ATOMIC

ABSORPTION SPECTROSCOPY.
By Ms. Swarupa Verekar Ist sem M.Pharma (Q.A.) (2011-2012)
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Contents:

Introduction Principle Instrumentation Single beam Atomic Absorption Spectrometer Double beam Atomic Absorption Spectrometer Difference between AAS and FES Detection limit & sensitivity Advantages Disadvantages Interferences Applications
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Introduction:
WHAT IS AAS?

Atomic absorption spectroscopy is a quantitative as well as qualitative method of analysis that is applicable to many metals and a few nonmetals.

 The technique was introduced in 1955 by Walsh in Australia.

The first commercial atomic absorption spectrometer was introduced in 1959

Principle:
A much larger number of the gaseous metal atoms will normally remain in the ground state. These ground state atoms are capable of absorbing radiant energy of their own specific resonance wavelength.

 If light of the resonance wavelength is passed through a flame containing the atoms in question, 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. The concentration of an absorbing species in a

sample is determined by applying BeerLamberts Law. A=bc Concentration measurements are usually determined from a calibration curve generated with standards of known concentration

The relationship between absorbance & concentration of atoms

Kd=(e2/mc)N0

K-the absorption coefficient at the frequency ethe electronic charge mthe mass of an electron cthe velocity of light f the osillator strength of the absorbing line N0the number of metal atoms per milliliter able to absorb the radiation
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Schematic diagram of an atomic absorption spectrometer

Instrumentation:
Light source Chopper Nebulizer / atomizer Monochromator Detector Amplifier Read-out device

Light sources:
Hollow cathode lamp Electrode-less Discharge Lamp

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Hollow-cathode lamp:

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working:
electric discharge ionization of rare gas atoms acceleration of gas into cathode metal atoms of the cathode are sputtered

into gas phase collision of sputtered atoms with gas atoms or electrons excite metal atoms to higher energy levels decay to lower energy levels by emission of light
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 The cathode contains the element that is

analysed. Light emitted by hallow-cathode lamp has the same wavelength as the light absorbed by the analyte element.
Different lamp required for each element.

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Electrode less Discharge Lamp

Volatile elements Element Evacuated tube argon sealed Microwave discharge argon turns plasma Excitation Emission

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Chopper:
pulsating light Steady light by flame not detected

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Nebulizer / Atomizer

Nebulizer: To produce fine mist of test

solution
Atomizer: To convert the test solution to

gaseous atoms

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Atomizers:
2 types: Flame atomizers :

total combustion burner premixed burners Electrothermal atomizers : graphite tube furnace carbon rod tantalum ribbon
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Flame atomizers:

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Advantages:
inexpensive (equipment, day-to-day

running) high sample throughput easy to use high precision

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Disadvantages:
only solutions can be analysed relatively large sample quantities required

(1 2 mL) less sensitivity (compared to graphite furnace) problems with refractory elements

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Electrothernal atomiser:
graphite tube furnace

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Working principle:
Drying the solvent is evaporated Pyrolysis the majority of the matrix

constituents is removed Atomization the analyte element is released to the gaseous phase

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Advantages:
Solutions, slurries and solid samples can be

analysed. much more efficient atomization greater sensitivity. smaller quantities of sample (typically 5 50 L) provides a reducing environment for easily oxidized elements.
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Disadvantages:
expensive low precision low sample throughput requires high level of operator skill

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Monochromator:
isolation of the absorption line from

background light and from molecular emissions originating in the flame, i.e. tuned to a specific wavelength

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Detector:
A photomultiplier measures the intensity of the incident light and generates an electrical signal proportional to the intensity

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Amplifier:
Amplifies the signal from detector & feeds it

to read out device.

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Read-out devices
Meters Chart recorders Digital display

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Single beam Atomic Absorption Spectrometer

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Double beam Atomic Absorption Spectrometer

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Detection limit & sensitivity

Detection limit is the concentration required

to give a signal equal to 3 times the standard deviation of the baseline (blank). AAS shows superior detectability for those elements that emit below 300 nm because of high thermal energy required to excite the atoms for emission at these wavelengths.

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Sensitivity
Sensitivity is the concentration required to

give 1% absorbance. Sensitivity depends upon choice of analytical wavelength and identity of the element. The lower limit of reliable detection of an element ranges from 0.002 g/ml (beryllium) to 360 g/ml (thorium), but detection limits below 1 g/ml are found for many elements.

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Difference between AAS & FES

AAS Absorption of incident light measured FES Emitted light is measured. AAS beer-Lamberts law obeyed over wide

concentration range. FES not true in this case.

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 AAS absorption depends upon no. of

unexcited atoms and therefore not affected by flame temperature directly. FES emission intensity depends upon no. of exciting atoms, so influenced by temperature variations.

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Advantages over flame emission spectroscopy

Comparatively less spectral interferences. Atoms absorb their characteristic

wavelength.
Independent of temperature variations.

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Disadvantages of AAS
Separate lamp for each element to be

determined. Not suitable for estimation of Al, Ti, Mo, W, Si etc. they form oxides in flame. In aqueous solutions predominant anion affects signal to a negotiable degree.

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Interferences:
Spectral interferences Due to overlapping of radiation characteristic to

element being determined. use of chopped light source or selecting other spectral lines
Chemical interferences Incomplete dissociation into atoms Raise flame temperature Ionization interferences Too high flame temperature & high ionization

potential of element addition of more readily ionizable element

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Interferences:
Matrix or bulk interferences

Change in viscosity of solution due to change in solvent or concentration Solvent interferences organic v/s aqueous Dissociation of metal compounds Formation of refractory oxides use nitrous oxide-acetylene flames
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Applications:

Qualitative analysis Quantitative analysis Simultaneous Multicomponent analysis Determination of metallic elements in biological materials Determination of metallic elements in food industry Determination of Ca, Mg, Na and K in blood serum Determination of lead in petrol
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References:
www.wikipedia.org Gurdeep R. Chatwal and Sham K. Anand, Atomic

absorption spectroscopy, Instrumental methods of chemical analysis, 5th edition, page no. 2.340-2.366. Willard H.H., Merritt L.L., Dean J.A. and Settle F.A., Instrumental methods of analysis, 7th edition, page no. 247-248. Richard D. Beaty and Jack D. Kerber, Concepts, Instrumentation and Techniques in Atomic Absorption Spectrophotometry, 2nd Edition, page no. 2.2-2.16 Gary D. Christian, Absorption Spectroscopy Methods, Analytical Chemistry, 5th edition, page no. 476-478. Kenneth A. Connors, Physical & Instrumental Methods: Absorption Spectroscopy, A Textbook of Pharmaceutical Analysis, 3rd edition, page no. 215 40

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