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Atomic Spectrophotometry

Atomic spectrophotometry is a technique that analyzes the absorption, fluorescence, or emission of electromagnetic radiation by atoms, involving an atomization process to convert samples into atomic gas. It includes methods like Atomic Absorption Spectrometry (AAS), Atomic Emission Spectrometry (AES), and Atomic Fluorescence Spectrometry (AFS), and is widely used in pharmaceutical analysis due to its high specificity and sensitivity. The document details the instrumentation, atomization processes, and interferences encountered in AAS.
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0% found this document useful (0 votes)
10 views60 pages

Atomic Spectrophotometry

Atomic spectrophotometry is a technique that analyzes the absorption, fluorescence, or emission of electromagnetic radiation by atoms, involving an atomization process to convert samples into atomic gas. It includes methods like Atomic Absorption Spectrometry (AAS), Atomic Emission Spectrometry (AES), and Atomic Fluorescence Spectrometry (AFS), and is widely used in pharmaceutical analysis due to its high specificity and sensitivity. The document details the instrumentation, atomization processes, and interferences encountered in AAS.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Atomic Spectrophotometry

Outline
 Introduction

 Types of atomic spectrophotometric techniques

 Instrumentation

 Applications in pharmaceutical analysis

Atomic Spectrophotometry 2
Introduction

 Atomic spectroscopy is based upon absorption, fluorescence, or


emission of electromagnetic radiation by atoms

 The sample is decomposed and converted to atoms by means of an


atomization process

 The resultant spectra are simple and consist of a number of narrow


and discrete lines

Atomic Spectrophotometry 3
Introduction….
Advantages

 Highly specific

 Wide application

 Excellent sensitivity (ppm-ppb)

 Speed

 Convenience

Atomic Spectrophotometry 4
Introduction….
Characteristics of Atomic Spectroscopy

 Involves EMR in the UV and visible regions of the EMR


spectrum

 Based on excitation of a (valence) electron to an excited state

 Involves atoms or ions in the gaseous state

 Involves a process called “atomization”

 Capable of analyzing up to 70 elements

Atomic Spectrophotometry 5
Atomization

Atomization

 A process by which molecular constituents (analyte) of a sample


are simultaneously decomposed and converted to atoms (and
ions) in the gaseous atoms state

 Atomic spectroscopy methods are categorized based on the type


of atomization

 The atomization process is the “signal generator”

Atomic Spectrophotometry 6
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.

Volatilization - Solid atoms are


converted to a vapor in
the flame.
There are three types of particles that exist
in the flame:
1) Atoms
2) Ions
3) Molecules

Atomic Spectrophotometry 7
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)

Atomic Spectrophotometry 8
Atomic Absorption Spectroscopy
(AAS)

Atomic Spectrophotometry 9
Introduction to AAS
 AAS is the study of the absorption of radiant energy by
atoms.

 It is a technique for determining the concentration of a


particular metal in a sample.

 Although atomic absorption spectrometry is quite expensive,


the technique is very wide-spread, due to the fact that by
AAS it is possible to determine about 70 elements (mainly
metals) at very low concentrations.

Atomic Spectrophotometry 10
Elements that are highlighted in pink are detectable by AAS

Atomic Spectrophotometry 11
Introduction to AAS…
Basic Principle
 In AAS, the sample solution is first vaporized and atomized in
a flame or furnace.

 A light beam from a lamp whose cathode is made of the


element in question is passed through the flame.
 Radiation is absorbed, transforming the ground state atoms
to an excited state.

 The amount of radiation absorbed depends on the amount of


the sample element present.

Atomic Spectrophotometry 12
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

Analyte solution Nebuliser, spray


chamber, and
burner
Atomic Spectrophotometry 13
1. Radiation Sources for AAS
a. Hollow Cathode Lamps (HCL)
 Lamps receive an applied potential of ~
300 V DC
 Filled with an inert gas (Ne or Ar) at low
vacuum (1-5 torr) that is easy to be ionized
 Exit window composed of pyrex glass or
quartz; depending on wavelength produced
 The cathode is made from the same metal
to be determined in the sample.

