1

Atomic Absorption Spectrometry(AAS)

Introduction:
-It is a measurement & interpretation of the absorbed radiation in atomic level.
-Robert W. Bunsen , Gustav R. Kirchoff & Alan Walsh first proposed & introduced Theory/Principle.
-Versatile method(60-70 elements determination)
--Separation of the test element from other elements present in the sample is unnecessary.

-Sample solution may be aqueous & non-aqueous.

-Does not demand the sample preparation.

-Widely used because of its simplicity, effectiveness & relatively low cost.
Theory/Principle:

-The absorption of energy by ground state atoms in the gaseous state forms the basis of AAS.

-If light of the resonance wavelength is passed through a flame containing the atoms in gaseous state, then
part of the light will be absorbed.

-The extent of absorption will be proportional to the number of ground state atoms present in the flame.

(Resonance WL is the same WL as they would emit if excited)


2

-Some of the atoms in the flame may be raised to the higher energy levels.

-On returning back to ground state, emit the characteristic radiation of the metal.

-But a large percentage of the metal atoms remains in the non-emitting Gr. State.
Mathematically, the total amount of light absorbed may be given by the expression as follows.
At , total amount of light absorbed= e
2
Nf
mc
Where,
e=charge on the electron of mass m,
c=velocity of light,
N=Total number of atoms absorbing at frequency ,
f= Oscillator strength or ability of each atom to absorb at ,

As , e, m & c are constant,

So, the total amount of light absorbed = Const.x N x f.

-Absorption is independent of WL(other than the indicated) & Temp.


3

Instrumentation(In brief)

i)Source (Hollow cathode lamp, Electrodeless discharge lamp(EDL) ):

-The popular light source, called a hollow cathode lamp, that emits exactly the wavelength required for the
analysis.(without the use of a monochromator).

-Cathode of the lamp is made up of the analyte element.

-The generated light is directed at the flame containing the sample.

-The source EDL is less common.
-Contains envelope of quartz containing metal or its salt, inert gas.

-The metal is excited with the radio frequency.

-More expensive but less sensitive.

-A separate lamp source is needed for each element(or sometimes a group of elements are used as
cathode)
2)Sample atomiser( Flame , electrothermal atomiser & specialized atomization techniques

-The sample is aspirated & analyte is converted to gaseous atomic state by the series of process in the
atomiser.

-The atomiser provides a reasonably long pathlength for detecting small concentrations of atoms in the flame.

-The radiant power or intensity of the radiation coming from the source is absorbed ie.reduces from P
0
(or I
0
)
to P(or I)

-The absorbance is proportional to the No. of atomic state element.
3)Monochromator(Prism/Gratings):

-The light beam then enters the monochromator, which is
tuned to a wavelength that is absorbed by the sample.

-Its function is to convert polychromatic light to monochromatic light of the interest.

4)Transducer(Photomultier):
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The detector measures the light intensity, alternatively for sample beam & reference(blank) & convert to
electricity.

-The outputs are sent to a data processor & readout device.
5)Data processor & readout:

-Here the signals are converted to transmittance or absorbance.
Function of a chopper:

-The light is "chopped" with a rotating half-mirror so that the detector sees alternating light intensities.

-At one moment, only the light emitted by the flame is reach since the light from the source is cut off.

-The light emitted from the flame contains radiation due to the thermal excitation followed by emission.
-While at the next moment, the light from both the flame emission and the transmission of the source's light
is measured since the source's light is allowed to pass.

-The electronics of the detector is such that the emission signal is subtracted from the total signal

-From this difference ,T is measured & absorbance (A) however, is usually what is displayed on the readout.
-As with the molecular absorption, the atomic absorption
behavior follows Beer's Law and concentrations of unknowns are determined in the same way.

Beer's Law,

A = a b c
Sample Atomization(Flame Atomization):

-A solution of the sample is nebulised by a flow of gaseous
oxidant,

-Mixed with the gaseous fuel,

-Carried into a flame where atomization occurs.

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Nebulization


Desolvation

Volatilization








Process occurring during atomization
-Series of interconnected processes occur,

-First, desolvation occurs with evaporation to produce a finely divided solid molecule aerosol.

-The aerosol volatilizes to form gaseous molecules.

-Dissociation of the molecules to an atomic gas.

-Part of the atomic gas ionizes to form cations & electrons.

