Atomic Absorption Spectroscopy (AAS)

• Technique to determine metal element

• Qualitative and quantitative analysis of more
than 70 elements
• Detect ppm or ppb concentration
• Rapid, convenient, high selectivity

Dr. Maha Daghestani

 Principle of AAS
• AAS is based upon the principle that-
➢ Free atoms in the ground state can absorb light
of a certain wavelength.
➢ The amount of light absorbed at this wavelength
is directly proportional to the concentration of
the absorbing ions or atoms.
➢ These very specific wavelengths give the
technique excellent specificity and detection
limits in the AAS analysis.
➢ Absorption for each element is specific, no other
elements absorb this wavelength.
Energy levels in a lead (Pb) atom
energy equivalent to light at 283.3 nm.
Introduction to the Principles of Atomic Spectroscopy
• Liquid sample is aspirated to become aerosols of fine particles
(nebulization)
• Flame vaporizes the aerosols (atomization)
• Elevated temperatures in a flame or furnace changes the
chemistry of atoms
• Temperature affects the ratio of excited and unexcited atoms
• Beer’s law is used to calculate concentration
Process occurring in flame for a solution
containing CaCl2
Processes Occurring in Flame and Flameless Furnace
• e.g. Calcium present as a salt (CaCl2):
1. Removal of water produces gaseous CaCl2
2. gaseous CaCl2 is further dissociated into gaseous Ca0 atoms
At elevated temperatures Ca can have other electronic states:
3/4. Ca0* (excited Ca atom),
5. Oxide/Hydroxide formation
6. Ca+ (ionic Ca),
7. Ca+* (ionic Ca with excited e-)
Atomic absorption spectroscopy is based on the same
principle as the flame test used in qualitative analysis.
❑Each element has a characteristic spectrum.
Example: Na gives a characteristic line at 589 nm.

❑Atomic spectra feature sharp bands.

There is little overlap between the spectral lines of different

elements.
Instrumentation
Schematic diagram of an atomic absorption spectrometer
Schematic representation of a double-beam atomic
absorption spectrophotometer
• Basic instrument components:

1. Light source: Hollow cathode lamp (HCL) of the

element being measured. Provides the spectral line for the element of
interest.
Working:
When a high voltage is applied across the anode and
cathode, gas particles are ionized. As voltage is increased,
gaseous ions acquire enough energy to eject metal atoms
from the cathode. Some of these atoms are in an excited
states and emit light with the frequency characteristic to
the metal.
• The type of hollow cathode tube depends on
the metal being analyzed.
• For analyzing the concentration of copper in an
ore, a copper cathode tube would be used, and
likewise for any other metal being analyzed.
• The electrons of the atoms in the flame can be
promoted to higher orbitals for an instant by
absorbing a set quantity of energy (a quantum).

Dr. Maha Daghestani

It is important to note that both emission &
absorption lines for sodium occur at identical
wavelengths since transition involved are between
same energy levels.
• https://www.youtube.com/watch?v=M5jyQp
Nkjcw&t=175s
• https://www.youtube.com/watch?v=CzULc31y
YkU
 The Lamps

From bottom to top,

the lamps are for Mg,
Ca, K, and a
combination of Fe,
Co, Ni, Mn, Cu, and Cr.
Each element uses a
specific wavelength of
light.
What is a nebulizer?

SAMPLE
AEROSOL
 Cross-flow

Concentric Tube
Fritted-disk
Babington
(FAAS) (GFAAS)
 Nebulization
– In FAAS a liquid sample is nebulized – aspirated into small
liquid particles (aerosols), remaining larger droplets condense
out (only around 10 % of fine aerosols reach the burner)
• Atomization = conversion of element into atomic vapor
– In FAAS nebulization takes place prior to atomization making
the process far less efficient than GFAAS
– In GFAAS the entire sample is atomized inside the graphite
boat leading to lower detection limits
Atomization
Desolvation and vaporization of ions or
atoms in a sample:

In a flame system (a), the

nebulizer sucks up the
liquid sample, creates a fine
aerosol, mixes the aerosol
with fuel/air. Flame creates
vaporized atoms.
• Two flames are normally used in AAS
Air-acetylene flame : slot length 100 mm, most
commonly used , cooler flame 2500 K
Nitrous oxide-acetylene flame: slot length 50 mm,
higher burning velocity, hotter flame 3150 K reserved
for more refractory elements e.g Al
Limitations of Flame AAS
✓ Require large volumes of aqueous sample
✓ The residence time i.e. the length of time that the
atom is present in flame, is limited due to high burning
velocity of the gases, ths leading to high detection
limits
✓ Inability to analyse solid samples directly
ElectroThermal AAS (ETAAS or GFAAS)
• A small discrete sample (5-100µl) is introduced on to the inner
surface of a graphite tube through a small opening.
• Graphite tube is arranged so that light from HCl can pass
directly through the unit. The tube is 3-5 cm long, 3-8 mm
diameter
• Pyrolytic graphite (heating tube in methane atmosphere) as it
has low gas permeability & resistant to chemical attack.
• The furnace is heated by passing an electrical current through
it (thus, it is electro thermal) via water cooled contacts at each
end of the tube
• To prevent oxidation of the furnace, it is sheathed in gas (Ar
usually)
• There is no nebulization, etc. The sample is introduced as a
drop (usually 5-20 uL), slurry or solid particle (rare)
 ElectroThermal AAS (ETAAS or GFAAS)
• The furnace goes through several heating steps…

