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• AAS was employed in the 1950’s

• Used for qualitative and


quantitative detection.

• It’s used for the determination of


the presence and concentrations of
metals in liquid samples.

• Metals that can be detected include


Fe, Cu, Al, Pb, Ca, Zn, Cd and
many more.

• Concentrations range is in the low


mg/L (ppm) range.
4. The element in the sample
will absorb some of the light,
thus reducing its intensity

5. The monochromator
3. A beam of UV light will isolates the line of
be focused on the sample interest

1. We set the instrument


at certain wavelength
suitable for a certain 2. The element in
element the sample will
be atomized by 6. The detector
heat measures the change in
intensity

7. A computer data system


converts the change in
intensity into an absorbance
1.Light source

Hollow Cathode Lamp Laser


Laser:
They are intense enough to
excite atoms to higher energy
levels. This allows Atomic
Absorption and atomic
fluorescence measurements in
a single instrument.
The disadvantage of both the HCL and laser is that they
have narrow-band light sources and so only one element is measurable
at a time.
2. Atomiser

Flame Graphite Furnace Hydride


3.Light Separation

Monochromator:
used to isolate the absorption line from
background light due to interferences.

Note:
Simple dedicated Atomic Absorption (AA) instruments often replace the
monochromator with a bandpass interference filter.
4.Detectors

Photomultiplier tubes
• The technique requires a
liquid sample to be
aspirated, aerosolized,
and mixed with
combustible gases, such as
acetylene and air or
acetylene and nitrous
oxide.
• The mixture is ignited in a
flame whose temperature
ranges from 2100 oC to
2800 ºC.
4. The mixture flows
immediately into the
burner head.
5. It burns as a smooth,
laminar flame evenly
distributed along a narrow
slot.

1. mixes acetylene (the fuel)


and oxidant
(air or nitrous oxide). 3. The result is a heterogeneous mixture
of gases (fuel + oxidant) and suspended
aerosol (finely dispersed sample).

2. A negative pressure is formed


at the end of the small diameter,
plastic nebulizer tube
(aspiration).
6. Liquid sample not
flowing into the flame
collects in the waste.
The process of lighting the AAS flame involves:
turning on first the fuel then the oxidant and then lighting
the flame with the instrument's auto ignition system.

The flame breaks down the analyte's matrix  create the


elemental form of the analyte atom.
During combustion, atoms of the element of
Interest in the sample are reduced to free,

unexcited ground state atoms, which absorb light at


characteristic wavelengths,
as shown in the figure.
Consists of a cathode and an anode. The cathode is made of
the element of interest

1) A large voltage across the anode and cathode will cause the inert gas to ionize.

2) The inert gas ions will then be accelerated into the cathode, sputtering off atoms
from the cathode.

3) Both the inert gas and the sputtered cathode atoms will in turn be excited by
collisions with each other.
4) When these excited atoms decay to lower energy levels
they emit a few spectral lines characteristic of the
element of interest.

5) The light is emitted directionally through the lamp's


window, a window made of a glass transparent in the UV
and visible wavelengths.

6) The light can then be detected and a spectrum can be


determined.
1. Aspirating a solution containing the element

2. Adjusting the fuel/oxidant mix until the maximum light


absorbance is achieved.

3. Careful control of the fuel/air mixture is important


because each element's response depends on that mix in
the burning flame.
The light passes from the HCL
through the element in the
sample to the
monochromator.
Its function is:
It isolates the specific
light of the element of
interest from the other
background lights and
transfers it to the
photomultiplier tube
(detector).
Before an analyte is aspirated, a
measured signal is generated by the
PMT as light from the HCL passes
through the flame.

When analyte atoms are present in


the flame--while the sample is
aspirated--some of that light is
absorbed by those atoms.

This causes a decrease in PMT


signal that is proportional to the
amount of analyte
The PMT detects the amount of reduction of the light
intensity due to absorption by the analyte, and this can be
directly related to the amount of the element in the sample.

