Atomic Absorption Spectroscopy

（ AAS ）

BY

PANKAJ KUMAR
OCS-GmbH
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Atomic Absorption Spectroscopy
（ AAS ）

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

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 Introduction
Atomic Absorption Spectroscopy (AAS)
is an analytical technique that measures
the concentrations of elements.
AAS is a standard instrument for
the determination of metal, widely
applied of samples, such as
water , agriculture chemical, clinical and
biochemistry, minerals, food and
drugs, environmental and other.
 AAS Applications
Atomic absorption spectrometry has many uses in different areas of chemistry
( Fe, Mg, Al, Ca, Na, K, V, Cu, Cr, Zn and other metal).

1.Clinical analysis :Analysing metals in biological fluids such as blood and urine
(Fe,Na,K and other).
2.Environmental analysis: various elements in rivers, seawater, drinking water, air,
petrol and drinks such as wine, beer and fruit drinks (Na,K,Ca,Fe,Zn and other).
3.Industry: (Na ,Fe, K,Ca,Zn,Mg,V,Al)

Test method ASTM

Total Metal D 4309 02
Iron D 1068 05
Sodium D 4191 08
Aluminium D 857 07
Arsenic D 2972 08

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 What is AAS ?

• An atomic absorption spectrophotometer

consists of main three part ,a light source,
a sample compartment and a detector.

3.Detector 1.Light Source

2.Sample
Compartment
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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, 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.
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 Principle of Atomic Absorption
Spectrophotometer

Principle of the Atomic Absorption

Method
The atomic absorption method uses as its
light source a hollow cathode lamp which
emits light of a wavelength that is
particular to each element. Elements
within a solution are heated in a flame or
electrically (2000°C to 3000°C) and
subsequently determined using the fact
that the degree of absorption will vary Light absorption
process of atoms
with its concentration.

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Principle of Atomic Absorption
Spectrophotometer

Atomic Absorption Spectroscopy,

AAS
Excited state E1

Absorption

Ground state E0

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 Relation between light
absorption and concentration
• When light of a certain intensity is given to
many atom in ground state, part of this light is
absorbed by atoms. Electronic Transition
C

I0 I

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Relation between light absorption
and Concentration
Lambert-beer’s Law

Concentration C

I0 I
Abs = -logI/I0 = k .l. C

Abs ᾀC
l
k : proportional constant
l : path length
C : concentration
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 Instrumentation

Line
source Atomization Monochromator Detector

Nebulizer Read-out

Schematic diagram of a flame spectrophotomer

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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)

Elements WL(nm) WL(nm)

Al 309.3 396.2
Na 589.0 589.6
Mg 285.2 202.6
K 766.5 769.9
Ca 422.7 239.9
Ti 364.3 365.4
V 318.5 306.6
Cr 357.9 429.0
Fe 248.3 372.0
Cu 324.8 327.4
Zn 213.9 307.9
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SpectrAA - AAS

Hollow
cathode
Lamp

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 Sample atomization technique
Flame 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

flame Auxiliary
oxidant

Fuel

b Air – acetylene
b Nitrous oxide – acetylene

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 Flame Method
Flame selection
• These flames vary in temperature, reducibility and
transmission characteristics.
• Selected according to the element being analyzed,
and properties of the sample.
• Air-acetylene : Temp. (max 2,300) 0C
(For (Mg, Zn, Fe, Cu, etc.))
• Nitrous oxide-acetylene : Temp.(max 2,955 )0C
(For elements (Al,V, Ti, etc.)

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Disadvantages of flame atomization

Only 5 – 15 % of the nebulized sample

reaches the flame

A minimum sample volume of 5.0 – 10.0

mL is needed to give a reliable reading

Samples which are viscous require dilution

with a solvent

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Detector

--- photomultiplier

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Atomic absorption spectrophotometer

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Interferences

Physical interferences

Spectral interferences

Chemical interferences

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 Physical interference
Spray efficiency fluctuations due to difference in viscosity and
surface tension between the standard and sample.(Food sample)

Spectral interference
Spectral absorption line overlapping with the absorption line of the target
element,Absorption and scattering by molecules

Target element Spectral line Interfering Spectral line

(nm) element (nm)
Al  V 
Ca  Ge 
Cd  As 
Co  In 
Cu  Eu 
Fe  Pt 
Ga  Mn 
Hg  Co 
Mn  Ga 
Sb  Pb 
Si  V 
Zn  Fe 

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 Chemical interference
Generation of non-separable compounds by
coexisting matrices
Example : influence of PO4-, SO4-2, relative to Ca, Mg

in flame analysis
(generation of Ca2PO4)

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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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Preventive Maintenance / Calibration
of
Atomic Absorption
Spectrophotometry

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AAS Instrument Calibration
1. Absorption
- Using Cu hollow cathode lamp
- Standard Cu 5 ppm
- Measured value more than0.50 Abs
2. Repeatability
- Using Cu hollow cathode lamp
- Standard Cu 5 ppm
- Measure 5 time and CV(coeffient of variation) value < 2%

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 Preventive Maintenance
1. Cleaning the Burner head

Clogged Normal
(by carbide or salt
etc.)
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 2. Cleaning the Chamber with diluted
water
3. Cleaning the Nebulizer

Cleaning wire

4. Periodically checked o-ring if damanged please

changed.
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Pre-analysis checklist
The general preparation procedure is as follows:
1. Ensure the exhaust system is working. To do this, hold a thin
single-ply tissue up to the mouth of the extraction hood. The
tissue should be drawn towards the hood.
2. Check the gas supplies to make sure you have enough gas to
complete your analysis. You must also check that the acetylene
cylinder pressure is above 700 kPa (about 100 psi) to ensure that
acetone is not drawn into the instrument. (Acetone in the spectrometer can
damage seals, O-rings and hoses, degrade analytical performance and
precipitate flashbacks. Minimize the amount of acetone which is carried
over).
3. Set the delivery pressure of the gases to the following:
Recommended Permissible
Acetylene 9.5–14.5 psi
Air 35–65 psi
Nitrous oxide 35–65 psi
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4. Inspect the gas hoses for damage, replacing any damaged hoses.
Turn on the gas supplies to your instrument and test all hoses and
connections for leaks. If a leak is found, rectify the problem
immediately.
5. Load a worksheet and develop the method(s) as per your
analytical requirements.
6. Optimize the system.
7. Start an Autorun.

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Thanks

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