-A fraction of molecules, atoms & ions are excited by the heat of flame to obtain atomic, ionic & molecular
spectra.
-Atomisation is the most critical steps in flame spectrometry.

-It limits the precision of the methods.
Sample solution
Spraying
Solid/gas aerosol
Gaseous molecule
Atoms
Excitation
Excitation
Atomic ions Excitation
AAS
-Atomisation is the most critical steps
in flame spectrometry.

-It limits the precision of the method
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Types of flames:
________________________________________________
Fuel Oxidant Temp. Max.
C burning velocity
_______________________________ cm/s______
Natural gas Air 1700-1900 39-43
Natural gas Oxygen 2700-2800 370-390
Hydrogen Air 2000-2100 300-440
Hydrogen Oxygen 2550- 2700 900-1400
Acetylene Air 2100-2400 158-266
Acetylene Oxygen 3050-3150 1100-2480
Acetylene Nitrous 2600-2800 285
oxide
-Various fuels-air flame(Temp. 1700-2400C)
Easily decomposed samples are atomised.

-Various fuels-Oxygen or nitrous oxide oxidants
(2500-3100)C.
Used for more refractory samples.

-Flow rate of fuel-oxidant mixture should be controlled
appropriately Stable flame.

-If the gas flow rate is less than the burning, the flame propagates back into the burner(flashback).

-Gas flow rate= burning rate Stable flame.
-At higher flow rate, the flame rises causing blow off the burner.





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Flame structure:

A flame can be divided into three parts:
a)Primary combustion zone.
b)Interzonal region.
(Reaction free zone)
c)Secondary combustion zone.

-The appearance of the flame is controlled by :
fuel to-oxidant ratio & the type of fuel & oxidant.
a)Pri.combustion zone:
-It represents blue luminescence.
-It arises from band emission of C
2
, CH & other radicals.
8

-Thermal equilibrium is usually not achieved in this region.Conc. of ions & free radicals is V.high.
-Hence is rarely used for flame spectroscopy.
b)Interzonal or Rxn. free zone.
-Relatively narrow.
-May reach several centimeters in height in fuel-rich acetylene- oxygen or acetylene-nitrous oxide
source.
-Free atoms prevails the region.
-So that the most widely used part of the flame for spectroscopy.
c)Secondary combustion zone:
-The products of the inner core or combustion processes are burnt to stable molecular oxides by the
surrounding air.
-The molecular species are then dispersed in the surrounding.
Temp. profile of the flame:

-The maximum temperature is located in the flame about 2.5cm above the Pri. combustion zone.

-Important from the view point of emission methods.

-This part of the flame is focused on the entrance slit for all calibrations & analytical measurements.
Flame absorption profiles:

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1)Magnesium:
-Exhibits a max. in absorbance at about the middle of the flame.
-Initially, as the distance from the base increases, absorbance also increases.
-It is because of increased no. of Mg. atoms due to the longer period of exposure the heat of the flame.
-Near to the secondary zone,
appreciable oxidation of Mg begins.
-It is followed by the decrease in absorbance.
-It is because the oxides so formed do not absorb at the observation wavelength.
-To achieve max. analytical sensitivity ,the flame must be adjusted up & down.(w.r.t. to the beam)
2)Silver:
-It is not easily oxidised.
-Continuous increase in no. of atoms from base to the periphery of the flame.
-It is followed by the increase in absorbance.
3)Chromium:
-Oxide formation predominates from the start.
-It is followed by the continuous decrease in absorbance beginning close to the burner tip.
Hence, a different portion of the flame should be used for the determination of each of these elements.

Atomic Absorption Instrumentation(in detail)
1)Radiation sources
2)Atomizers(Sample holder)
3)Monochromator
4)Transducers
5)Data processor & readout.
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1)Radiation sources:
-Atomic absorption method is highly specific as atomic absorption lines are very narrow(0.002-0.005nm) &
electronic transition energy are unique for each element.

-Extreme narrowness of the absorption line in the source causes problems.

-Conventional tungsten lamps & deuterium or xenon discharge lamps are not satisfactory for atomic
absorption.
-Because the bandwidth of the radiation emerging from the the monochromator is very broad in comparison
with the absorption band of the ground state atom.

-The light source must supply radiation of a line width less than that of the absorption line width of the
element being determined.
-This is achieved by vapour discharge lamps for certain easily excited elements, e.g. sodium & potassium.

