopy
in optical spectroscopy, the energy absorbed to move an
Atomic Spectroscopy
every element has a unique electronic structure, therefore the
Atomic Spectroscopy
Atomic Spectroscopy
divided into
Atomic
Absorption
Atomic
Emission
Atomic
Fluorescence
Atomic Spectroscopy
Atomic absorption spectra
energy of radiation absorbed by a vaporized atom is identical with
that needed to bring about excitation to a higher electronic state
transitions: excitation of an electron from ground state to a higher
energy level
Atomic Spectroscopy
Method: Atomization
A process in which the constituents of a solution are
converted into gaseous atoms / elementary ions.
Applicable to perhaps 70 of the elements in the periodic
table
Quite sensitive
Determine analyte concentration ppm to ppb range
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Instrument
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Block diagram
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Functions
(i)
(ii)
Nebulizer
(iii)
Burner head
(iv)
Monochromator
(v)
Photomultiplier tube
Atomic Spectroscopy
(based on Flame Atomization)
Spectrophotometer (AA); double beam
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Atomic Spectroscopy
(based on Flame Atomization)
Spectrophotometers
Radiation from hollow cathode lamp is split into 2 beams
One passes thru the flame
The other around the flame
A half-silvered mirror returns both beams to a single path then pass thru the
monochromator then detector
Note: monochromator placed between sample and detector
Eliminates most of the radiation emanating from the flame
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Line sources
i.
ii.
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Atomic Spectroscopy
(based on Flame Atomization)
Light source
called hollow cathode tube
lamp emits exact l required for the analysis (without the use of
monochromator)
light directed at the flame, containing sample (aspirated)
flame wide ( 4 6 inches)
Reasonably long path length for detecting small concentration of atoms in the
flame
Atomic Spectroscopy
(based on Flame Atomization)
1. Hollow Cathode Lamp
light source in AA instrument
light from this lamp exactly light required for the analysis, even no
monochromator is used
atoms of metal tested are present within the lamp
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Atomic Spectroscopy
(based on Flame Atomization)
So how does the Hollow Cathode Lamp works?
lamp on, atoms are supplied with energy
since the analyzed metal with exactly the same energy levels that undergoes
excitation
Atomic Spectroscopy
(based on Flame Atomization)
Illustration of the fact that the light emitted by hollow cathode lamp is exactly the
l needed by the atoms in the flame
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mirror
open
2. Atom Cell
the atom cell (2), is the part with two major functions:
1. nebulization of sample solution into a fine aerosol solution,
2. dissociation of the analyte elements into free gaseous ground
state form.
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ii.
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Flame Atomizers
Turbulent flow burner:
Nebulizer & burner are combined into a single unit
Sample is drawn up the capillary & nebulized
caused by the flow of gases around the capillary tip
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Flame Atomizers
Turbulent flow burner:
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Flame Atomizers
Laminar flow (premix ) burner:
Sample is nebulized by the flow of oxidant past a capillary tip
Resulting aerosol then mixed with fuel & flows past a series of baffles that
remove all but the finest droplets
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Flame Atomizers
Disadvantage:
Lower rate of sample introduction
Possibility of selective evaporation of mixed solvents in the mixing chamber;
create analytical uncertainties
Mixing chamber contains a potentially explosive mixture that can be ignited
by flashback (overcome: pressure-relieve vents)
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Flame Atomizers
Laminar flow
(premix burner)
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Aqueous solution
(sample)
burner
(laboratory type)
dispersed/
nebulized
swept
into
gaseous fuel
+
oxidant
into small
droplets
mixed
with
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Process: Atomization
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Inner cone: atoms & elementary ions formed from solid particles
Atoms/ elementary ions carried to outer cone (outer edge)
Oxidation process occur
Then atomized particles disperse into atmosphere
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Atomic Spectroscopy
Typical Gases for flames
Fuel Gas
Oxidizer gas
Maximum flame
temperature, oC
Natural gas
Air
1700
Acetylene (C2H2)
Air
2500
H2
O2
2940
Acetylene
N2O
2970
Acetylene
O2
3400
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Atomic Spectroscopy
proper flame temperature
fuel gas must be compound that can be burned in a controllable
manner to give a reproducible, as well as a hot flame
e.g. 1 Natural gas used in Bunsen burners
low flame
capable of exciting alkali metals (Group 1A) & some
alkaline metals (Group IIA)
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Atomic Spectroscopy
proper flame temperature
fuel gas must be compound that can be burned in a controllable
manner to give a reproducible, as well as a hot flame
e.g. 2 Acetylene nitrous oxide flame
Atomic Spectroscopy
Atomic absorption spectroscopy
(based on flames)
currently the most widely used of all the atomic methods
simplicity, effectiveness, relatively low cost
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Atomizer (Flame)
AA spectroscopy requires that the analyte atoms be in the gas phase.