The PMT converts the light signal into an electrical


signal and a computer system translates it into
absorbance.
Light Photocathode
e-

Dynode

Dynode

Dynode

Current

Convert light energy to electrical energy


Different flames can be achieved using different mixtures
of gases, depending on the desired temperature and burning
velocity.

Some elements can only be converted to atoms at high


temperatures.

Some metals form oxides that do not re-dissociate into


atoms. To inhibit their formation, conditions of the flame
may be modified to achieve a reducing, non-oxidizing flame.
(GFAAS) Graphite Furnace
Atomic Absorption
Spectroscopy

(ETAAS) Electro thermal


Atomic Absorption
Spectrometry
5. The monochromator isolates the light of the
element of interest from the background lights 4. The graphite tube is 1. The source of light (lamp)
to the PMT. The PMT tube measures the permanently flushed with argon emits light with a wavelength
change intensity. while it is in operation specific to the element of
interest

2. A controlled voltage is applied at the


3. Samples are deposited in the graphite tube 
ends of the graphite tube, which is
heated to vaporize and atomize the analyte  atoms
heated rapidly to high temperatures (up
absorb ultraviolet or visible light and make
to 2600°C).
transitions to higher electronic energy levels.
Small sample
Formation of stable Thermal oxide (Al, Mo, Ti)
Residual elements
Biological samples
Effective atomization
Sample stay for Long time in graphite tube>>>high sensetivety
Suitable for solid samples
Ionic interferase rather than chemical or physical due to high
temp.
Free mercury atoms can exist at room temperature can be
analysed using atomic absorption without employing flame and
graphite furnace techniques at high temperatures.
• Mercury is reduced in solution using stannous chloride or
sodium borohydride in a closed system.
• The reaction quantitatively releases mercury (from the
sample solution) and is carried by a stream of air or argon
through a quartz sample sell placed in the light path of an
AA instrument for analysis.
• The detection limit for mercury by this cold vapor technique
is approximately 0.02 mg/L.
It’s used for elements that are forming volatile hydrides
(e.g. As, Se, pb, Sb, Te, Sn, Bi)
(HAAS) is very useful in case of interferences, poor
reproducibility, and poor detection limits.
4. The PMT detects the amount of
reduction of the light intensity due to 1. The HCL emits the light
absorption by the analyte and can be with a wavelength
directly related to the amount of the characteristic to the element
element in the sample of interest

3. The monochromator isolates


analytical lines' photons passing
through the optical cell 2. The Light passes from the HCL
and removes the scattered light of through the optical cell to the
other wavelengths from the optical cell monochromator then to the
detector
4. In the optical cell the flame is ignited automatically by the
air/C2 H 4 and the gaseous 3. The liquid mixture flows
metal hydride form decomposes into the elemental form which into a gas/liquid separator where
can absorb the the hydride and some gaseous hydrogen are
HCL's beam. The light passes to the Mon. and then to the PMT purged (via a high purity inert gas) into the optical cell
via a gas transfer line

Optical cell

Volatile Hydride
Gas liquid
separator

Mixing
peristaltic
pump
reaction
coil
1. The metal oxyanions reacts with Sodium 2. The peristaltic pump and the flowing reagents along with
Borohydride and HCl and produces a the tubing of specific lengths controls the time from reagent
volatile hydride: H2Te, H2Se, H3As, H3Sb, mixing and separation of
etc. the volatile hydride from the
liquid and sending the sample to the optical cell.
Any factor that affects the ground state population of the analyte
element.
Factors that may affect the ability of the instrument to read this
parameter.

A) Spectral interferences: due to radiation overlapping than


of the light source.

B) Formation of compounds that do not dissociate in the


flame.
The most common example is the formation of calcium and
strontium phosphates.
C) Ionization of the analyte reduces the signal.
This is commonly happens to barium, calcium, strontium,
sodium and potassium.

D) Matrix interferences: due to differences between surface


tension and viscosity of test solutions and standards.

E) Broadening of a spectral line

1. Doppler effect
2. Lorentz effect
3. Quenching effect
4. Self absorption or self-reversal effect

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