-Normally, however hollow cathode lamps of the appropriate elements are used.

i)Hollow cathode lamp

ii)Electrodeless discharge lamp


i)Hollow cathode lamp

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-The most common source for atomic absorption measurement.

-Consists of a tungsten anode & cylindrical cathode sealed in a glass tube filled with neon or argon.
-Pressure of inert gas is 1-5 torr.
-The cathode is of the same metal whose spectrum is to be measured or it can be used to support the layer of
that metal.
-P.D. of 300V is applied across the electrodes.
-Ionization of the gas occurs.
-The kinetic energy associated with the cations dislodge some of the metal atoms from the cathode surface.
-Sputtering occur with producing an atomic cloud.
-Some of the sputtered metal atoms are in excited state.
-They emit characteristic radiation as they return to the ground state.
-High voltage & resulting high current leads to greater intensities.

-There are some disadvanges of the high voltage & current as well.
i) It causes increase in Doppler broadening of emission lines from the lamps.
ii)Greater currents produce an increased no. of unexcited atoms in the cloud.

-The unexcited atoms are are capable of absorbing the radiation emitted by the excited ones.
- It leads to the lowered intensities in the center of band.
-Some cathodes contains a mixture of several metals permitting determination of more than a single
element.
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ii)Electrodeless discharge lamp

13

-Produces atomic line spectra with radiant intensities usually one to two orders of magnitude greater than
hollow- cathode lamps.
-A sealed quartz tube contains a few torr of an inert gas(argon) & small qty. of the metal or its salts.
-The lamp contains no electrode.
-But energized by an intense field of radio frequency or microwave radiation.
-Radio-frequency ionises & accelerates the argon.
-These ions excite the atoms of the metal whose spectrum is sought.
-EDL available for 15 or more elements.
-Its performance is less reliable than that of hollow cathode lamp.
-Expensive & less sensitive.
2) Sample atomizers(Sample holder)

a.Flame atomizer.

b.Electrothermal atomizer.

c.Specialized atomization techniques
a)Flame atomizer
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-Used for atomic absorption, fluorescence, & emission spectroscopy.
-Purpose is to convert the test solution to gaseous atoms.
-The function of the nebulizer to produce a mist or aerosol of the test solution.
15

-The solution to be nebulised is drawn up a capillary tube by the ventura action of a jet of air blowing across
the top of the capillary.
-A gas flow at high pressure is necessary to produce a fine aerosol.
-The aerosol so formed by the flow of oxidant, is mixed with fuel.
-Then passes a series of baffles that removes all but the finest solution droplets.
-The baffles cause most of the sample to collect in the bottom of the mixing chamber.
-From the bottom it drains to a waste container.
-The aerosol, oxidant, & fuel are then burned in a slotted burner.
-Height of the flame is maintained: (5.0-10.0)cm
-This burner produces a relatively calm flame & provide a long pathlength for maximizing the absorption.
-Result is the enhanced sensitivity & reproducibility.
Fuel & oxidant regulators:
-An important variable is to close control of flow rate of both fuel & oxidant.
-According to the nature of sample flow rate of fuel & oxidant is controlled.
-For metal that forms stable or refractory oxides, excess fuel is desirable.
-The flow rate is controlled by means of double diaphragm pressure regulators & needle valve.
-To measure the flow rate rotameter is used.
-This technique of flame atomisation is the most reproducible of all liquid-sample introduction methods.
-Less sensitive due to the sampling efficiency than other techniques.
-Causes of poor sensitivity:
i)A large portion of the sample flows down the drain.
ii)The residence time of individual atoms in the optical path in the flame is brief.

b)Electrothermal Atomizer
-Entire sample is atomised in a short period & average residence time of the atoms in the optical path is a
second or more.
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-So that, sensitivity is enhanced.
-Used for atomic absorption & atomic fluorescence measurement.
-Also used in inductively couple plasma spectroscopy.
-However, not useful in direct production of emission
spectra.