Atomic Spectrophotometry 14
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

Atomic Spectrophotometry 15
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.

 For this reason, a different hollow cathodes must be used for


measuring the different elements to be determined.
 And this is one of the main disadvantages in the use of
A.A.S. method as a large number of HCL must be used
Atomic Spectrophotometry 16
2- Atomizers For A.A.S.

Atomic Spectrophotometry 17
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.

 Fuel and oxidant are needed to produce a flame in which to burn a


sample, the choice being dependent upon the type of burner and analyte
used.
 The burner systems used are of two types the total consumption and the
premix burners.

Atomic Spectrophotometry 18
Simplest system: Flame Atomization

Atomic Spectrophotometry 19
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.

 The fuel (usually acetylene) and oxidant


(usually air) are forced, under pressure, into the
flame, whereas the sample is drawn by
aspiration into the flame through a small
diameter plastic tube .

 This type of burner head is not commonly used


for atomic absorption.
o The reason for this is that the resulting flame
is turbulent and non-homogenous

Atomic Spectrophotometry 20
I. Flame Atomizers…
(B) Premix burners

 In the premix burner the oxidant - sample mixture


flows into a chamber, located upstream from the
flame, where the larger drops are separated from
the mixture and discarded.

 As the sample is swept through the chamber by


the gaseous mixture, all except the smaller drops
strike obstacles placed in the path of the flow and
fall into the bottom of the chamber.

 Small drops (5-10% of the total sample size) pass


through the chamber to the burner head and into
the flame.

Atomic Spectrophotometry 21
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.

 This easy decomposition results in an efficient atomization of


sample in flame, that leads to increased emission intensity and
increased analytical sensitivity and results in a higher signal to
noise ratio, thus premix burner is preferred for most
quantitative analysis.

Atomic Spectrophotometry 22
 Disadvantages:

 Selective evaporation of the sample in the spray chamber

o e.g. If the sample is dissolved in 2 solvent system,


the more volatile solvent may preferentially
evaporates in the spray chamber, leaving the element
of interest in the less volatile solvent so its atoms
never reach the flame.

Atomic Spectrophotometry 23
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

 produce results that are H2 2100 2900 2900


satisfactory for most
purposes.
Acetylene 2200 3100 3200
 The most commonly used
oxidants and fuels in such Propane 1900 2800 ----
burners are shown in the table.
Butane 1900 2800 ----
 A range in atomization
temperatures can be achieved by
changing and varying the Cyanogen 2600 4500 ----
fuel/oxidant mixtures
Atomic Spectrophotometry 24
Flames Atomization….
 Flame temperature and
position are critical for
achieving reproducible
atomization

Interconal region: Pretty


narrow in stoichiometric
flames, rich in free atoms,
widely used for analytical
spectroscopy

1o combustion region: Not at Outer zone: Atoms from inner


thermal equilibrium, not used core are converted to stable
for analytical spectroscopy molecular oxides, cooler

Atomic Spectrophotometry 25
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

Mg -atomized by longer exposure to flame, but is


eventually oxidized.
Ag -slow to oxidize, the number of atoms
increases with flame height.
Cr -oxidizes readily, highest concentration of
atoms at the base ofAtomic
theSpectrophotometry
flame. 26
II. Electrothermal Atomizers (GFAAS).
 A significant improvement in sensitivity is achieved by using
resistive heating in place of a flame.

 A typical electrothermal atomizer, also known as a graphite


furnace, consists of cylindrical graphite tube approximately 1–3
cm in length, and 3–8 mm in diameter.

 The graphite tube is housed in an assembly that seals the ends of


the tube with optically transparent windows.

 The assembly also allows for the passage of a continuous stream


of inert gas, protecting the graphite tube from oxidation, and
removing the gaseous products produced during atomization.

