HACETTEPE UNIVERSITY

DEPARTMENT OF CHEMICAL ENGINEERING

KMÜ 359 Instrumental Analysis Laboratories

Experiment 5

Atomic Absorption Spectroscopy

Written by

Gamze İde

Group: 5

20722832
CONTENTS
The Purpose of the Experiment:.......................................................................................2
1. INTRODUCTION.................................................................................................2
1.1 Atomic Absorption Spectroscopy (AAS)...............................................................2
Instruments for Atomic Absorption Spectroscopy:.............................................................4
1.1.1 Light Source............................................................................................4
1.2.2 Atomizer...................................................................................................4
1.2.3 Monochromator........................................................................................5
1.3 Interferences in Atomic Spectroscopy...................................................................6
2. DATA AND CALCULATION.................................................................................8
3. DISCUSSION AND CONCLUSION........................................................................10
4. REFERENCES...................................................................................................12
REFERENCES

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The Purpose of the Experiment:
In this experiment, the main purpose is to understand principles of atomic absorption
spectroscopy and the terms related with this method. It has been aimed to learn the working
principle of the apparatus in block diagram, such as, the light source, atomizer,
monochromator etc.

It has been also aimed to determine the concentration of a solution by using atomic absorption
spectroscopy method.

1. INTRODUCTION

1.1Atomic Absorption Spectroscopy (AAS)

Atomic absorption spectroscopy is based on the absorption of discrete wavelengths of light by
ground state, gas phase free atoms. These free atoms are formed from a sample by the
atomizer at high temperature.

The AAS was developed in the 1950 by Alan Walsh which rapidly became a commonly used
analytical instrument.1

What atomic absorption spectroscopy mainly does (AAS) is to determine the presence of
metals in liquid samples. Such as Fe, Cu, Al, Pb, Ca, Zn, Cd etc. It also measures the
concentrations of metals in the samples (usually
in mg/L range).

Figure 1.1 The Atomic Absorption Process2

When metals are in their elemental form, they will absorb ultraviolet light because they are
excited by applied heat from the light source (Figure 1.1). Each metal has their specific
wavelength to be absorbed. The AAS tools looks for a particular metal by focusing a beam of
UV light at a specific wavelength through a flame into the detector. The sample of interest is
softened into the flame. If the sample has that metal in it, the metal will absorb some of the
light, therefore will reduce its intensity. The device measures the change in this intensity. In

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the instrument, there is a computer data system which converts the change in intensity into an
absorbance

There is a direct proportion between concentration and absorbance, if concentration increases,

the absorbance will increase. The researcher can construct a calibration curve by the running
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standards of different concentrations on the AAS and so observing the absorbances. An
example can be seen at Figure 1.2 below.

Figure 1.2 An example plotted graph of

absorbance vs. Concentration of
Phosphate 4

As an elemental analysis technique, AAS has the significant advantage in many cases of being
practically independent of the chemical form of the element in sample. For example if it is
considered a determination of Cd in a water sample is a determination of the total Cd
concentration. It does not matter whether the Cd exists as the chloride, sulphate or nitrate or
even if it exists as a complex or an organometallic compound, if the proper analysis
conditions are used. Concentrations as low as ppt levels of some elements in solution can be
determined and AAS is used routinely to determine ppb and ppm concentrations of most
metal elements.

Another principal advantage is that a given element can be determined in the presence of
other elements, which do not get in by absorption of the analyte wavelength. Thus, it is not
necessary to separate the analyte from the rest of the sample. This results in rapid analysis
times therefore the source of error will be eliminated. However this does not mean that AAS
measurements are completely free from interferences; both chemical and spectral
interferences do occur and must be compensated for, as will be discussed later on.

The major disadvantages of AAS are that no information is obtained on the chemical form of
the analyte (no “speciation”) and that often only one element can be determined at that time.

