Chapter 8

Atomic Absorption
Spectroscopy
AAS
Yang Yi
College of Science, BUCT
1

Atomic Absorption
Spectroscopy
AAS

Introduction
Elementary Theory
Instrumentation
Interferences
Experimental preliminaries
Applications
2

Introduction
What is AAS ?
Atomic absorption
spectroscopy is a quantitative
method of analysis that is
applicable to many metals and
a few nonmetals.

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

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
5

What is AAS ?
An atomic absorption
spectrophotometer consists of a light
source, a sample compartment and a
detector.
Sample
Sample
Compartment

Light Source

Detector

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.

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.
8

Elementary Theory
Characters of the atomic absorption
spectrum
Characteristic wavelength

E = E1 E0 = hc /
E1 - excited state
E0 ground state
h Plancks constant
c velocity of light
- wavelength

Characters of the atomic absorption

spectrum
Profile of the absorption line
K0 - maximal
absorption
coefficient
- half width

0 - central wavelength
10

Characters of the atomic absorption

spectrum
Natural broadening
determined by the lifetime of the excited state
and Heisenbergs uncertainty principle 10-5 nm

Doppler Broadening 10-3 nm

results from the rapid motion of atoms
as they emit or absorb radiation

Collisional Broadening
collisions between atoms and molecules
in the gas phase lead to deactivation of the
excited state and thus broadening the11
spectral lines

Characters of the atomic absorption

spectrum
Doppler Broadening 10-3 nm
results from the rapid motion of atoms
as they emit or absorb radiation

12

The relationship between absorbance and

the concentration of atoms

Beers law
It = I0e

-Kl

A = log I0/ 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)

13

The relationship between absorbance and

the concentration of atoms

Integrated absorption
K d=(e2/mc)N0
K - the absorption coefficient at the frequency
e the electronic charge
m the mass of an electron
c the velocity of light
f the oscillator strength of the absorbing line
N0 the number of metal atoms per milliliter able to
absorb the radiation
14

The relationship between absorbance and

the concentration of atoms

K d=(e2/mc)N0

The measurement of the integrated

absorption coefficient should furnish
an ideal method of quantitative
analysis
15

The relationship between absorbance and

the concentration of atoms
The line width of an atomic spectral line is
about 0.002 nm.
To measure the absorption coefficient of a
line would require a spectrometer with a
resolving power of 500 000.
The absolute measurement of the
absorption coefficient of an atomic
spectral line is extremely difficult.
16

The relationship between absorbance and

the concentration of atoms
This difficulty was overcome Walsh,
by
who used a source of sharp emission lines
with a much smaller half-width than the
absorption line. and the radiation
frequency of which is centred on the
absorption frequency.

17

The relationship between absorbance and

the concentration of atoms

In this way, the absorption coefficient at

the centre of the line, K0 , may be
measured instead of measuring the
integrated absorption.

18

The relationship between absorbance and

the concentration of atoms

2( v v 0 )

Kv K 0 log
ln 2
v 0

2
K0
D

ln 2 .e 2

fNov
mc

A = 0.4343 K0 l = K1N0v

A=
KC

19

Instrumentation

Line
source

Atomizatio
n

Nebulize
r

Monochromat
or

Detector

Read-out

Schematic diagram of a flame

spectrophotomer

20

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

21

Hollow cathode lamp (HCL)

Cathode--- in the form of a cylinder,

made of the element being studied in
the
flame
Anode---tungsten

22

A hollow cathode lamp for Aluminum (Al)

23

SpectrAA - AAS
HCL

motorized
Mirror
24

25

Sample atomization techniques

Flame atomization
Electrothermal atomization
Hydride atomization
Cold-Vapor atomization

26

Flame atomization
Processes occurring during
atomization

27

Flame atomization
Nebulizer - burner

A typical premix
burner

28

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
29
12 cm

Fuel and oxidant

flame

Auxiliary
oxidant

Air- propane

Fuel

Air- hydrogen

Air acetylene

Nitrous oxide acetylene

30

Common fuels and oxidants used in

flame spectroscopy

31

Disadvantages of flame
atomization
Only 5 15 % of the nebulized
sample reaches the flame
A minimum sample volume of 0.5 1.0
mL is needed to give a reliable
reading
Samples which are viscous require
dilution with a solvent

32

Eletrothermal atomization
Graphite furnace technique

33

Plateau Graphite Tube

34

Graphite furnace technique

process

drying

ashing

atomization

35

Graphite furnace technique

Advantages
Small sample sizes ( as low as 0.5
uL)
Very little or no sample preparation is
needed
Sensitivity is enhanced
( 10

-10

10-13 g , 100- 1000 folds)

Direct analysis of solid samples

36

Graphite furnace technique

Disadvantages
Background absorption effects
Analyte may be lost at the ashing
stage
The sample may not be completely
atomized
The precision was poor than the flame
method
(5%-10% vs 1%)
The analytical range is relatively
narrow
(less than two orders of magnitude)

37

Cold vapour technique

Hg2+ + Sn2+ = Hg + Sn (IV)

38

Hydride generation methods

For arsenic (As), antimony (Te) and selenium
(Se)
NaBH

As (V) 4
(sol)

[H+]

AsH3

hea
t
in
flame

As0(gas) + H2

39

40

Monochromator
--- diffraction grating

41

Detector
--- photomultiplier

42

Read-out system

--- meter
--- chart recorder
--- digital display

43

Atomic absorption
spectrophotometer

44

Interferences
Spectral interferences
Chemical interferences
Physical interferences

45

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
46

Spectral interferences
----- non-absorption line

----- molecular absorption +

combustion products (the fuel and

oxidant mixture)
Correct by making absorption
measurements while a blank is
aspirated into the flame
47

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

48

Spectral interferences
----- light scatter

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
49

Chemical interferences
----- Formation of compound of low
volatility

Ca 2+ PO43Mg2+,
Al3+
Increase in flame temperature
Use of releasing agents (La

3+

Use of protective agents (EDTA)

Separation
50

Chemical interferences
----- Ionization

Adding an excess of an ionization

suppressant (K)

51

Physical interferences
----- viscosity
----- density
----- surface tension
----- volatility

Matrix matching

52

Experimental preliminaries
Preparation of sample solutions
Optimization of the operating
conditions
----- resonance line
----- slit width
----- current of HCL
----- atomization condition

Calibration curve procedure

53

The standard addition

technique

54

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

55

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 3 / A

56

(ng/mL)
Sensitivity and detection limit

57

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
58

The end

59