Molecular Spectroscopy

UNIT 5 ATOMIC ABSORPTION AND

EMISSION SPECTROMETRY
Structure

5.0 Introduction
5.1 Objectives

5.2 Origin and Classificationof Atomic Spectra

5.3 Flame Atomic Absorption Spectrometry

5.3.1 Flame and its Structure

5.3.2 Principle of Flame Atomic Absorption Spectrometry
5.3.3 Instrumentation for Flame Atomic Absorption Spectrometry
5.4 Graphite Furnace Atomic Absorption Spectrometry (GFAAS)

5.4.1 Electrothermal Atomisers

5.4.2 Advantages and Disadvantages of GFAAS

5.5 Flame Atomic EmissionSpectrometry

5.5.1 Principle of Flame Atomic Emission Spectrometry
5.5.2 Instrumentation for Flame Atomic Emission Spectrometry
5.6 ICP- Atomic Emission Spectrometry

5.6.1 Plasma and its Characteristics

5.6.2 Inductively Coupled Plasma
5.6.3 Instrumentation for ICP-AES
5.7 Interferences in Atomic Absorption and Emission Spectrometry
5.7.1 Interferences in AAS and GFAAS
5.7.2 Interferences in AES
5.7.3 Interferences in ICP-AES

5.8 Environmental Applications of Atomic Absorption and Emission

Spectrometry
5.9 Let Us Sum Up

5.10 Terminal Questions

Answers

5.0 INTRODUCTION
In the previous unit you have learnt about molecular spectroscopic methods
viz., UV-VIS, fluorescence, and vibration Raman spectroscopies. In the present
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Spectroscopic Methods unit, you would learn about spectrometric methods based on atomic spectra.
Herein, we would take up atomic absorption and emission spectrometry.

We will begin the unit with an explanation of the origin of atomic spectra and
their classification. Thereafter, we would take up atomic absorption
spectroscopy in which we measure the absorption of radiation by the atomised
element in the ground [Link], we would explain the principle of,and
instrumentation required for flame atomic absorption spectroscopy(FAAS) and
graphite furnace flame atomic absorption spectroscopy (GFAAS). These differ
in the way we get the atomised atoms in the ground state. In the case of FAAS
we would first describe the structure of flame then explain the principle of
AAS before discussing about instrumentation. In the context of GFAAS we
would first describe electrothermal atomiser and then take up the merits and
demerits of GFAAS.

Having discussed atomic absorption spectroscopy, we would move on to atomic

emission spectroscopy (AES). Here, we would explain the principle of, and
instrumentation required for flame atomic emission spectroscopy (FAES) also
called flame photometry and ICP-AES i.e., inductively coupled plasma atomic
emission spectroscopy. In this context we would first discuss about inductively
coupled plasma, and then discuss about the instrumentation for ICP-AES.
Towards the end of the unit, we would take up some environmental applications
of these atomic spectroscopic methods.

In the next unit,you would learn about resonance spectrometry viz., ESR and
NMR spectrometry.

5.1 OBJECTIVES
After studying this unit, you will be able to:

™ explain the origin and typeof atomic spectra;

™ describe the structure and characteristics of a flame;

™ explain the principle of flame atomic absorption spectrometry;

™ outline the quantitative methodology of flame atomic absorption

spectrometry;

™ compare the flame and flameless atomisation of the analyte in terms of

sensitivity and detection limits,

™ draw schematic diagrams illustrating different components of flame atomic

absorption and flame atomic emission spectrometers;

™ describe the functioning of pneumatic nebuliser used in atomic

spectrometry;

™ explain the principle of flame emission spectrometry;

™ enlist various excitation sources for atomic emission spectrometry,

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™ describe the different types of plasma sources and nebulisers used in ICP- Atomic Absorption and
Emission Spectrometry
AES;