-It consists of hollow graphite cylinder(50mm length, 9mm Dia.)
-Radiation beam passes along the axis of the tube.
-Graphite tube is surrounded by a metal jacket through which water is circulated.
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-The circulated water layer is separated from the graphite tube by a gas space.
-An inert gas, e.g. argon ,is circulated in the gas space.
-The same gas enters the graphite tube through openings in the cylinder wall.
-Quantity of the sample introduced is 1- 100l.
-The sample is introduced by a micropipette through a port in the outer(water) jacket, & into the gas inlet
orifice in the centre of the graphite tube.
-The graphite tube is then heated by the passage of an electric current.
-The temp. is high enough to evaporate the solvent from the solution.
-Then the current is gradually increased.
-Firstly the sample is ashed then ultimately vaporised to metal atoms.
-Temp. attained is about 3000K for vapourisation & atomisation
-Reproducibility depends upon the Temp., the timing of the drying, ashing & atomisation process.
-These parameters are selected according to the metal which is to be determined.
-The absorption signals may last for several seconds.

Performance characteristics of electrothermal atomizers:

-High sensitivity for small volumes of sample.

Sample(0.5l-10l) & detection limit 10
-10
g-10
-13
g.

-Precision(5%-10%) of electrothermal atomizers is inferior to flame or plasma atomization(1%).

-Slow.

-Analytical range is narrow(less than two orders of magnitude)

3) Specialized atomization techniques:
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Glow discharge atomization:
-It produces an atomized vapour that can be swept into a cell for absorption measurements.
-The glow-discharge occurs in a low-pressure argon gas atmosphere.
-In this atmosphere lies a pair of electrodes applying a DC voltage of 250 to 1000 V to break down the argon
gas into positively charged ions and electrons.

-These ions, under the influence of the electric field, are accelerated into the cathode surface containing the
sample.

-Bombarding the sample and causing neutral sample atom ejection through the process known as sputtering.

-The sputtered ground state atoms are drawn by a vacuum to the axis of the cell where absorption of
radiation takes place.
The atomic vapor produced by this discharge is composed of not only ground state atoms but fraction of
ions and excited atoms.

-The excited atoms relax back into their ground state, a low-intensity glow is emitted, giving the technique
its name.
Requirements:

-The sample must be an electrical conductor.
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-If the sample is not conductor, then be made into a pellet with a powdered conductor(graphite, copper).

-Solution sample is deposited on graphite, aluminum, or copper cathode.

Hydride atomization/Hydride generation method:

-Elements arsenic, antimony, & selenium are difficult to analyse by flame AAS.

-As it is difficult to reduce compounds of these elements to the gaseous atomic state.

-Sodium borohydride reduces compounds of the above element to volatile hydrides.

As(V) NaBH
4
AsH
3
Heat As
0
(gas)
+ H
2

solution [ H
+
] in flame
-Then hydride is dissociated into an atomic vapour by the relatively moderate Temp. of an argon-hydrogen
flame.

-Arsenic, antimony, & selenium can be determined using electrothermal atomization but hydride generation
is preferred.

-This method can be used for lead, bismuth, tin & germanium as well.
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Cold-vapour atomization:

-It is strictly confined to the determination of mercury.

-Elemental mercury shows appreciable vapour pressure at room temperature.

-No special treatment is required for gaseous atom formation.

-Mercury(II) compound is reduced with either sodium borohydride or tin(II) chloride(preferred) to form
elemental form.

Hg
2+
+ Sn
2+
Hg + Sn(IV)
-Apparatus for hydride generation is applied for this technique as well but without the facility of heating.

-Absorbance is measured at 253.7nm.

-Detection limits to ppb.

Spectrophotometers:
-Spectrophotometer should be capable to provide a sufficiently narrow bandwidth for the measurement.
-A separate filter & light source are used for each element.
-Flame/electrothermal atomizers are used.
-Most instruments use good quality UV/Vis monochromator for achieving the bandwidth on the order of 1.

-Generally photomultiplier tubes are used as transducer.

-Electronic system be capable of discriminating between the modulated signal from the source & the
continuous signal from the flame
i)Single beam instruments

ii)Double beam instruments

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i)Single beam instruments

Components:

a)Modulated power & radiation source

b)Atomizer/Flame

c)Monochromator

d)Transducer

e)Amplifier/readout.

-Modulated power source to eliminate the interference from emission of flame by the analyte.

-For modulation ,intermittent /pulse/Ac supply is used.

-To remove the interference a chopper also can be interposed between the flame & power supply.

-For resonance emission generally several hollow cathode lamps are used(not shown in diagram).
-Grating monochromator (Ebert monochromator) is used to select the resonance radiation of the metal under
study.

-Photomultiplier transducer is used to convert the intensity of radiation to electrical signals.

