ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ASSIGNMENT
ATOMIC ABSORPTION
SPECTROSCOPY
v, 2014

Submitted To Mam Khadijah

Submitted By Anum Shahid – CMS#8168
Aniqa Javed - CMS#13464
Faiza Iftikhar – CMS#8420
Saleha Sayyab – CMS#8571
Kalsoom Saleem – CMS#8107
Submission Date 06-11-2014
Semester 6th Section A
Total Pages 9
Remarks

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 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Table of Contents

Sr # Content Page #

1 Introduction 3

2 Basic Principle of AAS 4

3 Atomic Spectra 4

4 Instrumentation of AAS 5

5 Interpretation of AAS 7

6 Applications of AAS 8

7 References 9

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 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

1. Introduction
Atomic-absorption spectroscopy quantifies the absorption of ground state atoms in the gaseous state.
The atoms absorb ultraviolet or visible light and make transitions to higher electronic energy levels.
The analyte concentration is determined from the amount of absorption. Concentration
measurements are usually determined from a working curve after calibrating the instrument with
standards of known concentration. Atomic absorption is a very common technique for detecting
metals and metalloids in environmental samples.
When a solution containing metallic species are introduced into a flame, the vapor of metallic species
will be obtained. Some of the metal atoms may be
raised to higher energy level and emit characteristic
radiation. However, large amount of metal atoms
will remain in non-emitting ground state. These
ground state atoms of particular element are
receptive of light radiation of their own specific
resonance wavelength. Thus, when a light of this
wavelength passed through a flame having atom of
metallic species, part of light will be absorbed and
the absorption will be proportional to the density of
atom in the flame.

Elements determined from this technique as shown in Table 1.

Elements that can be detected by AAS

Aluminium (Al) Copper (Cu) Mercury (Hg) Cadmium (Cd) Calcium (Ca)
Antimony (Sb) Gallium (Ga) Molybdenum (Mo) Cobalt (Co) Chromium (Cr)

Arsenic (As) Hafnium (Hf) Niobium (Nb) Nickel (Ni) Lead (Pb)

Beryllium (Be) Indium (In) Ruthenium (Ru) Manganese (Mn) Lithium (Li)

Barium (Ba) Iron (Fe) Tin (Sn) Magnesium (Mg) Vanadium (V)

Tungsten (W) Vanadium (V) Zinc (Zn) Zirconium (Zr)

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 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

The atoms in the atomizer get promoted to higher orbitals (excited state) for a short period of time
(nanoseconds) by absorbing a defined quantity of energy (radiation of a given wavelength). This amount
of energy, i.e., wavelength, is specific to a particular electron transition in a particular element. In general,
each wavelength corresponds to only one element, and the width of an absorption line is only of the order
of a few Pico meters (pm), which gives the technique its elemental selectivity. The radiation flux without
a sample and with a sample in the atomizer is measured using a detector, and the ratio between the two
values (the absorbance) is converted to analyte concentration or mass using the Beer-Lambert Law.

2. Principle
The Beer–Lambert law:
Atomic absorption spectroscopy relies on the Beer-Lambert law to determine the concentration of a
particular analyte in a sample. The absorption spectrum and molar absorbance of the desired sample
element are known, a known amount of energy is passed through the atomized sample and by then
measuring the quantity of light, it is possible to determine the concentration of the element being
measured. There is a linear relationship between absorbance and concentration of an absorbing
species.

A= Absorbance
l= path lenth of cell (cm)
c=molar concentration
= wavelength-dependent molar absorptivity coefficient

Applying Lambert-Beer’s law in atomic absorption spectroscopy is difficult due to variations in the
atomization from the sample matrix and non-uniformity of concentration and path length of analyte
atoms. Concentration measurements are usually determined from a calibration curve generated with
standards of known concentration.