 A power supply is used to pass a current through the graphite


tube, resulting in resistive heating.
Atomic Spectrophotometry 27
II. Electrothermal Atomizers …

 Atomization occurs in an electrically heated graphite tube


 entire sample atomized at very high temperature (2000-3000°C)
 superior sensitivity (10-10-10-13 g of analyte)
 less reproducible (5-10 %) than FAAS.

Atomic Spectrophotometry 28
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
Atomic Spectrophotometry 29
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.

 A better precision when using flame atomization makes it the


method of choice when the analyte’s concentration is
significantly greater than the detection limit for flame
atomization.

 Electrothermal atomization is the method of choice when the


analyte’s concentration is lower than the detection limit for
flame atomization.

 Electrothermal atomization is also useful when the volume of


sample is limited.
Atomic Spectrophotometry 30
Flame Versus Electrothermal Atomization…

 Detection Limits of some analyzed elements (ppb)

Element Flame Atomizat. Electrothermal


Atomizat.
Ag 0.9 0.001
Al 20 0.01
As 20 0.08
Ba 8 0.04
Bi 20 0.1
Ca 0.5 0.01
Cd 0.5 0.0002
Co 2 0.008
Cr 2 0.004
Fe 3 0.01
Ga 50 0.01
Hg 200 0.2
Atomic Spectrophotometry 31
Graphite Flame
Advantages Solutions, slurries and solid Inexpensive (equipment,
samples can be analyzed. day-to-day running)
Much more efficient atomization High sample throughput
greater sensitivity Easy to use
Smaller quantities of sample High precision
(typically 5 – 50 µL)
Provides a reducing environment
for easily oxidized elements

Disadvanta- Expensive Only solutions can be


ges Low precision analyzed
Low sample throughput Relatively large sample
Requires high level of operator quantities required (1 – 2
skill mL)
Less sensitivity
(compared to graphite
furnace)

Atomic Spectrophotometry 32
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

Atomic Spectrophotometry 33
Interferences in AAS…
1- Chemical interference(C.I.)
 Most chemical interferences result from a change in the
atomization behavior of the analyte

 Usually the atomization signal is depressed due to formation


of stable compounds

 Chemical reactions remove atoms of elements being analyzed


and lead to low absorbance or emission readings.

 The most common type of C.I. is caused by anions that can


strongly bond with metal ions to form compounds of low
volatility with analytes and thus reduce the rate at which the
analyte is atomized.

Atomic Spectrophotometry 34
Interferences in AAS…
 An example is the decrease in calcium absorbance that is
observed with increasing concentration of sulfate or phosphate.

 Example: Determination of Calcium in presence of phosphate:


 An equilibrium exists in aqueous solutions between
calcium and calcium phosphate as:
Ca2+ + PO4-3 <-----> CaPO4-1
 CaPO4-1 is less volatile (i.e. more difficult to atomize) than
Ca2+
 The equilibrium tells us that [CaPO4-1] increases and [Ca2+]
decreases due to the stability of the former.

 Net result, the absorbance of atomic calcium decreases as


phosphate content in the sample increases

Atomic Spectrophotometry 35
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.
Atomic Spectrophotometry 36
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.

1. The condition can be minimized by adding a large concentration of


ionization suppressors, which is another species that easily
ionized; for example, in the measurement of Ca, a large amount
of sodium ion usually is added.
2. Ionization can be reduced or eliminated also by decreasing the
temperature of the cell.
Atomic Spectrophotometry 37
Interferences in AAS…
3. Spectral Interferences:
 Arises when absorption or emission of other species in solution lies
very close to the same wavelength
1. Can result from combustion products of flame fuel or
oxidant
2. Molecular oxides from sample itself
 Calcium is an example of an element which can lead to molecular
spectral interference.

