Chapter 8

Atomic Absorption Spectroscopy

（ AAS ）

College of Science, BUCT

1
Atomic Absorption Spectroscopy
（ AAS ）

 Introduction
 Elementary Theory
 Instrumentation
 Interferences
 Experimental preliminaries
 Applications
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Introduction

What is AAS ?

Atomic absorption spectroscopy is

a quantitative method of analysis
that is applicable to many metals.

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 What is AAS ?

The technique was introduced in 1955

by Walsh in Australia (A.Walsh,
Spectrochim. Acta, 1955, 7, 108)
The application of atomic
absorption spectra to
chemical analysis

Alan Walsh 1916-1998

http://www.science.org.au/academy/
memoirs/walsh2.htm#1
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What is AAS ?

The technique was introduced in 1955

by Walsh in Australia
(A.Walsh, Spectrochim. Acta, 1955, 7,
108)

The first commercial atomic absorption

spectrometer was introduced in 1959

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 What is AAS ?

• An atomic absorption spectrophotometer

consists of a light source, a sample
compartment and a detector.
Sample
Compartment

Light Source Detector

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What is AAS ?

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 extend of absorption will be proportional to
the number of ground state atoms present in
the flame. 7
What is AAS ?

the gaseous metal atoms

specific resonance wavelength

extend of absorption

the extend of absorption vs the number of

ground state atoms present in the flame.

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The relationship between absorbance and
the concentration of atoms

Beer’s law
It = I0νe -Kνl
A = log （ I0ν/ It ） = 0.4343 K l

It - intensity of the transmitted light

Io – intensity of the incident light signal
l – the path length through the flame
(cm) 9
The relationship between absorbance and
the concentration of atoms
2
 2( v  v 0 ) 
Kv  K 0 log   ln 2 
 v 0 

2 ln 2  .e2

K0   fNov
 D  mc

A = 0.4343 K0 l = K1N0v A = KC

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 Instrumentation

Line
source Atomization Monochromator Detector

Nebulizer Read-out

Schematic diagram of a flame spectrophotomer

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Atomic absorption spectrophotometer

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 Resonance line sources

Emit the specific resonance lines of the atoms in

question

--- Provide the sharp emission lines with a much

smaller half-width than the absorption line
--- Intensity
--- Purity
--- Background
--- Stability
--- Life-time
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 Hollow cathode lamp (HCL)

Cathode--- in the form of a cylinder, made

of the element being studied in the flame
Anode---tungsten
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A hollow cathode lamp for Aluminum (Al)

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SpectrAA - AAS

HCL

motorized
Mirror

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17
Sample atomization techniques

Flame atomization
Electrothermal atomization
Hydride atomization
Cold-Vapor atomization

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Flame atomization

Processes occurring during atomization

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Flame atomization

Nebulizer - burner

A typical premix burner

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Nebuliser - burner

To convert the test solution to gaseous atoms

Nebuliser --- to produce a mist or aerosol of the

test solution
Vaporising chamber ---
Fine mist is mixed with the fuel gas and the
carrier gas
Larger droplets of liquid fall out from the gas
stream and discharged to waste
Burner head --- The flame path is about 10 –12 cm
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Fuel and oxidant

Auxiliary
flame oxidant

Air- propane Fuel

Air- hydrogen

 Air – acetylene
 Nitrous oxide – acetylene

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Common fuels and oxidants used in flame
spectroscopy

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Monochromator

--- diffraction grating

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Detector

--- photomultiplier

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Read-out system

--- meter

--- chart recorder

--- digital display

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Interferences

Spectral interferences

Chemical interferences

Physical interferences

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Spectral interferences

----- spectral overlap

（ +, positive analytical error ）

Cu 324.754 nm, Eu 324.753 nm
Al 308.215 nm , V 308.211nm,
Al 309.27 nm

Avoid the interference by observing the

aluminum line at 309.27 nm

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Spectral interferences

----- non-absorption line （非吸收线）

----- molecular absorption （ +）

combustion products (the fuel and
oxidant mixture)
Correct by making absorption
measurements while a blank is aspirated
into the flame

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Spectral interferences

----- light scatter （ +）

Metal oxide particles with diameters

greater than the wavelength of light
When sample contains organic species
or when organic solvents are used to
dissolve the sample, incomplete
combustion of the organic matrix
leaves carbonaceous particles that are
capable of scattering light
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Spectral interferences

----- light scatter （光散射）

（ +）
The interference can be avoided by
variation in analytical variables, such
as flame temperature and fuel-to –
oxidant ratio
Standard addition method
Zeeman background correction

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 Chemical interferences

----- Formation of compound of low volatility

Ca 2+ ， PO43- Mg2+, Al3+

Increase in flame temperature


 Use of releasing agents (La 3+ )

 Use of protective agents (EDTA)

 Separation
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Chemical interferences

----- Ionization

 Adding an excess of an ionization

suppressant (K)

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Physical interferences

----- viscosity
----- density
----- surface tension
----- volatility

 Matrix matching

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Experimental preliminaries

Preparation of sample solutions

Optimization of the operating conditions

----- resonance line
----- slit width
----- current of HCL
----- atomization condition

Calibration curve procedure

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The standard addition technique

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Sensitivity and detection limit

Sensitivity

----- the concentration of an aqueous

solution of the elements which absorbs
1% of the incident resonance radiation

----- the concentration which gives an

absorbance of 0.0044

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Sensitivity and detection limit

Detection limit
----- the lowest concentration of an analyte
that can be distinguished with reasonable
confidence from a field blank

D = c × 3σ / A

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Sensitivity and detection limit (ng/mL)

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Advantages and disadvantages

High sensitivity
[10-10g (flame), 10-14g (non-flame)]
Good accuracy
(Relative error 0.1 ~ 0.5 % )
High selectivity
Widely used

A resonance line source is required for

each element to be determined

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The end

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