Ions or atoms in a sample must undergo desolvation and vaporization
in a high-temperature source such as a flame or graphite furnace.
Flame AA can only analyze solutions, while graphite furnace AA can
accept solutions, slurries, or solid samples.
Flame AA uses a slot type burner to increase the path length, and
therefore to increase the total absorbance.
Sample solutions are usually aspirated with the gas flow into a
nebulizing/mixing chamber to form small droplets before entering
the flame.
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samples are placed directly in the graphite furnace and the furnace
is electrically heated in several steps to (i) dry the sample, (ii) ash
organic matter, and (iii) vaporize the analyte atoms.
Atomizer (graphite
furnace)
http://faculty.plattsburgh.edu/robert.fuller/437web/lec7graphitefurnace
/TempProgram.htm
http://faculty.sdmiramar.edu/fgarces/LabMatters/Instruments/
AA/AAS_Instrument/AASInstruments.htm
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Flame Advantages
Simple
Convenient
Excellent Results
Relatively short measurement time ~14 seconds
Flame Disadvantages
Sensitivity Limitations
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Atomic Spectroscopy
(based on Flame Atomization)
Absorption behavior follows Beers Law & concentration of unknown
are determined the same way
All atomic species have an absorptivity, a
Pathlength, b is width of the flame
A = abc
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Interferences
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Analyte
+
Analyte
e66
Analyte
+
Analyte
e67
3 CaCl2
(aq)
2 PO43(aq)
Ca3(PO4)2
(s)
6 Cl
(aq)
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3 CaCl2
(aq)
2 PO43(aq)
Ca3(PO4)2
(s)
6 Cl
(aq)
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Quantitative Analysis
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Calibration curve
x
x
x
Concentration
in principal linear
analysis should NEVER be based on the measurement of
a single standard with assumption that Beers law is
being followed
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bVs cs
Vt
bVx cx
Vt
A kVs cs kVx cx
cs = known concentration
As = absorbance after each
addition
Vt = total volume of each flask
Vs = variable volume of standard
added
cx = unknown concentration
k = constant = b/Vt
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A mVs b
Concentration of unknown:
slope;
m = kcs
intercept;
b = kVxcx
bcs
cx
mVx
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Absorbance
1.000
0.800
0.600
0.400
0.200
0.000
-0.200
-10.000
-5.000
0.000
5.000
10.000
15.000
20.000
Concentration
unknown?
Volume of
of standard
solution
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Slope, m = 0.0382
Intercept (at y-axis),
b = 0.2412
Concentration of unknown:
Absorbance
1.000
bcs
cx
mVx
0.800
0.600
0.400
0.200
0.000
-0.200
-10.000
-5.000
0.000
5.000
10.000
15.000
20.000
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AAS Flame
Element
AAS Flame
Al
30
Cu
As
100
Fe
Ca
Hg
500
Cd
Pb
10
Cr
Zn
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