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This makes AAS of very limited use for qualitative analysis. AAS is used most exclusively
for quantitative analysis of elements, hence the use of the term “spectrometry” in the name of
the technique instead of “spectroscopy”.1,3

Instruments for Atomic Absorption Spectroscopy:

1.1.1 Light Source

Usually hollow- cathode lamps are used as the light source. Lasers are also used in research
instruments. Since the lasers are intense enough to excite atoms to higher energy levels, they
permit AA and atomic fluorescence measurements in one instrument. The disadvantage of
these narrow-band light sources is that only the element is measurable at a time.5

Hollow Cathode Lamps:

Hollow cathode lamps are a key component for atomic

absorption spectroscopy. They are a genre of discharge
lamp which produces narrow emission from atomic
species. Their name is coming from the cup-shaped
cathode that is made from the element of interest. The
electric discharge ionizes rare gas atoms, which are Figure 1.1.1 Hollow Cathode
Lamp6
accelerated into the cathode and spit metal atoms into the gas phase. The metal atoms get
excited, with the collisions with gas atoms or electrons, to higher energy levels, which decay
to lower levels by emitting light. 5

Discharge Lamps:

Discharge lamps, such as neon signs, pass an electric current through a rare gas or metal
vapor to produce light. The electrons collide with gas atoms, exciting them to higher energy
levels which then decay to lower levels by emitting light. Low-pressure lamps have sharp line
emission characteristic of the atoms in the lamp, and high-pressure lamps have broadened
lines superimposed on a continuum.

Deuterium lamps are the uv source in uv-visible absorption spectrophotometers. The sharp
lines of the mercury and rare gas discharge lamps are useful for wavelength calibration of
optical instrumentation. Mercury and xenon arc lamps are used to excite fluorescence. 5

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1.2.2 Atomizer
The atomizer is the sample cell of the AAS system. The atomizer must produce the ground
state free gas phase atoms necessary for the AAS process to occur. The analyte atoms are
generally present in the sample as salts, molecular compounds, or complexes. The atomizer
must convert these species to the reduced free gas phase atomic state. The atomizer generally
does this via thermal energy or some chemistry. The two most common atomizers are flame
atomizers and electrothermal (graphite furnace) atomizers.1

Comparison of Flame and Electrothermal Atomisers:

Flame atomizers use flame to separate the element into its atoms. Electrothermal Atomizer
does the same, however they both have advantages and disadvantages, and therefore the usage
area of them depends.

Flame atomizers are simpler than the electrothermal, they are cheap too. Moreover to this they
give convenient results. However they have relatively short measuring time which can be an
advantage and disadvantage at the same time (in electrothermal atomizer this time is longer
because the system is heated slowly). Flame atomizers are more sensitive and they have
restricted analytical scope, therefore they cannot be used for every samples. Because the
sample is sprayed to the atomizer, while doing spraying there is a loss of sample during the
process, which creates more need for sample.

Electrothermal atomizers (graphite furnace) are more sensitive than flame atomizers, which
gives an option to analyze sample in wide range concentrations. They also require low
volumes of samples; there is no need to have extra volumes of the sample. Moreover, they
have high conversion of efficiency of sample into free atoms. Compared to the measurement
time in flame atomizer, absorption signal is a well defined peak because of the long
measurement time. However the longer measurement time depends on the temperature
program which is used. This is an advantage that the peak heights and areas obtained from the
atomizer and areas can be also used in quantitative measurements. Temperature is the only
factor involved in production of free atoms compared with flame which also must factor in the
composition of the flame, gas flow and oxidant-fuel ratio. This atomizer can keep the spectral
interference low at high temperatures.

Depending on these factors, the optimum atomizer is chosen by experimentalists. 1

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 1.2.3 Monochromator
A monochromator is required to separate the absorption line of interest from other spectral
lines emitted from the HCL and from other elements in the atomizer that are also emitting
their spectra. Because the radiation source produces such narrow lines, spectral interference is
not common. Therefore the monochromator does not need high resolution for atomic
absorption spectroscopy.1

Photomultiplier Tubes

A photomultiplier tube, useful for light detection of very weak signals, is a photoemissive
device in which the absorption of a photon results in the emission of an electron. These
detectors work by amplifying the electrons generated by a photocathode exposed to a photon
flux.7