3. Atomic spectra
Atomic spectra feature sharp bands. For example hydrogen spectrum:

n=1
energy
n=2
DE
n=3

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4. Instrumentation of AAS
Atomic absorption instruments consist of a
a. Radiation Source
b. Monochromator
c. Flame or electrothermal atomizer in which sample is introduced
d. Atomizer
e. Detector

a. Radiation Source
Although radiation in the UV-Vis region is required, we cannot use broadband sources. This is because
even the best monochromators cannot provide a bandwidth that is narrower than the atomic
absorption line. If the bandwidth of the incident radiation is wider than the line width, measurement
will fail as absorption will be only a tiny fraction of a large signal which is difficult to measure and will
result in very low sensitivities (figure a). Therefore, line sources with bandwidths narrower than that
of the absorption lines must be used (figure b). This can be achieved by using a lamp producing the
emission line of the element of interest where analyte atoms can absorb that line. Conditions are
established to get a narrower emission line than the absorption line. This can in fact be achieved by
getting an emission line of interest at the following conditions:
1. Low temperatures: to decrease Doppler broadening
(which is easily achievable since the temperature of the
source is always much less than the temperature in
flames).
2. Lower pressures: this will decrease pressure
broadening and will thus produce a very narrow
emission line. Atomic Line Width Monochromator
Bandwidth (different Scales) this may suggest the need
for a separate lamp for each element, which is
troublesome and inconvenient. However, recent
developments lead to introduction of multi-element
lamps. In this case, the lines from all elements should
not interfere and must be easily resolved by the
monochromator so that, at a specific time, a single line of one element is leaving the exit slit.

Hollow Cathode Lamp (HCL)

This is the most common source in atomic absorption

spectroscopy. It is formed from a tungsten anode and
a cylindrical cathode the interior surface of which is
coated by the metal of interest. The two electrodes
are usually sealed in a glass tube with a quartz window
and filled with argon at low pressure (1-5 torr).
Ionization of the argon is forced by application of

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about 300 V DC where positively charged Ar+ heads rapidly towards the negatively charged cathode
causing sputtering. A portion of sputtered atoms is excited and thus emits photons as atoms relax to
ground state. The cylindrical shape of the cathode serves to concentrate the beam in a limited region
and enhances redisposition of sputtered atoms at the
hollow surface. High potentials usually result in high
currents, which, in turn, produce more intense radiation.
However, Doppler broadening increases as a result. In
addition, the higher currents will produce high
proportion of unexcited atoms that will absorb some of
the emission beam, which are referred to as self-
absorption (a lower intensity at the center of the line is
observed in this case).

b. Monochromators
This is a very important part in an AA spectrometer. It is used to separate out all of the thousands of
lines. Without a good monochromator, detection limits are severely compromised. A monochromator
is used to select the specific wavelength of light, which is absorbed by the sample, and to exclude
other wavelengths. The selection of the specific light allows the determination of the selected element
in the presence of others.

c. Atomizer
Atomization is separation of particles into individual molecules and breaking molecules into
atoms.This is done by exposing the analyte to high temperatures in a flame or graphite furnace. The
role of the atom cell is to primarily dissolvate a liquid sample and then the solid particles are vaporized
into their free gaseous ground state form. In this form, atoms will be available to absorb radiation
emitted from the light source and thus generate a measurable signal proportional to concentration.
There are two types of atomization: Flame and Graphite furnace atomization.

d. Flame Or Electrothermal Atomizer In Which Sample Is Introduced

There can be significant amounts of emission produced in flames due to presence of flame
constituents (molecular combustible products) and
sometimes impurities in the burner head. This emitted
radiation must be removed for successful sensitive
determinations by AAS, otherwise a negative error will
always be observed. The detector will see the overall signal,
which is the power of the transmitted beam (P) in addition
to the power of the emitted radiation from flame (Pe).
Therefore if we are measuring absorbance, this will result in
a negative error as the detector will measure what it appears
as a high transmittance signal (actually it is P + Pe). In case
of emission measurements, there will always be a positive

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error since emission from flame is an additive value to the actual sample emission. It is therefore
obvious that we should get rid of this interference from emission in flames.

e. Detector
The light selected by the monochromator is directed onto a detector that is typically a photomultiplier
tube, whose function is to convert the light signal into an electrical signal proportional to the light
intensity. A signal amplifier fulfills the processing of electrical signal. The signal could be displayed for
readout, or further fed into a data station for printout by the requested format.

