ATOMIC SPECROSCOPY (AS)

Atomic Absorption Spectroscopy

Flame Atomic Emission Spectroscopy

ICP Atomic Emission Spectroscopy

 ATOMIC ABSORPTION
SPECTROSCOPY

analytical technique that measures the concentrations

of elements. It makes use of the absorption of light
by these elements in order to measure their
concentration .
- Atomic-absorption spectroscopy quantifies the
absorption of ground state atoms in the
gaseous state .

- The atoms absorb ultraviolet or visible light

and make transitions to higher electronic
energy levels . The analyte concentration is
determined from the amount of absorption.
- Concentration measurements are usually
determined from a working curve after
calibrating the instrument with standards of
known concentration.

- Atomic absorption is a very common

technique for detecting metals and
metalloids in environmental samples.
Atomic absorption spectrometers have 4 principal
components

1. A light source (a hollow cathode lamp)

2. An atom cell (atomizer)
3. A monochromator
4. A detector and read out device .
 Schematic Diagram of an Atomic
Absorption Spectrometer

Detector and
Light source atomizer
(hollow cathode Lamp ) monochromator readout device
 Atomic Absorption
Spectrophotometer
 Light Source
• The light source is usually a hollow cathode lamp of
the element that is being measured. It contains a
tungsten anode and a hollow cylindrical cathode
made of the element to be determined. These are
sealed in a glass tube filled with an inert gas (neon or
argon). Each element has its own unique lamp which
must be used for that analysis .
 Light Sources
• Hollow-Cathode Lamps (most common).

• Lasers (more specialised).

• Hollow-cathode lamps can be used to detect one

or several atomic species simultaneously. Lasers,
while more sensitive, have the disadvantage that
they can detect only one element at a time.

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Hollow Cathode Lamp
Quartz window

Pyrex body
cathode

Anode

Cathode
Anode
 Hollow-Cathode Lamps
• Hollow-cathode lamps are a type of discharge
lamp that produce narrow emission from atomic
species.

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 Hollow-Cathode Lamps
*
M
*
M+e M
collision-induced
excitation *
M + Ar* M
M

*
M

spontaneous
emission M* M + h

M 12
 Reactions in the Hollow Cathode Lamp
• Apply sufficiently high voltage between the cathode and the
anode:
(1) Ionization of the filler gas:
Ne + e- = Ne+ + 2e-
(2) Sputtering of the cathode element (M):
M(s) + Ne+ = M(g) + Ne
(3) Excitation of the cathode element (M)
M(g) + Ne+ = M*(g) + Ne
(4) Emission of radiation
M*(g)  M(g) + h

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 Atomizer

Elements to be analyzed needs to be in

atomic state

Atomization is separation of particles into

individual molecules and breaking molecules
into atoms . This is done by exposing the
analyte to high temperatures in a flame or
graphite furnace .
The role of the atom cell is to primarily dissolve a liquid
sample and then the solid particles are vaporized
into their free gaseous ground state form. In this
form atoms will be available to absorb radiation
emitted from the light source and thus generate a
measurable signal proportional to concentration .
•
 Atomisation
• Atomic Absorption Spectroscopy (AAS) requires that
the analyte atoms be in the gas phase.

• Vaporization is usually performed by:

– Flames
– Furnaces
– Plasmas

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 Flame Atomisation
• Flame AAS can only analyse solutions.

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Flame Atomisation

19
 Flame Atomisation
• Degree of atomisation is temperature dependent.

• Vary flame temperature by fuel/oxidant mixture.

Fue l Ox ida nt Te mpe ra ture (K)

Ac e tyle ne Air 2,400 - 2,700
Ac e tyle ne Nitrous Oxide 2,900 - 3,100
Ac e tyle ne Oxyge n 3,300 - 3,400
Hydroge n Air 2,300 - 2,400
Hydroge n Oxyge n 2,800 - 3,000
Cya noge n Oxyge n 4,800
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Processes that take place in flame
 Furnaces

• Improved sensitivity over flame sources.

• (Hence) less sample is required.

• Generally, the same temp range as flames.

• More difficult to use, but with operator skill at

the atomisation step, more precise measurements
can be obtained.

