Chapter 5 - AAS - 2019

Instrumental analysis for Undergraduate level
Kathmandu University 23rd APR.2019
Atomic Absorption Spectroscopy
Mr. Prakash Lamichhane/ Apr 2019

Kathmandu University 06/10/2021
Atomic Absorption Spectroscopy
(AAS)
Introduction:
• Atomic absorption spectroscopy (AAS) is one of the commonest
instrumental methods for analyzing metals and some metalloids
• Are widely applied of samples, such as agriculture chemical,
clinical and biochemistry, minerals, food and drugs,
environmental and other.
• AAS is based on the “first half” of the excitation process, while
atoms absorb light getting their electrons from the ground state
to a higher energy level.
• By AAS it is possible to determine about 70 elements (mainly
metals) at very low concentrations/ ~1ppm.
Mr. Prakash Lamichhane/ Apr 2019 2

Principle of the Atomic Absorption Method

• Atomized elements each absorb energy of a
wavelength that is peculiar to that element.
• The atomic absorption method uses as its
light source a hollow cathode lamp which
emits light of a wavelength that is peculiar
to each element.
• Elements within a solution are heated in a
flame or electrically (2000K to 3000K) and
subsequently determined using the fact that
the degree of absorption will vary with its Light absorption
concentration. process of atoms

The AAS instrument
Line source
Monochromator
:
Nebulizer

Sample
Compartment
Light Source Detector
The different parts of AAS: • Wavelength selector

• Atomizer (monochromator)
• Radiation source • Detector
• Sample holder (atomizer • Signal processor and read out.
containing gaseous atoms)

Steps:
• Nebulization: converts the solvent
Sample atomization in Flame:
(A) Flame atomization:

into small droplets.
• A sequence of steps
• Desolvation: solvent is
convert a metallic
element M from a
evaporated to produce a finely
dissolved salt MX in the divided solid molecular aerosol.
sample solution to free M- • Volatilization: solid Molecules are
atom. converted into gaseous phase.
• Dissociation: gaseous molecules
dissociates into, gaseous atom.
• Ionization: the excited atom may
gives a cation and an electron.
These excited species may give
molecular/atomic/ionic emission.

Energy level diagram:
• The absorbed wavelength of sample atom is based
on energy level of the atom.
• For sodium the energy is shown in figure.
• Similar kinds of orbitals are placed vertically with
increasing energy.
• p-orbitals are splitted into two energy levels because
of electron spin & the orbital motion of electron.
Both of these motion generates magnetic field Spin-
orbit coupling.
if fields parallel - slightly higher energy
if fields antiparallel - slightly lower energy
• The transition of electron from one state to another
obeys selection rule. Transitions between(s-s, p-p, d-
d, s-d etc) types of orbital is forbidden
• Depending on the energy gap of these orbitals
Different wavelength of electromagnetic radiation
are observed.
• More intense absorbance will occur between ground
Fig: Energy level diagram of Sodium atom and first excited state (3s to 3p transtion)

• About 5.2 ev, energy is

required for the complete
removal of the single
electron
• By similar mechanism d- and
f-orbitals will be splitted into
different energy, but the
magnitudes are negligible.
Slightly
different in
• Mg+ and Al2+ also have
energy similar energy level diagram,
where the difference of
energy levels between 3s
and 3p or other are more
because of high nuclear
charge in them.

(a) Partial absorption spectrum for sodium vapor.
(b) Electronic transitions responsible for the
absorption lines
Kathmandu University
Mr. Prakash Lamichhane/ Apr 2019

9
06/10/2021
Origin of three sodium emission lines

(resonance line)
Atomic spectrum
Mg is more
complicated
Spins Spins are

are unpaired
paired Energy
No split splitting
Singlet Singlet Triplet

ground excited excited
state state state

• The excited state electron has short life time <<

1second, which rapidly decays back to the ground
state, It is the fundamental basis of emission
spectroscopy. emission spectra.
Emission/Absorption spectra of sodium:
• Na emits two intense lines at 5896 and 5890Ao yellow color.
• Are shown at far right, overlapped due to less resolving
power of monochromator.
• These two lines are

resonance lines
(…?...)
• Less intense peak at
around 5700Ao (4d-
3p) is non resonance
• otherless intense
~3303Ao. (4p-3s)