 In flames calcium combines with oxygen to yield an oxide-


hydroxide which emits a broad band of radiation which can interfere
with FAES analysis of Na and Ba.
 This type of interference can be eliminated:

 by using a different spectral line for the analysis or


 by adding a chemical reagent which prevents formation of
molecular species.
Atomic Spectrophotometry 38
Pharmaceutical applications of atomic absorption
 Analytical measurement of elemental concentrations is important
for analysis of the major and minor constituents of pharmaceutical
products.
Metals are major constituents of several pharmaceuticals such as
dialysis solutions, lithium carbonate tablets, anti-acid
formulations and multivitamin –mineral tablets.
 For these forms AAS analysis is an important tool.

 It is indispensable for the determination of trace metal


impurities in pharmaceutical products and the quantitative
analysis of metals, essential and toxic, in biological fluids and
tissues.
 Beyond this, several drugs which do not contain metallic
components themselves may be analyzed indirectly by AAS
methods utilizing metal complexation or precipitation reactions.
Atomic Spectrophotometry 39
Pharmaceutical applications …
 The elements Na, K, Li, Mg, Ca, Al and Zn are among the
common elements subjected to pharmaceutical analysis and
coincidentally are also among the elements most readily
determined by AAS.

 Sodium and potassium levels are difficult to analyze by


titrimetric or colorimetric techniques but are among the
elements most easily determined by atomic spectroscopy.

 Their analysis is important for the control of infusion and


dialysis solutions which must be carefully monitored to
maintain proper electrolyte balance.
 Flame emission spectroscopy is the simplest and least
expensive techniques for this analysis although the precision
of the measurement may be improved by employing atomic
absorption spectroscopy.
Atomic Spectrophotometry 40
Pharmaceutical applications …

 Atomic absorption spectroscopy (AAS) is used in a number of


limit tests for metallic impurities in BP.

 AAS is used to conduct limit test for

• lead and nickel in sugars and polyols,

• magnesium and strontium in calcium acetate,

• palladium in carbenicillin,

• sodium and lead in bismuth sungallate.

Atomic Spectrophotometry 41
Pharmaceutical applications …

 Lithium carbonate tablets are also readily analyzed by flame


atomic absorption spectroscopy after they have been dissolved
in mineral acids.

 Both lithium and sodium levels must be carefully controlled


in these tablets.

Clinically, lithium level in serum should be maintained


between 3.5 - 7ppm and may be monitored easily and
rapidly by either emission or absorption spectroscopy.

Atomic Spectrophotometry 42
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.

 Unfortunately, phosphate or other oxy-anions which are often


present in these products interfere by the formation of stable oxy-
metal compounds in the aerosol
 These are difficult to atomize in the flame.
 This complication can be eliminated simply by
o excessive addition of chemical releasing agents

 lanthanum or strontium salts,


o chelating agents such as EDTA

Atomic Spectrophotometry 43
Pharmaceutical applications …

 Zinc is present in a number of pharmaceuticals, the most


important of which is life sustaining insulin.

 Many topical preparations contain zinc as the oxide, sulfate or


stearate as an astringent or antipruritic.

 Some foot powders contain the anti fungal zinc undecenoate,


and zinc is used as antidandruff shampoos.

 After dissolving them in acid, the topical products can be


analyzed easily by atomic emission or atomic absorption
spectroscopy.

Atomic Spectrophotometry 44
Pharmaceutical applications …

 In the USP atomic absorption spectroscopy is also used in


dissolution and content uniformity tests.

 Dissolution and content for potassium in:

o potassium citrate extended release tablets,

o potassium gluconate tablets and

o potassium chloride extended release capsules and tablets

o and dissolution test for calcium gluconate tablets is done


in USP 2005 using atomic absorption spectroscopy.

Atomic Spectrophotometry 45
Atomic Emission Spectroscopy (AES)

Flame and Non-Flame Emission Spectroscopy

Atomic Spectrophotometry 46
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.