™ outline the quantitative methodology of the atomic emission spectrometry

using ICP as the source, and

™ discuss the interferences observed in different atomic absorption and atomic

emission spectrometric determinations,

5.2 ORIGIN AND CLASSIFICATION OF ATOMIC

SPECTRA
The atomic spectroscopic
As a chemist you would have performed a flame test for the identification of methods are based on the
some elements especially the alkali and alkaline earth metals in their salts. transitions amongst the
quantised electronic energy
You would have observed the beautiful colours imparted by the elements to levels of the atoms caused by
the flame. The colour is a consequence of the emission of radiation by the the absorption of radiation by
gaseous atoms / ions in the excited state. In mid 19th Century Bunsen and the atoms in ground state or
by the emission of radiation
Kirchhoff showed that the optical radiation emitted from flames is characteristic by the excited atoms in
of the elements present in the flame gases or the ones introduced into the vapour phase.
burning flame. It was also demonstrated that the intensities of the emitted
radiation, was dependent on the amounts of elemental species present.
Therefore, the wavelength and the intensity of the emitted radiation can Thebemaximum operating
used for the identification and quantification of the element. temperature is determined by
the identity of fuel and
Similarly, it was also shown that cold vapours (atoms in their ground state) of whereas, the exact
oxidant
temperature is fixed by the
an element absorb characteristic wavelength of radiation. This led to the
ratio of fuel and oxidant.
establishment of atomic spectroscopy as an instrumental method of elemental
[Link] us understand the origin of atomic spectrum in terms of the
transitions amongst different atomic energy levels.

Origin of Atomic Spectrum

You would recall from your earlier knowledge that an atom contains a set of
quantised electronic energy levels that can be occupied by the electrons
depending on the energy. The energy level with the minimum energy is called
ground state while the ones of higher energies are referred to as the excited
states. Further, an electron in an energy level can undergo a transition to
another level of a higher energy by absorbing a photon of appropriate energy
equal to the difference in the energies of the two levels. On the other hand, the
transition of an electron from a higher energy level to a level of lower energy
is accompanied by the emission of the difference in energy in the form of a
radiation of appropriate wavelength. A spread of the wavelengths of the
radiation absorbed or emitted versus their intensities is called a spectrum.

You would recall that the interaction of radiation and matter can manifest
itself in terms of absorption, emission, or fluorescence emission. Accordingly,
we have three different atomic spectroscopic methods viz., atomic absorption,
atomic emission, and atomic fluorescence respectively.

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Spectroscopic Methods

(a) (b) (c)

Fig. 2.1: Schematic representation of the transitions in atomic (a) absorption,(b)
emission and (c) fluorescence emission spectroscopy

A schematic representation of the transitions associated with the phenomenon

of atomic absorption, atomic emission and atomic fluorescence emission is
given in [Link] this unit we would take up atomic absorption and atomic
emission spectroscopies.

5.3 FLAME ATOMIC ABSORPTION

SPECTROSCOPY
Inatomic absorption spectroscopy, the atomic vapours containing free atoms
of an element in the ground state are subjected to a UV-VIS radiation source
emitting a characteristic frequency of the element present in atomic vapours.
A part of the radiation is absorbed, and the intensity of the radiation decreases.
The absorbed radiation causes excitation of electrons from the ground state to
an excited level. The extent of absorption is a quantitative measure of the
concentration of the atomic vapours of the element in the ground state. It is an
electronic excitation, and the energy of transitions lies in the UV-VIS region
of the electromagnetic spectrum. The process of converting the elements present
in a sample to gaseous atoms or elementary ions is called atomisation. It can
be accomplished by a flame, furnace, plasma, or electric arc. In flame atomic
absorption spectroscopy,we use flame as a source of energy for atomisation of
the element being analysed. Let us learn about flames and their characteristics.