Boltzmann Equation: Relates Excited

State Population/Ground State • The intensity of the peak depends upon
Population Ratios to Energy, Temperature the population of the energy state from
and Degeneracy which the transition starts.
N ∗ g∗ −(E / k T)
=( )× e
𝐍𝐨 𝐠𝐨

Effect of temperature on atomic spectra

statistical factors,
• Variation of depends on  -state of each level
According to
Energy difference
tempr fluctuates Nj Pj Boltzmann’s
the ratio  exp{ E j kT } Temp
r
N0 P0 equation
between no of -23 -1
excited and 1.38 X 10 JK
ground state No of atoms
ground state • Calculate the ratio of Na atoms at 3P & 3s at 2500 & 25100K.
atomic particles.
If ,   5893 A 0 (average)
6.626  10 34 Js  3  10 8 ms 1
E  hc /   10
 3 . 37  10 19
J
5893  10 m
At 2500 K , N j / N 0  1.72  10  4
At 2510 K , N j / N 0  1.79  10  4
Population increases by 4%

Flame property on the basis of fuel and

oxidant:
• Temperature of the flame depends on the
type of oxidant and fuel used. Fuel Oxidant Temp. oC
• Most of the flame provides temperature
greater than 2000K Natural gas Air 1700-1900
• The oxidant gas is usually air, oxygen and Oxygen 2700-2800
nitrous oxide. Hydrogen Air 2000-2100
• Gas flow rate also determine the Oxygen 2550-2700
temperature of the flame.
• Flame will be stable only at certain rate of Acetylene Air 2100-2400
gas flow it is determined by the burning Oxygen 3050-3150
velocity (cm.sec-1). Nitrous 2600-2800
– If gas (fuel) flow rate = burning velocity (at oxide
some part above the burner) flame will be
stable.
– If gas flow rate < burning velocity, flame
propagates back to the burner giving flask back.
– On further increasing the flow rate, Where, gas
flow rate > burning velocity, flame raises up and
blow off the burner.

Flame structure: secondary

• (a) Primary combustion zone: In the interzonal
case of hydrocarbon flame, it is

recognized by blue luminescence
arising from band spectra of C2, CH,
and other radicals. Thermal
Primary
equilibrium is not established in this zone
region so rarely used in flame
spectroscopy.
• (b) Inter-zonal region: It is narrow in Maximum
the case of hydrocarbon flame and temperature
several cm heights in the acetylene
nitrogen flame. This zone is rich in
free atoms and most widely used.
• (c) Secondary combustion zone: the
products from inner core are
converted to stable molecular oxides
and get dispersed in the
surrounding.

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.
(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.

(B) Flameless atomizer/ non flame techniques
i. Electro
thermal
atomization:
(HCL) (ETAAS
or
GFAAS)
 Evaporation:at low temperature

• interchangeable graphite tubes or rod 5cm long 
Ashing: at high temperaure
• internal diameter less than 1cm  Atomization : high temperature/few
• Sample size: Solid: μg/ Liquid: μL milli-seconds.
• High sensitivity (10 -10 g. analyte).
-10 -13
 Absorbance is measured immediately
• Precision 5-10% (error)
 Cleanout (quick ramp up to 3500 C or
• Short time response. Few seconds
so). Waste is blown out with blast of Ar.
• Applicable to analyze solid samples as well,
GF Design
Graphite cap Graphite holder
Sample
Cooling block inlet
Aperture
plate socket Seal
シール Graphite tube
Eject arm Spring Fixing knob

• GFA is held in a water cooled metal housing

(water jacket).
• Two inert gas streams (Ar /N2).
 In an actual
 One (external) prevents outside air and measurement heating
incineration of the tube
 internal stream flows into two ends of the is done in 3 stage.
tubes and out the sample port. This stream,
not only carry away the vapor generated drying
from the sample matrix during the first two
heating states. - Drying stage (100oC)
o Sample is placed on L’vov platform/ to
generate homogeneous temperature. ashing
o For reproducibility the temperature, timing of
drying and ashing and atomization process - Ashing stage (400-1000oC)
must be selected constant.
atomization
- Atomizing stage (1400-3000oC)

