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1. Chapter 21
Atomic Spectroscopy

2. 1- In atomic spectroscopy, samples are vaporized at 2 000–8 000 K
and decompose into atoms.
2- Concentrations of atoms in the vapor are measured by emission or
absorption of characteristic wavelengths of radiation.
3- Atomic spectroscopy is a principal tool of analytical chemistry
because of its high sensitivity, its ability to distinguish one element
from another in a complex sample, its ability to perform simultaneous
multi-element analyses, and the ease with which many samples can be
automatically analyzed.
4- The precision of atomic spectroscopy, typically 1–2%, is not as
good as that of some wet chemical methods.
5- The equipment is expensive, but widely available.

3. 1- An important difference between atomic and molecular
spectroscopy is the width of absorption or emission bands. Spectra of
liquids and solids typically have bandwidths of 100 nm.
2- Spectra of gaseous atoms consist of sharp lines with widths of
0.001 nm.
3- Lines are so sharp that there is usually little overlap between the
spectra of different elements in the same sample. Therefore, some
instruments can measure more than 70 elements simultaneously.

6. 4- In atomic fluorescence experiment. Atoms in the flame are
irradiated by a laser to promote them to an excited electronic state
from which they can fluoresce to return to the ground state.
5- Atomic fluorescence is potentially a thousand times more sensitive
than atomic absorption, but equipment for atomic fluorescence is not
common.
6- In atomic emission, collisions in the very hot plasma promote some
atoms to excited electronic states from which they can emit photons to
return to lower-energy states.
7- In atomic emission, no lamp is required.
8- Emission intensity is proportional to the concentration of the
element in the sample. Emission from atoms in a plasma is now the
dominant form of atomic spectroscopy.

7. Flame Atomization: In a flame atomizer, a solution of
the sample is nebulized by a flow of gaseous oxidant,
mixed with a gaseous fuel, and carried into a flame
where atomization occurs. The following processes then
occur in the flame.
•Desolvation (produce a solid molecular aerosol)
•Dissociation (leads to an atomic gas)
•Ionization (to give cations and electrons)
•Excitation (giving atomic, ionic, and molecular
emission)

10. Types of Flames:
Several common fuels and oxidants can be
employed in flame spectroscopy depending on
temperature needed. Temperatures of 1700
o
C to
2400
o
C are obtained with the various fuels
when air serves as the oxidant. At these
temperature, only easily decomposed samples
are atomized. For more refractory samples,
oxygen or nitrous oxide must be employed as
the oxidant. With the common fuels these
oxidants produce temperatures of 2500
o
C to
3100
o
C.

12. Burning Velocity:
The burning velocities are of considerable
importance because flames are stable in certain
ranges of gas flow rates only. If the gas flow rate
does not exceed the burning velocity, the flame
propagates itself back in to the burner, giving
flashback. As the flow rate increases, the flame
rises until it reaches a point above the burner
where the flow velocity and the burning velocity
are equal. This region is where the flame is stable.
At higher flow rates, the flame rises and
eventually reaches a point where it blows off of
the burner.

13. •Flame Structure:
Important regions of a flame include:
1.primary combustion zone
2.interzonal region
3.secondary combustion zone

1.Primary combustion zone: Thermal
equilibrium is ordinarily not reached in
this region, and it is, therefore, seldom
used for flame spectroscopy.

15. 2.Interzonal region: This area is relatively
narrow in stoichiometric hydrocarbon
flames, is often rich in free atoms and is
the most widely used part of the flame for
spectroscopy.

3.Secondary combustion zone: In the
secondary reaction zone, the products of
the inner core are converted to stable
molecular oxides that are then dispersed
into the surroundings.

16. Temperature Profiles:
A temperature profile of a typical flame for
atomic spectroscopy is shown in Fig. 9-3.
The maximum temperature is located in the
flame about 1 cm above the primary
combustion zone. It is important–
particularly for emission methods – to focus
the same part of the flame on the entrance
slit for all calibrations and analytical
measurements.

18. Flame absorbance Profiles:
Fig. 9-4 shows typical absorption profiles for
three elements. Magnesium exhibits a
maximum in absorbance at the middle of the
flame. The behavior of silver, which is not
readily oxidized, is quite different, a
continuous increase in the number of atoms,
and thus the absorbance, is observed from the
base to the periphery of the flame. Chromium,
which forms very stable oxides, shows a
continuous decrease in absorbance beginning
close to the burner tip.

20. Flame Atomizers:
Figure 9-5 is a diagram of a typical
commercial laminar flow burner that
employs a concentric tube nebulizer. The
aerosol is mixed with fuel. The aerosol,
oxidant, and fuel are then burned in a
slotted burner that provides a flame that is
usually 5 or 10 cm in length.