5.3.1 Flame and its Structure

A flame can be described as a gas phase reaction which takes place with the
emission of light. It is produced by burning a mixture of fuel and air (or an
oxidant) in a burner. In flame based spectroscopic methods a variety of fuels
can be used and generally air, oxygen, or nitrous oxide (N2O) is used as the
oxidant. The flame temperature depends on fuel-oxidant ratio. Combination
of a given fuel gas with air produces lower temperatures as compared to when
O2 is used as oxidant. Alkali and alkaline earth metals are easily excited at low
temperatures obtained by using air. However, for heavy metals O2 or N2O are
employed as oxidants. The requisite temperature for analysis can be obtained
by varying the fuel-oxidant ratio. Table 2.1 lists some common fuels and
oxidants along with range of temperature attainable by using them.

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 Table 2.1: Fuel-oxidant mixtures and the attainable temperature Atomic Absorption and
Emission Spectrometry
Fuels Oxidants

Air Oxygen Nitrous oxide

Propene 2250 3070 —-

Acetylene 2470 3320 3220

Hydrogen 2370 3050 —-

There are two types of flames commonly used in atomic spectroscopy. In one
of these, the fuel and oxidant as air (or oxygen) are well mixed before
combustion, these are called premix or laminar flames as they exhibit laminar
flow. On the other hand, in second type of flame the fuel gas and the oxidant
are mixed in the flame itself. They are called unpremix or turbulent flames
since they exhibit turbulence. We would take up the premix or laminar flame
here.

Premix or laminarflame

Flames are not uniform in composition, length, or cross section. A schematic

structure of a premixed or laminar flameis given in Fig. 2.2.

It may be noted that as only

ground state atoms are
involved in this process.
Therefore, the ionisation
occurring due to high
temperature of the flame
needs to be kept to a
minimum.

In AAS the absorption of

Fig. 2.2: Schematic structure of a laminar flow flame showing various zones
resonant radiation by ground
state atoms of the analyte is
The laminar flame may be divided into the following four regions or zones. used as the analytical signal.

i) Preheating zone

ii) Primary reaction zone or inner zone

iii) Interconal zone

iv) Secondary reaction zone

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Spectroscopic Methods The first or the innermost region of the flame is the preheating zone where the
fuel-oxidant mixture is heated to the ignition temperature by thermal conduction
from the primary reaction zone. The second zone is the primary reaction
zone or inner zone. This zone is about 0.1 mm thick at atmospheric pressure
and is visible by virtue of its blue green light. This region is not used for flame
photometry. The maximum temperature is achieved just above the tip of the
inner zone. The higher temperature favours the production of free atoms, and
it is this zone that is used for flame based atomic spectroscopic methods.

Immediately above the primary reaction zone lies the third orinterconal zone
which can extend up to considerable height. The outermost fourth zone is the
secondary reaction zone. In this zone, the products of the combustion processes
are burnt to stable molecular species by the surrounding air. A laminar flame
makes a strong hissing noise which gets louder when a liquid is atomised into it.

The shape of an unmixed flame is generally different. The inner zone can still
be recognised, but it is very vague and is thickened. We will not discuss the
unmixed flame here. Let us now learn about the principle of flame atomic
absorption spectrophotometry. However, before that answer the following
simple question.

SAQ 1

List different zones of a laminar flow flame. Which of these zones is

used in flame based atomic spectroscopic methods?

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5.3.2 Principle of Flame Atomic Absorption Spectrometry

The concept of atomic absorption spectrometry (AAS) was proposed by two
groups in 1955, A. Walsh of Australia andC T J Alkamade and J M W Milatz
fromthe Netherlands. You have learnt that in atomic spectroscopy, the analyte
must be present in the atomic vapour state. In flame atomic absorption
spectrometry, the atomisation is performed by aspirating the sample solution
into a flame where the analyte element is converted into gaseous phase atoms.