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Furnaces

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 Inductively Coupled Plasmas

• Enables much higher temperatures to be achieved.

Uses Argon gas to generate the plasma.
• Temps ~ 6,000-10,000 K.

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The Atomic Absorption Spectrometer
Sample Introduction System

Nebuliser

Capillary

Solution
 Detector and Read out Device
The light selected by the monochromator is directed
onto a detector that is typically a photomultiplier
tube , whose function is to convert the light signal
into an electrical signal proportional to the light
intensity.

The processing of electrical signal is fulfilled by a

signal amplifier . The signal could be displayed for
readout , or further fed into a data station for
printout by the requested format.
 Calibration Curve
A calibration curve is used to determine the unknown
concentration of an element in a solution. The
instrument is calibrated using several solutions of
known concentrations. The absorbance of each
known solution is measured and then a calibration
curve of concentration vs absorbance is plotted.

The sample solution is fed into the instrument, and

the absorbance of the element in this solution is
measured .The unknown concentration of the
element is then calculated from the calibration curve
 Atomic Absorption Spectroscopy
• It is possible to measure the concentration of an
absorbing species in a sample by applying the
Beer-Lambert Law:

 I  Abs  cb
Abs   log 
Io 

 = extinction coefficient 28
Atomic Absorption Spectroscopy
• But what if  is unknown?
• Concentration measurements can be made from a
working curve after calibrating the instrument
with standards of known concentration.

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 AAS - Calibration Curve

The instrument is calibrated before use by testing the •

.absorbance with solutions of known concentration

Consider that you wanted to test the sodium content •

.of bottled water

The following data was collected using solutions of •

sodium chloride of known concentration

Concentration (ppm) 2 4 6 8
Absorbance 0.18 0.38 0.52 0.76
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 Calibration Curve for Sodium

A
b 1.0

s
o 0.8

r 0.6
b
a 0.4

n
c 0.2

e
2 4 6 8

Concentration (ppm) 31
 Use of Calibration curve to determine sodium
concentration {sample absorbance = 0.65}

A
b 1.0

s
o 0.8

r 0.6
b
a 0.4

n Concentration
c 0.2
Na+ = 7.3ppm
e
2 4 6 8

Concentration (ppm) 32
 Interferences
The concentration of the analyte element is
considered to be proportional to the ground state
atom population in the flame ,any factor that affects
the ground state atom population can be classified
as an interference .

Factors that may affect the ability of the instrument to

read this parameter can also be classified as an
interference .
 The different interferences that are encountered in atomic
absorption spectroscopy are :

- Absorption of Source Radiation : Element other than the

one of interest may absorb the wavelength being used.

- Ionization Interference : the formation of ions rather than

atoms causes lower absorption of radiation. This problem
is overcome by adding ionization suppressors.
- Back ground Absorption of Source Radiation :
This is caused by the presence of a particle from
incomplete atomization . This problem is overcome
by increasing the flame temperature.

- Transport Interference :
Rate of nebulization, or transport of the sample (e g
viscosity, surface tension, vapor pressure, and
density) .
 1. Spectral Interferences:

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

e.g. a vanadium line at 3082.11Å interferes in an analysis
based upon the aluminum absorption line at 3082.15 Å.

• to choose an alternate analytical wavelength. The

interference of aluminium from vanadium can be avoid by
employing the aluminum line at 3092.7 Å instead.
• to remove the interfering element from the sample.
(II) A common occurrence that results in spectral interference is absorption of
the HCL radiation by molecules or polyatomic species in the atomizer.
This is called “background absorption”; it occurs because not all of the
molecules from the sample matrix and the flame gases are completely atomized.
This type of interference is more commonplace at short wavelengths
(<250 nm) where many compounds absorb.
Incomplete combustion of organic molecules in the atomizer can cause
serious background interference problems. If a flame atomizer is used,
incomplete combustion of the solvent may take place.
The molecular absorption may come from hydroxyl radicals generated
from water in the flame, incomplete combustion of organic solvent, stable
molecular residues, metal oxides, and so on.
• The extent of the interference depends on flame
conditions, the flame temperature used, the solvent
used, and the sample aspiration rate.

• Matching the solutions in the working standards to the

sample solutions can compensate for matrix or solvent
interferences.

