Atomic Spectrophotometry
Atomic Spectrophotometry
Outline
Introduction
Instrumentation
Atomic Spectrophotometry 2
Introduction
Atomic Spectrophotometry 3
Introduction….
Advantages
Highly specific
Wide application
Speed
Convenience
Atomic Spectrophotometry 4
Introduction….
Characteristics of Atomic Spectroscopy
Atomic Spectrophotometry 5
Atomization
Atomization
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Atomization…
The Atomization
Three steps are involved in turning a liquid
Process
sample into an atomic gas:
Nebulization - Conversion of the
liquid sample to a fine
spray.
Desolvation - removal of solvent.
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Atomic spectrometric techniques
There are three basic analytical atomic spectrometric techniques:
1- Atomic Absorption Spectrometry (AAS)
2- Atomic Emission Spectrometry (AES)
3- Atomic Fluorescence Spectrometry (AFS)
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Atomic Absorption Spectroscopy
(AAS)
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Introduction to AAS
AAS is the study of the absorption of radiant energy by
atoms.
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Elements that are highlighted in pink are detectable by AAS
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Introduction to AAS…
Basic Principle
In AAS, the sample solution is first vaporized and atomized in
a flame or furnace.
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Instrumentation
The main parts of the A.A.S. equipment is similar to that used in other
spectroscopic absorption methods, but with addition of a device for
atomization and other small differences in light sources and data correction.
I0 It
Light Source Detector Amplifier
E.g. Hollow
Fuel (e.g. acetylene)
cathode lamp Atomizer Air
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Radiation Sources for AAS…
How a HCL Works?
An applied potential of ~ 300 V DC ionizes the inert gas present
at the anode surface;
Ne (g) -----> Ne+* (g) + e-
These gaseous ions bombard the cathode and eject metal atoms
from the cathode in a process called sputtering.
Some sputtered atoms are in excited states and emit radiation
characteristic of the metal as they fall back to the ground state
The light lines emitted are so narrow that they can be almost
completely absorbed by the sample atoms
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Radiation Sources for AAS…
Each HCL emits only spectrum of the metal used in the cathode
e.g. copper cathodes emit copper spectrum and only the copper
atoms (in sample) absorb copper resonance lines generated.
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I. Flame Atomizers
The most important component in any flame emission or atomic
absorption spectroscopy is the nebulizer-burner system.
This system converts the test substance in the sample solution to atomic
vapor and, also in emission, excites the neutral atoms (or molecules) to
emit their characteristic radiation.
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Simplest system: Flame Atomization
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I. Flame Atomizers…
(A) Total consumption Burners
In total consumption burner the oxidant, fuel
and sample all meet for the first time at the base
of the flame.
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I. Flame Atomizers…
(B) Premix burners
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I. Flame Atomizers…
About 90% of the sample is lost in the premix chamber this
resulting in less liquid sample entering the flame than in total
consumption burner, but with very small droplets and very
easily decomposed.
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Disadvantages:
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I. Flame Atomizers…
Atomization by using burners Oxidant
(Flame) is not very efficient but
generally easy to be used, Fuel Air O2 N2O
non expensive and
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I. Flame Atomizers…
Temperature Profiles
Flame temperature and position are critical for
achieving reproducible atomization
Flame Absorption Profiles
Note that: The most sensitive part of flame for
AAS varies with the type of analyte
Consequences?
-sensitivity varies with the type of elements
-must maximize the burner position
-makes multielement detection difficult
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II. Electrothermal Atomizers …
Atomization process is achieved and
temperature is controlled by using a series
of heating steps:
(1) Drying (1500C) - evaporation of solvents
(10 -100 s)
(2) Charring & Ashing (6000C) –destroy
organics & removal of volatile hydroxides,
sulfates, carbonates (10-100 s)
(3) Fire/Atomize (2000-30000C)- atomization
of remaining analyte (1 s)
Small sample size typically from 10-50 µL
is used.
Enhanced sensitivity over flame
atomization
The entire sample is analyzed
Much of the background matrix can be
eliminated
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Flame Versus Electrothermal Atomization
Choice of atomization method is determined primarily by
analyte’s concentration in samples being analyzed.
Because of its greater sensitivity, detection limits for most
elements are significantly lower when using electrothermal
atomization.
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Interferences in AAS
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 interference.
Factors that may affect the ability of the instrument to read this
parameter can also be classified as interference.
The different interferences that are encountered in atomic
absorption spectroscopy are:
1. chemical
2. ionization
3. spectral
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Interferences in AAS…
1- Chemical interference(C.I.)