Advantages of non flame atomizer

-Small sample size volume (as low as 0.5 uL).
- Unusual high sensitivity ( 10 -10 –10-13 g , 100- 1000 folds)
-Very little or no sample preparation is needed/ Solid sample can be used directly.
- Heat distribution is uniform and temperature is steady.
- No need for fuel -oxidant mixture.
- No flame noise.
Disadvantages
oBackground absorption effects
oAnalyte may be lost at the ashing stage
oThe sample may not be completely atomized
oThe precision was poor than the flame method (5%-10% vs 1%)
oThe analytical range is relatively narrow (less than two orders of
magnitude)

Some especial atomization techniques:
1. Hydride Vapor Generation Technique

• As, Se, Sb, Sn, Te, Bi, Hg and other metals
produce a metal hydride by this method
Elements Concentration (ppb)
As 5~20
Sb 5~20
Te 5~20
Bi 5~20
Se 10~40
Hg 20~80 - 3+ +
6BH4 +As + 3H 3B2H6+3H2 +AsH3 ↑(gas)
Sn 30~90
3BH4- + 3H+ + 4H3AsO3 → 3H3BO3 + 4AsH3↑ + 3H2O

Absorption Cell
Burner Head
Peristaltic of AAS
Pump Manifold
Gas Liquid
Reaction Separator
Coil
Drain
Sample HCl NaBH4
Carrier Gas Ar
Structural Diagram of Hydride Vapor Generator

2. Cold Vapor Technique

 253.6 nm
Hgo(g)
SnCl2
5%KMnO4
5%H2SO4
SnCl2 + Hg2+ reduce Hgo(gas) Hg2+ + Sn2+ = Hg + Sn (IV)

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.

Line width (Band width):

Atomic absorption peaks are very narrow
(~10-4Ao).
 The peak is symmetric distribution of
wavelength about mean (λo).
Energy associated with λo is the exact
energy differences between two quantum
states.
The line width or effective line width
(Δλ1/2) is defined as its width in wavelength
unit when measured at one half the
maximum signal (FWHM).

Resonance line sources/Radiation source

Emit the specific resonance lines of the atoms present in sample
Provide
--- the sharp emission lines with a much smaller half-width
than the absorption line
Hollow cathode lamp (HCL)
internally coated
potential (300-500V)
with a metal
10-20mm in diameter transparent

 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.

Doppler broadening （ 10-3 nm ） of

emission, lines (arises due to rapid motion of
absorbing particles w.r.t. the source. Shorter
wavelength is observed for atoms moving
towards the source and longer for those
moving away from source).
Also greater current produce large number of
un excited atoms in the cloud, which
themselves absorb radiation emitted by
excited atoms (self absorbing) this will
decrease the intensity.
Collisional Broadening Pressure effect:
 High potential i.e. current leads to
greater intensity but increases the band collisions between atoms and molecules in the gas
width phase lead to deactivation of the excited state and
Natural broadening /Uncertainty effect: thus broadening the spectral lines
Determined by the lifetime of the excited state
and Heisenberg’s uncertainty principle （ 10-5 nm ） Electric and magnetic field effect:

Spectrophotometer: Both single and

double beamed instruments are available.
• (a) Single beamed instrument: Contains,
- Hollow cathode lamp

- A chopper or a pulsed power supply
- An atomizer
- A simple grating spectrometer a photo multiplier
- Detector.