• This correction method is totally automated in modern

AAS systems. The HCL are monitored alternately in
time; instrument electronics compare the signals, and
calculate the net atomic absorption.
 (III) Source of absorption or scattering can be
originated in the sample matrix. An example of
a potential matrix interference due to
absorption occurs in the determination of
barium in alkaline earth mixture.
Exampel: 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.
 (IV) Concentrated solution of elements
such as Ti, Zr and W which form refractory
oxides can cause spectral interference due
to scattering.

• Interference due to formation of refractory

oxides can often be eliminated or
moderated by use of higher temperatures.
 2. Chemical Interferences:

(I) Formation of Compounds of Low Volatility: The most

common type of interference is by ions that form
compounds of low volatility with the analyte and thus
reduce the rate at which the analyte is atomized.
For example, a solution of calcium chloride, when atomized in
an air–acetylene flame, decomposes to calcium atoms more
readily than a solution of calcium phosphate.
Calcium phosphate is more thermally stable than calcium
chloride.
A solution of calcium chloride containing 10 ppm Ca will give a
higher absorbance than a solution of calcium phosphate
containing 10 ppm Ca.
If phosphate ion is added to a solution of calcium chloride,
the absorbance due to Ca will decrease as the concentration
of phosphate increases.
Interference due to formation of species of low volatility
can often be eliminated or moderated by use of higher
temperatures.

• Releasing agents which are cations that react

preferentially with the interferant and prevent its
interaction with the analyte, can be employed.
For example, lanthanum forms a very thermally stable
phosphate, more stable than calcium phosphate.

• Protective agents prevent interference by forming

stable but volatile species with the analyte. Three
common reagents for this purpose are EDTA, 8-
hydroxyquinoline, and APDC (ammonium salt of 1-
pyrrolidinecarbodithioic acid).
(II) Ionization Equilibria: Ionization of atoms and
molecules is small in combustion mixtures that
involve air as the oxidant, and generally can be
neglected. In higher temperatures of flames
where oxygen or nitrous oxide serves as the
oxidant, however, ionization becomes important,
and a significant concentration of free electrons
exists as a consequence of the equilibrium
M M+ + e -
The equilibrium constant K for this reaction takes
the form
K= [M+][e-]
[M]
If the flame is hot enough for significant excitation and
ionization to occur, the absorbance signal is decreased
because the population of ground state atoms has
decreased as a result of ionization and excitation.

• Adding an excess of a more easily ionized element to all

standards and samples eliminates ionization interference.
This addition creates a large number of free electrons in the
flame. The free electrons are “captured” by the analyte ions,
converting them back to atoms. The result is to “suppress”
the ionization of the analyte.
• Elements often added as ionization suppressants are
potassium, rubidium, and cesium.
 3. Physical Interferences:
• Variation of instrument parameters such as
uptake in the burner and atomization
efficiency (gas flow rate, sample viscosity etc.)
• Differences in viscosity between the standard solutions
and the samples, or between different samples, will
result in interference.
Interference due to viscosity occurs in the nebulization
process.
For FAAS, different volumes of solution will be
aspirated in a given period of time and nebulization
efficiency will change as a result of the solvent
characteristics.
Metals in aqueous solutions give lower absorbance
readings than the same concentration of such metals
in an organic solvent.
 AAS APPLICATIONS
The are many applications for atomic
absorption:
- Clinical analysis : Analyzing metals in
biological fluids such as blood and urine.
- Environmental analysis : Monitoring our
environment – e g finding out the levels of
various elements in rivers, seawater, drinking
water, air, and petrol.
- Pharmaceuticals. In some pharmaceutical
manufacturing processes, minute quantities of a
catalyst used in the process (usually a metal) are
sometimes present in the final product. By using
AAS the amount of catalyst present can be
determined.
- Industry : Many raw materials are examined and
AAS is widely used to check that the major elements
are present and that toxic impurities are lower than
specified – e g in concrete, where calcium is a major
constituent, the lead level should be low because it is
toxic.
- Mining: By using AAS the amount of metals
such as gold in rocks can be determined to see
whether it is worth mining the rocks to extract
the gold .

- Trace elements in food analysis

- Trace element analysis of cosmetics
- Trace element analysis of hair