As the temperature of atomisation is low; most of the atoms remain in the

ground state which can absorb characteristic radiation from the radiation source
made from the analyte element. One such source is halogen cathode lamp
(HCL) in which the cathode is made of the element that needs to be determined
and gives radiations characteristic of the [Link] would learn about HCL
in subsection 2.3.3. The radiation is absorbed by the atomic vapours and its
intensity decreases. The degree of absorption is a quantitative measure of the
concentration of ground state atoms in the vapours. The analysis is done by
comparing the observed absorption with the one obtained by suitable standard
samples of the analyte under similar experimental conditions, i.e., a calibration
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curve method is generally employed. For this we need to understand the Atomic Absorption and
Emission Spectrometry
concentration dependence of the absorption.

Concentration Dependence of Absorption

The absorption follows Lambert-Beer’slawaccording to which the extent of

Typical absorbance must be in
radiation absorbed by the absorbing species is a function of the path length the range 0.1 to 0.3 or else
and the concentration of the absorbing species. You have learnt about this law precision is poorer at the
in Unit 1. extremes due to instrumental
noise.
P
Mathematically, log 0 Hbc … (2.1)
P
where,

P0 = radiant power of incident light,

P = radiant power of transmitted light,
b = thickness of the absorbing medium,
å = absorption coefficient, and
c = concentration of absorbing analyte atoms.

The term, log Po/P is called absorbance and is represented as ‘A’. Therefore,
we can write it as follows.
P
log 0 A Hbc … (2.2)
P
Thus, absorbance of the sample is directly proportional to the concentration of
the analyte. The routine analytical methodology for quantitative determinations
using AAS is based on calibration method. Let us learn about the calibration
plot method.

Calibration plot method

In this method, a series of solutions of different known concentrations prepared

by diluting a standard solution are aspirated into the flame and absorbance for
each solution is measured. Then a graph is plotted between absorbance and
concentration, Fig.2.3. The concentration of the element in the unknown sample
can then be found out from the standard plot as is done in visible
spectrophotometry. Further, it is very important to measure theabsorbances of
the standard and unknown solutions under conditions that are as nearly identical
as [Link] though Beer’s law is followed, in practice the departures
from linearity are encountered.

Fig. 2.3: Calibration plot: Absorbance versus Concentration of the sample solution
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Spectroscopic Methods The nonlinearity is due to the transmission of unabsorbed light from the
radiation source. In addition, several uncontrolled variables in atomisation
and absorbance measurements may also affect the measurements. Therefore,
we need to find the concentration range in which the Lambert-Beer’s law holds
i.e., we get a straight linein the concentration versus absorbance plot. If the
analyte concentration happens to be outside the limits of the standards used
for calibration, then the analyte sample should be suitably diluted or
concentrated.

As the test solution is often a complex whoseall constituents are not known, it
becomes almost impossible to prepare standard solutions having a similar
composition to the analyte sample to obtain a calibration plot. In such cases
we use internal standard method orthe standard addition method. These methods
are beyond the scope of this course.

Let us now learn about the instrumental aspects of flame atomic absorption
spectrometry. However, before that answer the following simple question to
assess your understanding.

SAQ 2

What is the importance of calibration plot in flame atomic absorption

spectrophotometry?

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5.3.3 Instrumentation for Flame Atomic Absorption

Spectrometry
You have learnt above that in AAS the absorption of radiation by ground state
atoms of the analyte is used as the analytical signal. Accordingly, a source
delivering the characteristic radiation of the analyte is required along with an
atom reservoir into which the analyte is introduced and atomised. The basic
requirements of atomic absorption spectrophotometer instrument are like any
regular spectrophotometer; the sample holder cell being replaced by a flame.
Let us learn about the different components used in flame atomic absorption
spectrophotometer.

Components of Flame Atomic Absorption Spectrometer

A typical flame atomic absorption spectrophotometer consists of the following

components.