5. Interpretation of AAS
Atomic theory tells us that the electrons in all atoms are in well-defined orbitals. For example, in
uranium, the electron shells with principal quantum number 1-6 are all filled and the shell with
principal quantum number 7 is partially filled. Numerous orbital are available in each shell that are s,
p, d orbitals, etc. in the filled shell, each orbital accommodates an electron. In the unexcited atoms,
these electrons reside in the orbital with the lowest energy level. However, the upper empty orbital
is available to accommodate an electron. During excitation the electrons with the lowest electron
moves from normal low-energy level to an orbital with a higher energy. This orbital may be in the
same shell or in a higher shell, inasmuch as each orbital is available to accommodate an electron
unless excluded by quantum theory-forbidden transitions.
Example:
In atomic sodium, electron fill the shells with quantum numbers 1 and 2, and one electron is in the
shell with the quantum number 3. When the sodium is in the ground state, this will be in orbital with
the lowest energy, i.e., 3s. if we excite sodium, the 3s electron can move to n orbital with higher
energy. The energy level next to the 3s level is the 3p energy level, hence it is possible for an electron
to go from a 3s to 3p orbital. It is also possible for the 3s electron to go into orbitals of even higher
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energy, such as 4p, 4d, 5p, 5d, etc. When the valence electrons of sodium is in the 3s orbital, its lowest
energy state, the sodium is said to be in the ground state. When the electron is in any orbital with
higher energy, the sodium is said to be in excited energy state, or excited sodium. When radiation
energy is absorbed, the atom becomes excited. If we use a prism to disperse the radiation falling on
the atoms, the absorption spectrum appears as a series of narrow lines opposed to wide bands. If the
transition is between the ground state and lowest
excited state, then it is said that the absorption line is
the resonance line. Transitions between the ground
state and the upper excited states are possible but are
not often used. The energy levels of sodium are shown
in figure, for sake of clarity, upper state transitions are
omitted. In sodium, the transition between the 3s
orbital and a 3p orbital can be achieved by absorbing
radiations at 589 or 589.5 nm. Similar absorption of
radiation at 33.03 nm will cause sodium to be excited
from the 3s ground state to the 5p excited state orbital.
Transitions between the 3s orbital and orbitals with
principal quantum number 6 requires more energy.

6. Applications
1. It is used for water analysis for the presence of following content (e.g. Ca, Mg, Fe, Si, Al, Ba )
2. Also used in food analysis and soil analysis
3. In clinical analysis it is used for analyzing metals in biological fluids and tissues such as whole
blood, plasma, urine, saliva, brain tissue, liver, muscle tissue, semen
4. In Pharmaceuticals it has applications in some pharmaceutical manufacturing processes, minute
quantities of a catalyst that remain in the final drug product
5. It is used in petroleum industry, metallic impurities in petrol, lubricating oils have been
determined.
6. It is used in alloys, metallurgy and in inorganic analysis.
7. Used in analysis of many ores and minerals.
8. It is used in biochemical analysis such as used in estimation of sodium, potassium, zinc, lead,
cadmium, mercury, calcium, iron and magnesium.
9. Also used in pharmaceutical analysis, for estimation of zinc in insulin preparations, creams and in
calamine, oils, calcium in calcium salts, lead in calcium carbonate and also as impurity in number
of chemical salts have been done.
10. Sodium, calcium, and potassium in saline and ringer solutions are estimated by this method.
11. Analysis of ash for determining the contents of sodium, potassium, calcium, magnesium and iron
is carried out in boiler deposits.
12. Used in cement industry.
13. Used in agriculture, soil, forestry, fertilizer and oceanography etc.
14. Used in assay of intraperitoneal dialysis, activated charcoal, cisplatin.

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7. References
a. James W. Robinson, Atomic Spectroscopy, Second Edition, page 100-102
b. M.Arora, Aseem Anand, Instrumental Method Of Chemical Analysis, Himalaya Publishin
House, Fifth Edition, 2005, Page 240-242
c. Aurora Biomed Inc., Aurora Instruments. 2014. http://www.aurorabiomed.com/atomic-
absorption-spectroscopy/
d. Hitachi High-Technologies Corporation. 2011-2014.
http://www.hitachi-hitec.com/global/science/aas/aas_basic_3.html
e. Galbraith Laboratories, Inc. 2011-2014. http://www.galbraith.com/spectroscopy.htm
f. M.Arora, Aseem Anand, Instrumental Method Of Chemical Analysis, Himalaya Publishin
House, Fifth Edition, 2005, Page 240-241

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