The monochromator
receives light from the
hollow-cathode lamp
through the flame
together with the light
emitted from the flame.
The signal arising at the
detector from the flame
emission will be rejected
Figure 1.2.3 Photomultiplier Tube working
principle7

and only that from the hollow-cathode lamp will be accepted. The photomultiplier detector
assembly consists of a 0.50 inch, side-on photomultiplier tube with a high voltage power
supply, voltage divider and buffer amplifier to measure low level light signals. The current
output corresponds to the intensity of the light falling on its photocathode. This feeds the
amplifier and output device, which displays the measured signals.1,8

1.3 Interferences in Atomic Spectroscopy

Since 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 population of the

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analyte element 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 most common
intereferences can be seen below:

Spectral interferences: They are due to radiation overlapping that of the light source. The
interference radiation may be an emission line of another element or compound, or general
background radiation from the flame, solvent, or analytical sample. This usually occurs when
using organic solvents, but can also happen when determining sodium with magnesium
present, iron with copper or iron with nickel.9

Chemical Interferences: They are the results of unwanted reactions of analyte element and
oxygen (especially in flame atomiser). The product of these reactions, are strong compounds,
do not want to be broken, therefore the atom concentration decreases in the solution. Thus the
absorption value calculated by the instrument according to these interferences is obtained
lower than the actual absorption value. In the other words, formation of compounds that do
not dissociate in the flame. The most common example is the formation of calcium and
strontium phosphates.1
Ionization of the analyte reduces the signal. This is commonly happens to barium, calcium,
strontium, sodium and potassium.
Matrix interferences: These interferences are due to differences between surface tension and
viscosity of test solutions and standards.
To overcome these intereferences some methods are being used.

For chemical interferences, using of releasing agents can be helpful. Especially cations that
react preferentially with interferent should be used. For example, Sr acts as releasing agent
for Ca with phosphate. Moreover protecting agents also can be used. The form of them is
stable, however they turn to volatile compounds with the analyte.
For spectral interferences, the not crossing line of the element should be used. By doing this,
the element will not do absorption at the same wavelength, just required element will be
analysed. 1

For ionisation, the decrease in the working temperature of the atomiser, can block the
interference. If the flame atomiser is used, propan-air flame should be used to decrease the
effect of the ionisation. However decreasing temperature is not always satisfying, because it

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also blocks the atomisation of the element. Another solution can be, the addition of another
element which has lower ionisation energy.

For background correction of the system,

The narrow line widths of hollow cathode lamps make spectral overlap rare. That is, it is
unlikely that an absorption line from one element will overlap with another. Molecular
emission is much broader, so it is more likely that some molecular absorption band will
overlap with an atomic line. This can result in artificially high absorption and an improperly
high calculation for the concentration in the solution. Three methods are typically used to
correct for this:

• Zeeman correction - A magnetic field is used to split the atomic line into two
sidebands. These sidebands are close enough to the original wavelength to still
overlap with molecular bands, but are far enough not to overlap with the atomic
bands. The absorption in the presence and absence of a magnetic field can be
compared, the difference being the atomic absorption of interest.
• Smith-Hieftje correction (invented by Stanley B. Smith and Gary M. Hieftje) - The
hollow cathode lamp is pulsed with high current, causing a larger atom population
and self-absorption during the pulses. This self-absorption causes a broadening of
the line and a reduction of the line intensity at the original wavelength.
• Deuterium lamp correction - In this case, a separate source (a deuterium lamp) with
broad emission is used to measure the background emission. The use of a separate
lamp makes this method the least accurate, but its relative simplicity (and the fact
that it is the oldest of the three) makes it the most commonly used method. 9

1. DATA AND CALCULATION

The experiment system was not working accurate. Therefore the data obtained for this
experiment was an old data of the same experiment.

Concentration (ppm) Absorbance

5 0.039

10 0.079

20 0.153

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 Unknown concentration 0.078

Graph 2 Concentration vs Absorbance according to the data

According to this data, a graph plotted concentration vs absorbance. From the graph equation ,
which is y=0.0076x+0.002 the unknown concentration can be calculated, by using its
absorbance value.

y=0.0076x+0.002

0.078=0.0076x+0.002

x=10 ppm

The correct concentration of the unknown solution was 10 ppm, therefore there is no need to
do experimental error calculation.