A. Radiation source
B. Atom reservoir (flame)
C. Monochromator
D. Detector
E. Readout device
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A block diagram showing the basic components of a flame atomic absorption Atomic Absorption and
Emission Spectrometry
spectrophotometer is given in Fig. [Link] a typical flame atomic absorption
spectrophotometric determination, the radiation from a hollow cathode lamp
is made to fall on the sample of the analyte aspirated into the flame, where a
part of it is absorbed. The transmitted radiation is then dispersed by a
monochromator and sent to the detector. The detector output is then suitably
processed and is displayed by appropriate readout device.

Fig. 2.4:Schematic diagram of an atomic absorption spectrophotometer showing its

basic components

Suchsingle channel instruments can perform measurements at asingle

wavelength. Nowadays, dual-channel instruments are also available that permit
simultaneous measurements at two different wavelengths. These contain two
independent monochromators for the purpose. Thus, these can be used for the
simultaneous determination of two elements; one can be the analyte to be
determined and the other may be a reference element. Let us learn about the
components of a flame atomic absorption spectrophotometer.

A. Radiation Sources

All commercially available flame atomic absorption spectrophotometers use

a radiation source that emits the characteristic spectrum of the element to be
determined. The essential requirement of the radiation source is that it gives a
constant and intense output. Generally,the hollow-cathode lamp (HCL), is
widely used as the radiation source. The electrodeless discharge lamps(EDL)
- another line sourcesare also frequently employed for the purpose and in fact
are superior for the elements such as As, Se and Te with low melting [Link]
us learn about HCL and EDL.

Hollow cathode lamp (HCL):It consists of a sealed cylindrical glass tube

with a quartz window at one end and a hollowed cylindrical cathode along
with an anode wire made of tungsten.

Fig. 2.5: Schematic diagram of hollow cathode lamp illustrating different

components
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Spectroscopic Methods The cathode is fabricated from the analyte element and the lamp is filled with
an inert gas such as argon or neon under vacuum (100-200 Pa). A schematic
diagram of a hollow-cathode lamp is shown in Fig. 2.5. When a voltage of
~300 V corresponding to 5-50 m A current is applied between the two
electrodes, a low-pressure glow discharge confined to the inside of the cathode
material is produced.

Basic function of the gas in the tube is to bombard the cathode and vapourise
the atoms from the cathode surface. For this the gaseous cations are accelerated
towards the cathode. The collision energy is sufficient to cause some atoms of
the cathode to be transformed into gaseous atoms in a process called sputtering.
These metal atoms are then excited by collisions with electrons and ions thus
emitting characteristic emission lines.

The emission spectrum of the cathode material includes several intense, sharp
lines due to transitions between excited states and the ground state, often called
resonance lines. Intensity of resonance lines from an HCL increases with
increasing current. As of now, HCL for over 60 elements are available.

Electrodeless discharge lamp (EDL): It contains a few milligrams of a

volatile element or a volatile compound such as halide, along with neon or
argon, under vacuum in a quartz tube. On the application of voltage, a discharge
is produced, and the gaseous atoms are excited by application of microwave
field or radio frequency of typical frequency. As the excited atoms decay to
the ground state or to other low energy levels, characteristic radiation of the
atom is emitted. The radiations emitted by EDLs are about 10-100 times more
intense than for the corresponding [Link] electrodeless discharge lamps
are available for many elements. However, their performance is not as reliable
as of the halogen cathode lamps.

B. Atomisers

The purpose of atomiser is to provide a small portion of the sample in the

optical path and convert it into free neutral ground state atoms. In flame atomic
absorption spectrophotometry, the flames arecommonly used for atomisation.
Let us learn about flame atomisers.

Flame atomiser

The flame atomiser assembly consists of two components viz., a nebuliser and
a [Link] a typical flame atomisation process, the sample solutions are
generally nebulised with the help of a nebuliser in which the sample in the
form of a solution is drawn in and is converted into a fine mist or an [Link]
aerosol so produced along with a mixture of a burning gas and an oxidant is
directed into the second component i.e., a [Link] have learnt above that
the flame temperature depends on fuel-oxidant ratio. The temperature required
for analysis is obtained by varying the fuel-oxidant ratio. Let us first learn
about the nebulisers.

