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BASED ON FLAME
ATOMIZATION; THEORY,
INSTRUMENTATION AND
APPLICATION
CHAPTER 3
FLAME ATOMIC ABSORPTION
SPECTROSCOPY
LECTURE 7
This lecture covers:
Fundamental Principals
Sample Atomization
Flame atomizer
Properties of flame
Instrumentation for Flame Atomic Absorption
Spectroscopy
Interferences
Quantitative Analysis by Atomic Absorption
Spectroscopy
Detection Limits and Accuracy
Introduction
Atoms are the simplest and purest form a matter
and cannot rotate or vibrate as a molecules does.
Atoms only undergoes electronic transitions when
energy is absorbed.
Because the electronic transitions are discrete
(quantized), line spectra are observed.
Applications of atomic spectroscopy:
Analysisof heavy metals contaminations in
environmental samples.
◼ Examples of heavy metals are the transition metals, some
metalloids, lanthanides and actinides.
Metal impurities in pharmaceutical samples
Three techniques (methods) included in atomic
spectroscopy:
Atomic Absorption Spectroscopy (AAS)
Atomic Emisssion Spectroscopy (AES)
Absorbance = -log(P/Po)
P = Power of transmitted radiation
Po = Power of incident radiation
A = -log(P/Po)
Po P
Nebulizer
Aspiration
Fine capillary
tube
The absorption is shown on a read out by the data
system.
This absorption follows Beer’s law i.e. absorbance is
directly proportional to the path length in the flame
and to the concentration of atomic vapor in the
flame.
Concentration of atomic vapor directly proportional
to the concentration of the analyte in the solution
being aspirated.
Sample Atomization
In order to perform atomic spectroscopy, atoms of the
analyte must first be formed, usually in the form of an
atomic vapor.
Atomization: The process by which a sample is
converted to an atomic vapor or elementary ions.
Atomizer: Device used to converted a sample to an
atomic vapor.
Two common methods of sample atomization:
Flame atomization
Electrothermal atomization
Process occurs during atomization
Nebulization
Conversion of the liquid
sample to a fine spray.
Desolvation
Solid atoms are mixed with
the gaseous fuel.
Volatilization
Solid atoms are converted to
a vapor in the flame
(molecules/atoms/ions.)
There are three types of particles that exist in the flame:
Atoms
Ions
Molecules
QUESTION
1. Define the terms (3m – Mar 2016)
Nebulization
Atomizations
Types of Flames
Acetylene / N2O flame is
the best for refractory
elements.
Elements that form
stable compounds that
are not completely
atomised at the
temperature of the
flame or graphite
furnace.
Selection of flame type depends on the depends on the
volatilization temperature of the atom of interest.
Flames are only stable at certain flow rates:
at low flow rates (less than the maximum burning
velocity) the flame propagates into the burner body
causing flashback and, in some cases, an explosion.
when the flow rate is increased, the flame starts to rise
above the burner body.
best flames are obtained when the flow rate of the gas
is equal to the maximum burning velocity. At this equity
ratio the flame is most stable.
at higher ratios, flames will reach a point where they
will no longer form and blow off the burner.
Flame Structure
Interzonal region is the hottest
part of the flame and best for
atomic absorption.
Oxidation of the atoms occurs
in the secondary combustion
zone where the atoms will form
molecular oxides and are
dispersed into the surroundings.
Temperature Profile
Disadvantages
1. A relatively short path length through flame.
2. Problems with clogging of the tip.
3. Burners noisy from electronic and auditory stand point.
◼ Laminar flow burner
◼ Sample is nebulized by the flow of oxidant past a capillary tip.
◼ Resulting aerosol then mixed with fuel and flows past a series of
spoilers (baffles) that allow only the finest droplets to reach the burner
head.
Fine
droplets
◼ The larger droplets of the resulting aerosol condense and drain out of
the chamber to a waste container (~90%).
◼ Aerosol, oxidant and fuel are burned in a slotted burner that provided
a flame, 5 – 10 cm in length.
Fine
droplets
Function of nebulizer:
Suck up liquid sample at a controlled rate.
Create a fine aerosol (nebulization) for introduction into
the flame.
Mix the aerosol and fuel and oxidant thoroughly for
introduction into the flame (desolvation).
Disadvantages
1. Lower rate of sample introduction.
2. Possibility of selective evaporation of mixed solvents in the
mixing chamber could create analytical uncertainties.
3. Mixing chamber contains a potentially explosive mixture
that can flash back if the flow rates are too low.
Performance characteristics of flame
atomization
Flame atomizers have good precision (<1% relative precision).
Relatively low sensitivity compared to electrothermal
atomization.
There are two reasons for the low sampling efficiency of flame
atomizers:
Most of the sample is wasted due to the nebulization
process.
Atoms have a short residence times in the flame (~10-4 s).
Instrumentation
The absorption of the lamps
emission spectrum by atoms
in the flame
Monochromator Detector
Laminar- Readout
flow burner
(consist of
nebulizer)
chopper
Sample
AAS
Furnace
AA Spectrophotometers
Single Beam Instrument
◼ Components in HCL:
◼ A cylindrical hollow cathode made of the element to be
determined or an alloy of it.
◼ Tungsten anode.
◼ Enclosed in a glass tube usually with a quartz or pyrex window
since the lines of interest are often in UV region.
◼ Tube is under reduced pressure and filled with inert gas such as
Ne or Ar.
Hollow cathode lamp element Na
Ar + e- Ar+ + 2e-
2. Cation interferences
◼ Example: Determination of Mg in the presence of Al
C = kVxCx
m kCstd
Cx = CCstd
mVx
For single-point standard addition
Dividing the 2nd equation by the first & then rearrange it
will give.
Cx = A1 Cs Vs
(A2 – A1 ) Vx
Example
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