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-A shutter is interposed in front of the transducer to nullify the dark current.

-After elimination of the dark current, the 100% transmittance adjustment is then made.

-During the transmittance adjustment, a blank is aspirated or ignited in a non-flame atomizer.
-Amplifier & readout are used to digitalize & display of the result.

ii)Double beam instruments

a)Radiation source

b)Chopper

c)Atomizer/Flame

d)Monochromator

e)Transducer

f)Amplifier/readout.


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-A chopper split the beam from the hollow-cathode lamp source.

-One half passing through the flame & the other half is by passed.

-Two beams are then recombined by a half-silvered mirror, each is sent alternatively to a Czerny-Turner
grating monochromator.

-Photomultiplier tube serves as the transducer.

-Output of the transducer is input to a lock-in amplifier.
-The amplifier is in synchronization with the chopper drive.

-The ratio between the reference & sample signal is then amplified and fed to the readout.

-The readout may be a digital meter or a computer.



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Interferences in AAS:
-Mainly two types of interferences are encountered in atomic absorption method.
i)Spectral interferences , ii)Chemical interferences
-Sometimes physical interferences also become apparent:
i)Spectral interferences:

a)It is due to the overlap or lying near the absorption of interfering species with the analytical absorption.

-As a result, resolution by the monochromator becomes impossible.

-But is happens only in rare case.

-If difference between two lines is less than 0.01nm, then such problem appears.
Some typical interferences:
-----------------------------------------------------------------------
Resonance source WL, Analyte WL,
(nm) (nm)
------------------------------------------------------------------------
Aluminium 308.216 Vanadium 308.211
Antimony 231.147 Nickel 231.095
Copper 324.754 Europium 324.755
Gallium 403.307 Manganese 403.307
Iron 271.903 Platinum 271.904
Mercury 253.652 Cobalt 253.649
-The vanadium line interferes in the determination of aluminium.

-The interference can be avoided by observing the aluminium line at 309.27nm.

b)Interference due to the presence of combustion products:
by broadband absorption & scattering the radiation(particulate products).

-Both effects lead to positive analytical errors( by reducing the power of radiation).
-Fuel & oxidant mixture is the source of these products :

The analyte data can be corrected by measuring absorption during a blank being aspirated into the flame.
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-This correction should be conducted in the both single & double beam instruments.

-Absorption or scattering originates in the sample matrix:

Mere a blank correction is not sufficient.

The interference can be removed by adjusting the temp. & fuel-to-oxidant ratio. e.g
-In the analysis of mix. of alkaline earth metals, barium line appears in the centre of broadband for Ca(OH)
2
.

-This effect can be easily removed at higher Temp. of nitrous oxide flame decomposing Ca(OH)
2
.

-Interference by scattering may occur by products of atomization & incomplete combustion of organic
solvents

Ti, Zr & W form refractory oxides during atomization.

-Diameters of particles of the oxides are greater than the WL of the incident beam resulting the scattering of
the beam.
Finally:
-If the sources of interference is known, an excess of the interfering substances can be added to both sample
& standards.

-Excess added in standard sample , makes the effect of sample matrix effect insignificant.

-The added substance is called a radiation buffer.

-The method of standard addition may be proved advantageous in some cases.

Other important methods for the background/matrix effects:

i)Two-line correction method.

ii)Continuum-source correction method.

iii)Background correction method:
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a)Zeeman effect b)Source self-reversal.

i)Two-line correction method.

- An additional line appearing from the source is used as reference.

- This line should lie near to the line of the analyte but must not be absorbed by the analyte.

-Decrease in the intensity of the reference line is attributed to the absorption & the scattering effects of matrix
product.

-The decrease in the intensity is used to correct the absorbance of the analyte line.
ii)Continuum-source correction method.

-Deuterium lamp provides a source of continuum radiation through out the UV region.



-The radiation from the source covers throughout the UV region.

-Radiation from the continuum & the hollow-cathode lamp are passed alternatively through the electrothermal
atomizer.

-The Abs. of the deuterium radiation is then subtracted from that of the analyte beam.
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-Reduction in the intensity of continuum source corresponds to the broadband absorption or scattering by the
sample matrix.
-Background correction is thus achieved.
iii)Background correction based on the Zeeman effect

-A strong magnetic field splits electronic energy levels of atom to several absorption lines.

-It is applied to each electronic transition.