Nebuliser is a device used for sample introduction into the flame. It consists
of thermal vapourisation and dissociation of aerosol particles at high
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temperatures producing small particle [Link] nebulisation methods are Atomic Absorption and
Emission Spectrometry
available. A few are listed below.

z Pneumatic nebulisation
z Ultrasonic nebulisation
z Electrothermal vapourisation
z Hydride generation

However, we would discuss about the pneumatic nebuliser only. A common

type of pneumatic nebuliser is called concentric pneumatic nebuliser. It The premix type of burner
consists of a fine capillary surrounded by concentric tube with a small opening usually produces an
near one end of the capillary. The capillary is dipped into the sample solution approximately laminar flame
and is commonly combined
while the outer tube is connected to a high-pressure gas supply. The sample with a separate unit for
solution is sucked into the capillary by the high-pressure gas stream flowing nebulising the sample.
around the tip of the capillary using the Bernoulli effect. The process is called
aspiration. The high velocity gas breaks up the liquid into various sized fine
droplets.

Fig. 2.6: Concentric type pneumatic nebuliser

Burners

Two major types of nebuliser burners used in atomic absorption

spectrophotometer are premix nebuliser-burner system and total consumption
[Link], in flame atomic absorption spectrophotometer the premix
burner is generally used. Let us learn about it.

Premix burner

In a premix burner, fuel and oxidant are thoroughly mixed inside the burner
housing before they leave the burner ports and enter the primary-combustion
or inner zone of the flame. In this type of burner, the solution of the analyte is
aspirated with the help of a nebuliser from the sample container into the mixing
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Spectroscopic Methods chamber in which the fuel gas is also introduced. The mixture of aerosol, fuel
gas and oxidant burn to yield stable noiseless flame. A schematic diagram of
premix nebuliser burner system is given in Fig.2.7.

Premix burners are called Bunsen, Méker, or slot burners depending on whether
they have one large hole, several small holes, or a slot as outlet port(s) for the
gas mixture, respectively. In case the burner contains several parallel slots, it
is called a multislot burner (e.g., a three-slot burner). The advantage with the
premix burner is that it is quiet to operate, and the analytical signal is
significantly less noisy. However, it also has certain disadvantages like; low
sensitivity in the determination of a given analyte.

Fig. 2.7: Schematic diagram of premix nebuliser burner system used in AAS

Flame atomisationis a simple method;however,it has the following

disadvantages.

i) Only about 10% of the nebulised sample reaches the flame and it is then
further diluted by the fuel and oxidant gases so that test material has very
small concentration in the flame.
ii) A minimum sample volume of 0.5-1.0 mL is needed to give a reliable
measurement.
iii) Viscous samples such as blood, serum, oils etc require dilution with a
solvent.

To avoid such problems, nonflame methods involving electrical heating have

been developed which are beyond the scope of this course.

C. Monochromators

You know that monochromators are the devices that can selectively provide
radiation of a desired wavelength out of the range of wavelengths emitted by
the source. In flame atomic absorption instruments, the monochromators select
a given emission line and isolate it from other lines due to molecular band
emissions and all non-absorbed lines. Some of these lines originate from the
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filler gas in the hollow cathode lamp while some others are the spectral Atomic Absorption and
Emission Spectrometry
emissions of various sample components during atomisation. Most
commercialflame atomic absorption instruments use diffraction gratings as
monochromators.

D. Detectors

As the wavelengths of resonance lines fall in UV region, the commonly used

detector in flame atomic absorption spectrophotometry is a photomultiplier
(PM) tube whose output is fed to a readout system. The radiation received by
the detector may originate not only from the selected resonance lines but also
from the emission within the flame. Therefore, in addition to absorption signal
intensity IA, the detector may receive signal intensity of (IA+S) where S is the
intensity of emitted radiation from flame. Since, we need the signal intensity
due to absorption only, therefore, the effects due to flame emission need to be
eliminated. This is achieved by using a mechanical chopper device.