Atomic Spectrophotometry 47
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.
Atomic Spectrophotometry 48
Atomization and Excitation

 Atomic emission requires a means for converting an analyte in


solid, liquid, or solution form to a free gaseous atom.

 The same source of thermal energy usually serves as the


excitation source.

 The most common methods are flames and plasmas, both of


which are useful for liquid or solution samples.

 Solid samples analyzed after dissolving it in a suitable


solvent and then using a flame or plasma atomizer.

Atomic Spectrophotometry 49
Atomization and Excitation…
A. Flame Sources

 Atomization and excitation in flame atomic emission is


accomplished using the same nebulization and spray chamber
assembly used in atomic absorption.

 Older atomic emission instruments often used a total


consumption burner in which sample is drawn through a
capillary tube and injected directly into the flame.

Atomic Spectrophotometry 50
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.
Atomic Spectrophotometry 51
Atomization and Excitation…

Types of Plasma sources

1- Inductively Coupled Plasma (ICP);


 It is the most commonly used type

 Consists of radio frequency ac coupled to the gas through


electromagnetic induction.

2- Direct-Current Plasma (DCP);


 Uses the dc excitation sources.

3- Laser-Induced Plasma (LIP);


 Where microwave sources are used to induce plasma.

Atomic Spectrophotometry 52
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.

 The sample is mixed with a stream of Argon using a spray


chamber nebulizer similar to that used for flame emission and is
carried to the plasma through the torch’s central tube.

 Plasma formation is initiated by a spark from a Tesla coil.

 An alternating radiofrequency current in the induction coils


creates a fluctuating magnetic field that induces argon ions and
electrons to move in a circular path.

Atomic Spectrophotometry 53
 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.

• At these high temperatures the outer quartz tube must be


thermally isolated from the plasma. This is accomplished by
tangential flow of argon shown in the schematic diagram.

Atomic Spectrophotometry 54
Atomization and Excitation…

Atomic Spectrophotometry 55
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

 Temperature profile quite stable and uniform

Atomic Spectrophotometry 56
Atomization and Excitation…

Choice of atomization and excitation source:

 Except for alkali metals, detection limits when using an ICP


are significantly better than those obtained with flame
emission.

 Plasmas are also subject to lower and fewer spectral and


chemical interferences.

 For these two reasons a plasma emission source is usually the


better choice.

Atomic Spectrophotometry 57
Multielemental Analysis

 Atomic emission spectroscopy is ideally suited for


multielemental analysis because all analytes in a sample are
excited simultaneously.
 A scanning monochromator can be programmed to move
rapidly to an analyte’s desired wavelength, pausing to record
its emission intensity before moving to the next analyte’s
wavelength.
 Proceeding in this fashion, it is possible to analyze three or
four analytes per minute.

Atomic Spectrophotometry 58
Atomic Fluorescence Spectroscopy (AFS)

 AFS uses radiation from a line (HCL) or continuous (Xenon


arc lamps) sources to excite atoms to a higher electronic state

 The fluorescence radiation emitted due to the return of excited


atoms to the ground sate is measured.

 The atomization takes place by the use of flame or plasma


techniques.

 The fluorescence emission is measured at an angle of 90 from


the exciting radiation

 Applications , the same as AAS and AES.


Atomic Spectrophotometry 59
Comparison Between Atomic Absorption and Emission
Spectroscopy
Absorption Emission
• Measure trace metal • Measure trace metal
concentrations in complex concentrations in complex matrices
matrices
• Depends upon the number of • Depends upon the number of
ground state atoms excited atoms
• It measures the radiation absorbed • It measures the radiation emitted by
by the ground state atoms the excited atoms

• Presence of a light source (HCL ) • Absence of the light source

• The temperature in the atomizer is • The temperature in the atomizer is


adjusted to atomize the analyte big enough to atomize the analyte
atoms in the ground state only atoms and excite them to a higher
energy level

Atomic Spectrophotometry 60

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