-Separation of each line is 0.05nm.

-Sum of the absorbance of all lines is equal to that of the original line.

-The simplest splitting pattern shows 3 lines.
-The Central prominent line & two satellites .

-The two type of absorption lines differ in response to the polarized radiation.

- absorbs only that radiation which is plane polarized in a direction parallel to the Ext. magnetic field.

- absorbs only radiation polarized at 90 to the field.
-Unpolarized light from a hollow-cathode lamp is passed through a rotating polarizer.

-The polarizer separates the beam into two polarized beams perpendicular to each other

-These beams are sent alternatively into a graphite furnace surrounded by a magnet.
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-The absorbs only a plane polarized light parallel to the field(Absorption by the analyte).

-In the next cycle, no absorption of analyte can occur.
- In the both cycles:

Absorption by the both broadband molecular absorption & scattering by the matrix products occur.

-The data-acquisition system gives the back ground corrected value by subtraction.


iii)Background correction based on source Self-Reversal
(Smith-Hieftje background correction method)

-For the corrected absorbance, the lamp is run alternatively at low & high current.

-High current produces large concentrations of non- excited atoms.

-These atoms absorb radiation produced from the excited atoms & additionally broaden the emission line of
the excited species.
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-Net effect is to produce a line that has a minimum in its center.

-The minimum is exactly in the wavelength of the abs. peak.

-Total absorbance is obtained during the low-current.

-The background absorbance is addressed during the second part of the cycle when radiation at the
absorption peak is at a minimum.
-The data-acquisition system gives a corrected value by subtraction.

-The technique is inexpensive & offers most of the advantages of a Zeeman effect instrument.
ii)Chemical interferences

Production of ground-state gaseous atoms which is the basisof flame spectroscopy may be inhibited by two
main forms of chemical interference:

a)By stable compound formation b)By ionization
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a)Stable compound formation:
-leads to incomplete dissociation of the substance to be analysed or formation of refractory compounds within
the flame.

-The refractory compounds Fail to dissociate into the constituent atoms

-Such difficulty is encountered in:
i)Determination of calcium in the presence of sulphate & phosphate(less volatile compd. formation)
ii)Formation of refractory oxides of titanium, vanadium & aluminium.
iii)Determination of mag./calc. presence of aluminum forming alu-magnesium or alu-calcium compound.
Techniques to overcome the chemical interferences:
1)Increase in flame temperature:

-leads to formation of free gaseous atoms. e.g

Aluminum determination:
Alu.oxide Aluminium

Calcium/magnesium determination
calcium-aluminate Calcium.

magnesium-aluminate Magnesium.

Fuel gas & oxidant used is acetylene-nitrous oxide.
2)By the use of releasing agent.

M-X + R R-X + M
(More stable than M-X) (Analyte)
-Excess of releasing agent(R) ensures the required gaseous metal atoms M.

-In the determination of calcium phosphate /sulphate , lanthanum chloride or strontium chloride is added to
the tested solution.

-Result is the formation of sulphate/phosphate salts of lanthanum/strontium.

-Then calcium can be determined in acetylene air flame.
-The same reagent are used in the analysis of magnesium/ calcium in the presence of aluminum.

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-Addition of EDTA (protective agent) into calcium solution before analysis gives volatile, stable compound
which is readily dissociated in the flame.

(useful in the presence of phosphate/sulphate ions)

3)Solvent extraction
-Analyte is separated from interfering substance by simple solvent extraction technique.

-Then the analyte aspirated into the atomizer.
b)By ionisation

M = M
+
+ e
-Ionisation of ground state atom in flame reduces the extent of absorption in AAS.

-To solve this problem , flame is operated at the lowest possible temperature to reduce the ionisation.

-High temp. causes ionisation of alkali metals, calcium, strontium & barium.

-To reduce the ionisation of gaseous atom of analyte effectively, ionisation suppressants are used.
-It is usually a solution containing a cation having a lower ionisation potential than that of the analyte.

-The flame is saturated with the electrons of ionisation suppressant which reduces the extent of ionisation of
analyte atom.
-A solution of potassium ions(2000mg/L) is added to a solution of calcium or barium or strontium ions.
Physical interferences:

-Physical factors e.g.
viscosity,

density,

surface tension &

volatility of the solvent used.

-These influence the amount of sample reaching the flame.