Most chemical interferences result from a change in the
atomization behavior of the analyte
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Interferences in AAS…
An example is the decrease in calcium absorbance that is
observed with increasing concentration of sulfate or phosphate.
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Interferences in AAS…
Solution:
1. Interference due to formation of species of low volatility can
often be eliminated or moderated by use of higher
temperatures.
2 Alternatively, releasing agents, which are cations that react
with the interfering species and prevent its interaction with
analytes, can be employed.
For example, addition of an excess of strontium or
lanthanum ions minimizes interference of phosphate
determination of calcium.
3. Protective agents prevent interference by forming stable but
volatile species with analytes.
EDTA eliminates interference of aluminum, silicon,
phosphate, and sulfate in the determination of calcium.
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Interferences in AAS…
2- Ionization
interference:
If the temperature in the cell becomes too high, atoms of low
ionization energy can ionize and leads to a decreased concentration of
atoms in the cell.
If a large quantity of the test element is ionized, a very weak
absorption is observed.
This is due to ionic absorption occurring at wavelengths different
from that of the atomic one.
• palladium in carbenicillin,
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Pharmaceutical applications …
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Pharmaceutical applications …
Calcium and magnesium compounds are often added to dialysis and
infusion solutions and are also extensively used, along with aluminum
compounds in antacid, homogenous solutions of these metals are
easily determined by either emission or absorption spectroscopy.
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Pharmaceutical applications …
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Pharmaceutical applications …
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Atomic Emission Spectroscopy (AES)
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Atomic Emission Spectroscopy…
AES is an analytical method that uses the intensity of light emitted
from atoms excited by a proper source at a particular wavelength to
determine the quantity of an element in a sample.
The wavelength of the atomic spectral line gives the identity of the
element while the intensity of the emitted light is proportional to
the number of atoms of the element.
AES uses quantitative measurement of the emission from excited
atoms to determine analyte concentration.
Analyte atoms in solution are aspirated into the excitation region
where they are desolvated, vaporized, and atomized by a an
atomization sources.
These high-temperature atomization sources provide sufficient energy
to promote the atoms into high energy levels. The atoms decay
back to lower levels by emitting light.
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Atomic Emission Spectroscopy…
Instrumentation for atomic emission spectroscopy is similar in design
to that used for atomic absorption.
In fact, most flame atomic absorption spectrometers are easily
adapted for use as flame atomic emission spectrometers by turning
off the hollow cathode lamp and monitoring the difference between
the intensity of radiation emitted when aspirating the sample and
that emitted when aspirating a blank.
Many atomic emission spectrometers, however, are dedicated
instruments designed to take advantage of features unique to atomic
emission, including the use of plasmas, arcs, sparks, and lasers, as
atomization and excitation sources and have an enhanced capability
for multi-elemental analysis.
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Atomization and Excitation
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Atomization and Excitation…
A. Flame Sources
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Atomization and Excitation…
B. Plasma Sources:
A plasma consists of a hot, partially ionized gas, containing an
abundant concentration of cations and electrons that make the plasma
a conductor.
The plasmas used in atomic emission are formed by ionizing a
flowing stream of argon, producing argon ions and electrons.
The high temperatures in a plasma result from resistive heating that
develops due to the movement of the electrons and argon ions.
Because plasmas operate at much higher temperatures than flames,
they provide better atomization and more highly populated excited
states.
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Atomization and Excitation…
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Atomization and Excitation…
The inductively coupled plasma (ICP) torch consists of three
concentric quartz tubes, surrounded at the top by a radio-frequency
induction coil.
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The resulting collisions with the abundant unionized gas give rise
to resistive heating, providing temperatures as high as 10,000 K
at base of plasma, and between 6000- 8000 K at a height of 15–
20 mm above the coil, where emission is usually measured.
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Atomization and Excitation…
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Atomization and Excitation…
Plasma characteristics
Inductively coupled plasmas are at least 2X as hot as
flames or furnaces.
The Ar plasma is the result of the flow of Ar ions in a
very strong, localized radio field.
6000-10000 K are common plasma temperatures. Hot
enough to excite most elements so they emit light.
Hot enough to prevent the formation of most
interferences, break down oxides (REEs) and eliminate
most molecular spectral interferences.
Ionization interference small due to high density of
electrons.
Plasma chemically inert, little oxide formation
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Atomization and Excitation…
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Multielemental Analysis
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Atomic Fluorescence Spectroscopy (AFS)
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