(b) Double beamed instrument: Contains,

=> Hollow cathode lamp
=> Mirror chopper one half through mirror and half around.
=> Two beams are combined by ½ silvered mirrors and
passed into Czerney Turner grating monochromator.
=> A photo multiplier tube (transducer
Reference beam doesn’t pass from the flame
Note: the Ref bean does not pass

through the flame thus does not correct for the
interferences from the flame!
synchronized

Interferences with FES and AAS:

• The measurement by AAS and FES suffers different errors.
The error may be related to instrumental sensitivity or
chemical properties of the species. The deviation or the
shift in mrasured signal generated by analyte due to other
species in the sample is termed as interference.
• There are 3 types of interferences associated
with both FES and AAS:
(a) Spectral interferences
(b) Chemical interferences and
(c) Physical interferences

(a) Spectral line Interferences arise whenever the line of

interest cannot be easily resolved from another
element or from a molecular band present in the
background. Generally, the band pass of even very
good monochromators is a power of 10 greater than
the width of the lines of the HCL. In some cases,
amplitude modulation of the HCL helps to detect these
interferences.
– Overlapping
– Broadening absorption for air/fuel mixture
– Scattering or absorption by sample matrix
Mr. Prakash Lamichhane/Apr 2019 33

(I) Spectral interference can occur due to overlapping lines. Gives +,

positive analytical error ） e.g. a vanadium line at 3082.11Å
interferes in an analysis based upon the aluminum absorption line at
3082.15 Å. This type of interference can be avoided by employing the
aluminum line at 3092.7 Å instead.
Target element Spectral line Interfering Spectral line
(nm) element (nm)
Al  V 
Ca  Ge 
Cd  As 
Co  In 
Cu  Eu 
Fe  Pt 
Ga  Mn 
Hg  Co 
Mn  Ga 
Sb  Pb 
Si  V 
Zn  Fe 

(II) Presence of combustion products:

• Diameter> wavelength of incident radiation.
• Causes scatter of incident radiation. This will cause positive error
of the measurement.
• Example: Impure elements such as Ti, Zr and W which form
refractory oxides can cause spectral interference due to scattering.
{Source: Sample matrix}
Organic solvent can from carbonaceous particle because of
incomplete combustion and can cause scattering hence
interference. {Source: fuel/oxidant}
A blank can be aspirated into the flame to make the correction.

(III) Due to broadband absorption:

An example: in the determination
of barium in alkaline earth mixture.
The wavelength of Ba line used for
atomic absorption analysis appears
in the center of a broad absorption
band for CaOH.
The effect can be eliminated by
substituting nitrous oxide for air as
the oxidant which yields a higher
temperature that decomposed the
CaOH and eliminates the absorption
band.

• 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.

Elimination of interference due to …………..y:

• Interference due to formation of species of low volatility can often be eliminated or moderated
by use of
• Higher temperature
• Releasing agents
• Protection agents: form stable but volatile species with the analytes (i.e. EDTA,APDC….)
• Use of high temperature: using acetylene –oxygen flame.
• Use of Releasing agents: Releasing agents are cations that react preferentially with the
interferant and prevent its interaction with the analyte, and so the interference. Consider the
reaction
M–X + R = R-X + M R-X is a stable compound
Excess of releasing agent (R) will lead to an enhanced concentration of the required gaseous metal
atoms M.
Calcium determination in the presence of phosphate, the addition of an excess of lanthanum

chloride or of strontium chloride to the test solution will lead to formation of lanthanum (or
strontium) phosphate, the interference is minimized.

• Use of Protective agents: Protective agent are those that prevent interference by
forming stable but volatile species with the analyte.
• Three common reagents for this purpose are EDTA, 8-hydroxyquinoline, and APDC
(ammonium pyrrolidene dithio carbamate).
• The addition of EDTA to a calcium solution before analysis may increase the sensitivity, this
is possibly due to the formation of an EDTA complex of calcium which is readily dissociated
in the flame, the interference due to presence of Al, Si, phosphate and sulphate can be
minimized.
• Use of 8-hydroxyquinoline also removes interference of Al in the determination of Ca and
Mg.
• Extraction of the analyte or of the interfering element(s): The interfering species
and the analyte can be separated using different separation methods like
chromatography prior to AAS determination.
• Using Radiation Buffer: If interferant is known, a excess amount of the interfering
species is added to both sample and standard, so that the interfering intensity by the
contaminant will be relatively negligible.