22. Advantages:
1. Uniform dropsize
2. Homogeneous flame
3. Quiet flame and a long path length
Disadvantages:
1. Flash back if V
burning > V
flow
2. ~90% of sample is lost
3. Large mixing volume

23. Performance Characteristics
Of Flame Atomizers
In terms of reproducible behavior, flame
atomization appears to be superior to all other
methods for liquid sample introduction. In
terms of sampling efficiency and thus
sensitivity, however, other atomization
methods are markedly better. A large portion
of the sample flows down the drain and the
residence time of individual atoms in the
optical path in the flame is brief (~10
-4
s).

24. Electrothermal Atomization
It provides enhanced sensitivity because the entire
sample is atomized in a short period, and the
average residence time of the atoms in the optical
path is a second or more. A few microliters of
sample are first evaporated at a low temperature
and then ashed at a somewhat higher temperature
in an electrically heated graphite tube or in a
graphite cup. Then the current is rapidly increased
to several hundred amperes, which caused the
temperature to soar to perhaps 2000
o
C to 3000
o
C;
atomization of the sample occurs in a period of a
few milliseconds to seconds.

26. Performance Characteristics:
Electrothermal atomizers offer the advantage
of unusually high sensitivity for small
volumes of sample. Typically, sample
volumes between 0.5 and 10 L are used;
absolute detection limits lie in the range of
10
-10
to 10
-13
g of analyte. Furnace methods
are slow-typically requiring several minutes
per element. A final disadvantage is that the
analytical range is low, being usually less
than two orders of magnitude.

27. ATOMIC ABSORPTION
INSTRUMENTATION
Instruments for atomic absorption
spectrometry (AAS) consist of a radiation
source, a sample holder, a wavelength
selector, a detector, and a signal
processor and readout. The sample holder
in atomic absorption instruments is the
atomizer cell that contains the gaseous
atomized sample.

28. 1. Radiation Sources:
It is necessary that band width of the
radiation source must be narrow relative to
the width of an absorption peak. The
problem created by limited width of atomic
absorption peaks has been solved by the
use of line sources with bandwidths even
narrower than absorption peaks.

29. Fig. 9-10a shows the emission spectrum of a typical
atomic lamp source. With a suitable filter or
monochromator, all but one of these lines are
removed. Fig. 9-10b shows the absorption spectrum
for the analyte between wavelengths 
1 and 
2.
Passage of the line from the source through the
flame reduces its intensity from P
0 to P; the
absorbance is then given by log(P
o/P), which is
linearly related to the concentration of the analyte
in the sample. A disadvantage of the procedure is
that separate lamp source is needed for each
element.

31. Hollow Cathode Lamps:
It is the most common source for atomic
absorption measurements. This lamp consists
of a tungsten anode and a cylindrical cathode
sealed in a glass tube that is filled with neon or
argon at a pressure of 1 to 5 torr. The cathode
is constructed of the metal whose spectrum is
desired. Ionization of the inert gas occurs
when a potential on the order of 300 V is
applied across the electrodes, which generates
a current of about 5 to 15 mA.

32. … Hollow Cathode Lamps continued…
If the potential is sufficiently large, the
gaseous cation acquire enough kinetic energy
to dislodge some of the metal atoms from the
cathode surface and produce an atomic cloud
in a process called sputtering. A portion of the
sputtered metal atom are in excited states and
thus emit their characteristic radiation as they
return to the ground state. Eventually, the
metal atoms diffuse back to the cathode
surface or to the glass walls of the tube and are
redeposited.

34. Electrodeless Discharge Lamps (EDLs):
These provide radiant intensities that are
usually one to two orders of magnitude
greater than hollow cathode lamps. A
typical lamp is constructed from a sealed
quartz tube containing a few torr of an inert
gas such as argon and a small quantity of
the metal (or its salt) whose spectrum is of
interest.

35. …Electrodeless Discharge Lamps (EDLs) continued…
The lamp is energized by an intense field of
radio-frequency or microwave radiation.
Ionization of the argon occurs to give ions
that are accelerated by the high-frequency
component of the field until they gain
sufficient energy to excite the atoms of the
metal whose spectrum is sought.
Electrodeless discharge lamps are available
commercially for 15 or more elements.

37. Single-Beam Instruments: A typical
single-beam instrument, consists of several
hollow cathode sources, an atomizer, and
simple grating spectrophotometer with a
photomultiplier transducer. The 100% T
adjustment is then made while a blank is
aspirated into the flame. Finally, the
transmittance is obtained with the sample
replacing the blank.

38. Double-Beam Instruments: In double-beam
instrument the beam from the hollow cathode
source is split by a mirrored chopper, one half
passing through the flame and the other half
around it. The two beams are then recombined
by a half-silvered mirror and passed into a
grating monochromator; a photomultiplier
tube serves as the transducer. The ratio
between the reference and sample signal is
then amplified and fed to the readout, which
may be a digital meter or a signal recorder.