– Drying (usually just above 110 ˚C. for 30s):to remove residual
solvent
– Ashing (up to 350-1200 ˚C for 45 s)
– Atomization (Up to 2000-3000 ˚C for 2-3 s)
– Cleaning (quick ramp up to 3500 C or so). Removal of residual
material
there is an internal flow of inert gas N2 or Ar during drying &
ashing stages to remove extraneous material

• The light from the source (HCL) passes through the furnace and
absorption during the atomization step is recorded over several
seconds. This makes ETAAS more sensitive than FAAS for most
elements.
 The Calcium Flame

The calcium
flame is
red. This is
intensely
red
because
the calcium
content is
high.
The Copper Flame
The Potassium Flame
The Manganese Flame
The Cobalt Flame
 Category AAS AES or Flame
Photrometry
Definition Find concentration of Find concentration of metal by
metal by absorption emission
Principle Absorption of light by Emission of light by electrons
electrons
Transition Ground to excited state Excited to ground state
EMR Absorbed Emitted
Source of light Hollow cathode lamp Flame
Intensity of emitted Intensity of emitted radiation
radiation is directly is directly proportional to no.
proportional to no. of of atoms in ground state
atoms in excited state
Absorption does not depend on greatly influenced by temp
intensity & temp. variation
signal
response
Applications of Atomic Absorption Spectroscopy

❑ water analysis (e.g.Ca, Mg, Fe, Si, Al, Ba content)

❑ food analysis; analysis of animal feed stuffs ( e.g. Mn, Fe, Cu,
Cr, Se, Zn)
❑ analysis of additives in lubricating oils and greases (Ba,Ca, Na,
Li, Zn, Mg)
❑ analysis of soils
❑ clinical analysis (blood samples: whole blood, plasma, serum;
Ca, Mg, Li, Na, K, Fe)
Detection Limits
 Quiz
1. Which of the following is the principle of Flame
emission photometers?
a) Radiation is absorbed by non-excited atoms in
vapour state and are excited to higher states
b) Medium absorbs radiation and transmitted
radiation is measured
c) Colour and wavelength of the flame is measured
d) Only wavelength of the flame is measured
Answer: C
2.Which of the following is the principle of Atomic
Absorption Spectroscopy?
a) Radiation is absorbed by non-excited atoms in vapour state and
are excited to higher states
b) Medium absorbs radiation and transmitted radiation is
measured
c) Colour is measured
d) Colour is simply observed
Answer: a
 Quiz
3.In Atomic Absorption Spectroscopy, which of the
following is the generally used radiation source?
a) Tungsten lamp
b) Xenon mercury arc lamp
c) Hydrogen or deuterium discharge lamp
d) Hollow cathode lamp
Answer: d
 Quiz
4.In Atomic Absorption Spectroscopy, which of the
following is the generally used radiation source?
a) Tungsten lamp
b) Xenon mercury arc lamp
c) Hydrogen or deuterium discharge lamp
d) Hollow cathode lamp
Answer: d
 Quiz
5. In Atomic Absorption Spectroscopy, which of the
following is the generally used radiation source?
a) Tungsten lamp
b) Xenon mercury arc lamp
c) Hydrogen or deuterium discharge lamp
d) Hollow cathode lamp
Answer: d
6.In Total consumption burner, only samples of particular
droplet size will enter the burner.
false
7. In Flame emission photometers, the measurement of
_____________ is used for qualitative analysis.
a) Colour b) Intensity
c) Velocity d) Frequency
Answer- a

8.Which of the following is not an advantage of Laminar

flow burner used in Flame photometry?
a)Noiseless
b) Stable flame for analysis
c) Efficient atomization of sample
d) Sample containing two or more solvents can be burned
efficiently
Answer- d
• In AAS, with what material is the cathode in Hollow
cathode lamp constructed?
a) Tungsten
b) Quartz
c) Element to be investigated
d) Aluminium
Answer-C
Which of the following is the function of the chopper in
Atomic Absorption Spectroscopy?
a) To split the beam into two
b) To break the steady light into a pulsating light
c) To filter unwanted components
d) To reduce the sample into atomic state
Answer- b
Atomic Absorption Overview