-So that Std. and sample solutions should not differ too widely in their bulk composition.
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Summary of interference minimizing procedures:
1)Ensure if possible that standard & sample solutions are of similar bulk composition to eliminate physical
effects(somebody states matrix effects)

2)Alteration of flame composition or of flame temperature can be used to reduce the likelihood of stable
compound formation within the flame.

3)Selection of an alternative resonance line will overcome spectral interferences from other atoms or
molecules & from molecular fragments.

4)Solvent extraction technique/ion-exchange techniques are used to overcome the interfering substances.
5)Use an appropriate background correction facility.

Atomic Absorption Analytical Technique:
Sample preparation:
1)Sample solution preparation
2)Direct application of sample(liquid/solid)
1)Sample solution preparation

-Disadvantage of flame spectroscopy: sample should be introduced into the excitation source in a form of
liquid (generally aqueous solution).

-Many materials are not soluble in common solvents.
(Soils, animal tissues, plants, petroleum products, minerals)

-Extensive preliminary treatments are necessary to bring the analyte in solution form for atomization.
-For decomposition & dissolving samples to obtain in
solution form, it is treated with :

Hot mineral acids,

Oxidation with liquid reagents(nitric, suphuric, perchloric acid )
Combustion in closed container to avoid loss of analyte
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Ashing at high temp.,

High temperature fusion with reagents such as boric oxide, sodium carbonate, sodium peroxide, or
potassium pyrosulphate.
Disadvantages in sample solution preparation:

-Decomposition & solution steps = Time consuming + increase the risks of introducing more errors than
AAS itself.

-Rigorous treatment of sample at high temperature treatment poses risks of losing the analyte by olatilization
or as particulate matter in smoke.

-Reagents used in decomposing the sample may introduce interfering substances in the sample.

-Reagent may be larger source of analyte than the sample.
2)Direct application of sample(liquid/solid)

-Electrothermal atomization provides this facility.
(Advantageous).

-Liquid Sp.: Blood sample, petroleum products , & organic solvents are directly pipetted into the furnace.

-Solid Sp.: Plant leaves, animal tissues, & some inorganic substances are weighed directly into cup-type
atomizers or into tantalum boats.

-Then introduced into tube-type furnaces.
Quantitative application & calibration curve:

-Beers law gives the basis for quantitative application of
AAS.

-According to the law , absorbance is directly proportional
to concentration.

A = log I
0
= abc
I
t
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Where,

A= Absorbance.
I
0
=Incident radiation
I
t
=Transmitted radiation
a =Absorptivity/Specific absorbance
b =Pathlength
c =Concentration.
Calibration curves:

i)To ascertain linearity between instrument response & concentration, calibration curves should be prepared
periodically.

ii)Calibration curve should cover the range of concentration of analyte found in the sample.

iii)No. of uncontrolled variables in atomization & absorbance measurements exist.

So that at least 1-2 Std. solutions should be prepared each time the analysis is performed.
Any deviation of value of Std. solution from the original calibration curve leads to correct the analytical
result.

iv)Std. addition technique is widely used in AAS.

It is useful to eliminate or minimize partially & completely the chemical & spectral interferences
introduced by the sample matrix.

Applications:

-More than 60 metals or metalloids are quantitatively determined.

-For determination of non-metallic elements vacuum spectrophotometers are required.(Resonance line
<200nm)

-Used in analysis of trace elements in steel.
-Used in the quantitative determination of pot. in fertilizer.
-Used in the determination of arsenic in food components.
-Used in the analysis of oil for silicon.
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-Used in the gas analysis for purity.
-Used in the determination of lead in petrol.
-Used in the analysis of soil.
-Used in the determination of the As & Cd element.
-Used in the analysis of additives.
-Used in the clinical analysis.
-Used in the detection of the metal particles present in the
parenterals.


Advantages: Disadvantages:
High sensitivity Non- metals are not handled
High accuracy Time consuming
High selectivity/Specific Expensive method
Wide applicability Thermal interference
Each sample should be analysed separately
Relative precision is low
Advantages of AAS over Flame Emisison Spectrometry
a)AAS is specific because the atoms of a particular element can only absorb radiation of their own
characteristic.
Spectral interference is thus rare in AAS contrary to FES.
b)AAS is independent of flame temp. as much larger No. of atoms that contribute to AAS signal contrary to
FES.
c)In terms of detection limits AAS & FES are quite similar.









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