40. INTERFERENCES IN ATOMIC
ABSORPTION SPECTROSCOPY
1. Spectral Interferences:
(I) Spectral interference can occur due to overlapping
lines. e.g. a vanadium line at 3082.11Å interferes in an
analysis based upon the aluminum absorption line at
3082.15 Å. This type of interference can be avoid by
employing the aluminum line at 3092.7 Å instead.
(II) Spectral interferences result from the presence of
combustion products that exhibit broadband absorption or
particulate products that scatter radiation. Both diminish
the power of the transmitted beam. A blank can be
aspirated into the flame to make the correction.

41. …Spectral Interferences continued…
(III) Source of absorption or scattering can be
originated in the sample matrix. An example of
a potential matrix interference due to
absorption occurs in the determination of
barium in alkaline earth mixture. The
wavelength of Ba line used for atomic
absorption analysis appears in the center of a
broad absorption band for CaOH. The effect
can be eliminated by substituting nitrous oxide
for air as the oxidant which yields a higher
temperature that decomposed the CaOH and
eliminates the absorption band.

43. …Spectral Interferences continued…
(IV) Concentrated solution of elements such
as Ti, Zr and W which form refractory
oxides can cause spectral interference due to
scattering.
(V) Organic solvent or organic impurities in
the sample can cause scattering interference
from carbonaceous particle because of
incomplete combustion of the organic
matrix.

44. 2. Chemical Interferences:
(I) Formation of Compounds of Low Volatility:
The most common type of interference is by
anions that form compounds of low volatility with
the analyte and thus reduce the rate at which the
analyte is atomized. The decrease in calcium
absorbance that is observed with increasing
concentrations of sulfate or phosphate. Example of
cation interference have also been recognized.
Aluminum is found to cause low results in the
determination of magnesium, apparently as a
result of the formation of a heat-stable
aluminum/magnesium compound.

45. …Formation of Compounds of Low Volatility continued…
Interference due to formation of species of low
volatility can often be eliminated or moderated by
use of higher temperatures. Releasing agents
which are cations that react preferentially with the
interferant and prevent its interaction with the
analyte, can be employed. Protective agents
prevent interference by forming stable but volatile
species with the analyte. Three common reagents
for this purpose are EDTA, 8-hydroxyquinoline,
and APDC (ammonium salt of 1-
pyrrolidinecarbodithioic acid).

46. …Chemical Interferences continued…
(II) Dissociation Equilibria: Gaseous environment
of a flame or a furnace, numerous dissociation and
association reactions lead to conversion of the
metallic constituents to the elemental state. Some of
these reactions are reversible
MOM + O
M(OH)
2M + 2OH
Where M is the analyte atom.
VO
xV + O
x
AlO
xAl + O
x
TiO
x Ti + O
x

47. …Chemical Interferences continued…
(III) Ionization Equilibria: Ionization of atoms and
molecules is small in combustion mixtures that involve
air as the oxidant, and generally can be neglected. In
higher temperatures of flames where oxygen or nitrous
oxide serves as the oxidant, however, ionization
becomes important, and a significant concentration of
free electrons exists as a consequence of the
equilibrium
M M
+
+ e
-
The equilibrium constant K for this reaction takes the
form
K= [M
+
][e
-
]
[M]

48. ATOMIC ABSORPTION
ANALYTICAL TECHNIQUES
Sample Preparation: A disadvantage of flame
spectroscopic methods is the requirement that the
sample be introduced into the excitation source in
the form of a solution, most commonly an aqueous
one. Unfortunately, many materials of interest,
such as soils, animal tissues, plants petroleum
products and minerals are not directly soluble in
common solvents, and extensive preliminary
treatment is often required to obtain a solution of
the analyte in a form ready for atomization.

49. …Sample Preparation continued…
Indeed, the decomposition and solution steps
are often more time consuming and introduce
more error than the spectroscopic measurement
itself. Some of the common methods used for
decomposing and dissolving samples for
atomic absorption methods include treatment
with hot mineral acids; oxidation with liquid
reagents, such as sulfuric, nitric, or perchloric
acids; combustion in an oxygen bomb or other
closed container to avoid loss of analyte.

50. …Atomic absorption analytical techniques continued…
Calibration Curves: Atomic absorption should
follow Beer’s law with absorbance being
directly proportional to concentration. In fact,
however, departures from linearity are often
encountered, and it is foolhardy to perform an
atomic absorption analysis without
experimentally determining whether or not a
linear relationship does exist. A calibration
curve that covers the range of concentrations
found in the sample should be prepared.

51. …Atomic absorption analytical techniques continued…
Standard Addition Method: It is widely used in
atomic absorption spectroscopy in order to
partially or wholly counteract the chemical and
spectral interferences introduced by the sample
matrix.
Application of Atomic Absorption
Spectrometry: It is a sensitive means for the
quantitative determination of more than 60 metals
or metalloid elements. The resonance lines for the
nonmetallic elements are generally located below
200 nm, thus preventing their determination by
convenient, nonvacuum spectrophotometers.