Example For Calculation of Pb2+ Solution

How much kilograms of Pb(NO3)2 is needed to prepare a solution that is 100 ppm with 225
mL Pb2+ ?

100×10-6kg Pb2+ 1 L solution×225×10-3L solution×1 mol Pb207.1×10-3kg×1 mol

Pb(NO3)21 mol Pb×331.21×10-3kgPb(NO3)21 mol Pb(NO3)2=3.60×10-5 kg Pb(NO3)2
is needed

2. DISCUSSION AND CONCLUSION

In this experiment, it was aimed to determine the concentration of an unknown concentrated
Pb2+ solution by using atomic absorption spectroscopy method. This was done by using
principles of atomic absorption spectroscopy for three standard Pb2+ solutions, which have
concentrations of 5, 10 and 20 ppm.

First of all, these three already prepared solutions were sent to the system to observe
absorption values for each concentration. According to the data taking from this observation,
unknown solution was sent to the system. The absorbance of the unknown solution was also
recorded. From the graph which was drawn according to the taken data, the concentration of
the unknown solution was found 10 ppm, which was a 100% correct calculation; therefore
there was no percentage error.

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However if the unknown concentration was found different, it could be talked about the errors
in the system. As an atomiser, there was flame atomiser in the system. The usage of flame
atomiser, could create especially chemical interference in the system. Moreover, the usage of
flame atomiser, is not good enough, because some of the solution cannot be sprayed on
atomiser, therefore more solution is used than the system needs. The other interferences could
also be seen, because the system cannot be perfect.

It can be also said that the system may not be clean enough. Normally, system should have
been cleaned by distilled water, which was done for the system. However, because of the
pipeline of the system was taking the liquid so slowly, the water may not have been passed
from the all parts of the system. That slow action of the system can be also discussed for the
Pb analysis. The absorbance values were read in long time, therefore system may not have
been worked accurate enough, the calibration with 5, 10 and 20 ppm cannot be accepted as
totally correct.

Moreover, the calibration and known concentrated solutions were already prepared before the
experiment was started to be done. Therefore, it is not certain that the solutions are prepared
according to the values required and maybe the solutions lost their characteristic because of
laboratory conditions of them.

Consequently, there was no mistake made by the instrument. However, if there would be an
error, the error could come from the factors which were counted above. It was understood the
working principal of each instrumentation part. The experiment was useful for students to
learn the principals of the atomic absorption spectroscopy.

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3. REFERENCES
1. Undergraduate Instrumental Analysis, (2005),
2. Atomic Spectroscopy, ANDOR Technology, (2010), from the World Wide Web:
http://www.andor.com/learning/applications/Atomic_Spectroscopy/
3. Atomic Absorption Spectroscopy, (unknown author), (1998), from the World Wide
Web: http://www.gmu.edu/depts/SRIF/tutorial/aas/aas.htm
4. Phosphate Analysis, RUTGERS, (unknown date), from the World Wide Web:
http://genchem.rutgers.edu/phosA.html
5. Atomic Absorption Spectroscopy, Adelaide University, Australia, (unknown date)
from the World Wide Web : http://www.chemistry.adelaide.edu.au/external/soc-
rel/content/aa.htm
6. Hollow Cathode Lamps, HERAEUS, (unknown date), from the World Wide Web:
http://www.heraeus-noblelight.com/en/optics-analytics/products-for-optics-
analytics/hollow-cathode-lamps.html
7. Photomultiplier Tubes, Molecular Expressions, (2004) fromt he World Wide Web:
http://micro.magnet.fsu.edu/primer/digitalimaging/concepts/photomultipliers.html
8. Photomultiplier Tube , unknown author, (2000) from the World Wide
Web:http://www.files.chem.vt.edu/chem-ed/optics/detector/pmt.html
9. Atomic Absortpion Spectroscopy, Elena Svestianova,( unknown date), from the World
Wide Web:

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http://weather.nmsu.edu/teaching_material/soil698/student_reports/spectroscopy/repor
t.htm

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