(II) Dissociation Equilibria:

Gaseous environment of a flame or a furnace, numerous dissociation and
states. Some of these reactions are reversible and can be treated by the law
of thermodynamics.
• Dissociation of metal oxide and Metal Hydroxide:
Alkaline-earth metal oxide, The band
MO M+O spectra of hydroxide and oxide causes the
M(OH)2 M + 2OH interference at low temperature.
• Dissociation of salt with other ion: Intensity of line spectra by sodium is
NaCl Na + Cl decreased in presence of HCl.
Enhancement in the absorption by vanadium in presence of Al and TI
VOx V + Ox In lean of fuel rich flame concentration of
Ox is low. Its concentration will be further
AlOx Al + Ox decrease in presence of Al and Ti. This
TiOx Ti + Ox decrease causes the first equilibria to shift
right.
(III) Ionization of the ground state gaseous atoms:

• Ionization of atoms and molecules is small in combustion mixtures that involve air as the oxidant,
and generally can be neglected. But at high temperature flame ionization os possible. It will reduce
intensity absorbance/emission of the atomic spectral
lines. It is therefore clearly necessary to reduce the possibility of ionisation occurring to a minimum.
• Concentration of free electrons exists as a consequence of the equilibrium
M M+ + e-
The equilibrium constant K for this reaction takes the form [M+][e-]
Elimation or reduction of ……
K=
[M]
# use of lowest possible temperature,
# addition of an ionisation suppressor, Ionization buffer.
The effect in shift in the ionisation equilibria quantitatively by addition of an ionisation suppressor,
Ionization buffer.
which provide relatively high concentration of electron to the flame (B = B+ + e-)
for example, potassium concentration of 2000 ppm added to a solution containing calcium,
barium, or strontium ions creates an excess of electrons when the resulting solution is nebulised into
the flame, and this has the result that the ionisation of the metal to be determined is virtually
completely suppressed.

Experimental procedures
ATOMIC ABSORPTION ANALYTICAL TECHNIQUES
• Sample solution preparation:

• Preparation of standard
solutions:
• Calibration curve procedure:
• The standard addition technique.

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.

Application of Atomic Absorption Spectrometry:

• It is a sensitive means for the quantitative determination of more than 60 metals or
metalloid elements.
• 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.
ADVANTAGES & DISADVANTAGES:

• Precise and very sensitive
• accurate results can be obtained.
• Moderately expensive
• Can only process one element at a
time.
• Slower than ICP-AES
• Can only identify limited types of
elements

Atomic Emission Spectroscopy (AES)/

Flame Emission Spectroscopy(FES) (Flame
Photometry):
Flame Photo detector Read out
Amplifier
Filter
Gas
inlet
Nebulizer
Drain -
U tube
Air
Fig: Flame emission spectrometer

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 the total
number of atoms in the flame i.e. the sample concentration

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.

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

Chapter 5 - AAS - 2019

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Instrumental analysis for Undergraduate level

Kathmandu University 23rd APR.2019

Atomic Absorption Spectroscopy

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Principle of the Atomic Absorption Method

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The AAS instrument

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Light Source Detector

The different parts of AAS: • Wavelength selector

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(A) Flame atomization:

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• About 5.2 ev, energy is

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Origin of three sodium emission lines

Spins Spins are

Singlet Singlet Triplet

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• The excited state electron has short life time <<

• These two lines are

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Boltzmann Equation: Relates Excited

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Effect of temperature on atomic spectra

ground state No of atoms

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Flame property on the basis of fuel and

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Flame structure: secondary

case of hydrocarbon flame, it is

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(B) Flameless atomizer/ non flame techniques

 Evaporation:at low temperature

Eject arm Spring Fixing knob

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• GFA is held in a water cooled metal housing

- Atomizing stage (1400-3000oC)

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Advantages of non flame atomizer

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Some especial atomization techniques:

1. Hydride Vapor Generation Technique

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2. Cold Vapor Technique

SnCl2 + Hg2+ reduce Hgo(gas) Hg2+ + Sn2+ = Hg + Sn (IV)

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Line width (Band width):

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Resonance line sources/Radiation source

10-20mm in diameter transparent

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Doppler broadening （ 10-3 nm ） of

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Spectrophotometer: Both single and