E. Readout Devices

The readout systems include meters, chart recorders and digital display meters.
These days, however, microprocessor-controlled systems are commercially
available where everything can be done by the touch of a button. Modern
instruments provide a fast display of the experimental conditions, absorbance
data, statistical values, and calibration curves, etc.

Types of Flame Atomic Absorption Spectrometers

Having learnt about the essential components of an atomic absorption

spectrometer let us now learn about the different types of atomic absorption
spectrometers. There are two types of atomic absorption spectrophotometersas
given below.

z Single beam atomic absorption spectrophotometer

z Double beam atomic absorption spectrophotometer

Single Beam Atomic Absorption Spectrophotometer

A simplified sketch of a single beam flame atomic absorption

spectrophotometeris shown in Fig.2.8.

Fig.2.8:Schematic diagram of a single beam flame atomic absorption

spectrophotometer
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Spectroscopic Methods Double Beam Flame Atomic Absorption Spectrophotometer

In this type of instrument, the beam from the HCL is split into two parts by a
mirrored chopper, one half passing through the atomiser and the other half
around it, as schematically shown in Fig.2.9.

Fig.2.9:Schematic diagram of a double beam atomic absorption spectrophotometer

The two beams are then recombined by a half-silvered mirror and passed
through the monochromator. The ratio between the reference and sample signal
is then amplified and fed to the readout display and recorder. It must be noted
that reference beam in double beam instruments does not pass through the
flame and thus corrects for the loss of radiant power due to absorption or
scattering by the flame [Link] learnt about the instrumental aspects
offlame atomic absorption spectrometry, let us now take up the graphite furnace
atomic absorption spectrometry. However, before that answer the following
simple questions to assess your understanding.

SAQ 3
Name the line sources employed in flame atomic absorption
spectrophotometry.
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SAQ 4
In what way is a double beam atomic absorption spectrophotometer better
than a single beam spectrophotometer?
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 Atomic Absorption and
5.4 GRAPHITE FURNACE ATOMIC Emission Spectrometry
ABSORPTION SPECTROMETRY (GFAAS)
In case of FAAS the natural gas and air flame employed for excitation does
not have high enough temperature to excite transition metals, therefore the
method is selective towards detection of alkali and alkaline earth metals.
Further, the relatively low energy available from the flame leads to relatively
low intensity of spectra. To overcome these problems some flameless methods
of AAS have been developed. Two types of flameless atomisers are generally
used. These are graphite tube or L’Vov furnace and the carbon rod or filament.
AAS using graphite furnace is called GraphiteFurnace Atomic Absorption
Spectrophotometry (GFAAS) which is highly sensitive (100 to 1000 times as
compared to flame AAS) and requires a very small sample size. Let us learn
about the electrothermal or flameless atomic absorption spectrophotometry.

The basic principle of flameless AAS is similar to flame AAS. The analyte is
converted into vaporised atoms in ground state that are subjected to the
characteristic resonance radiation emitted by a suitable source. The absorption
of radiation and its extent form the basis of analytical applications. As regards
the instrumental aspects, the two techniques are similar to a good extent, the
difference being in the atomiser and the atom reservoir. Rest of the components
of the instrument are the same. Let us learn about the electrodeless or
electrothermal atomisers. GFAAS is also termed as electrothermal AAS because
of the electrothermal atomisers used.

5.4.1 Electrothermal Atomisers

The use of furnaces as atomisers for quantitative AAS goes back to the work
ofL’Vov, which led to the breakthrough of atomic absorption spectrometry
towards very low absolute detection limits. The essence of L’Vov method is to
completely vaporise a small amount of analyte sample in a graphite tube furnace
and obtain a good concentration of the analyte species in the vapour phase
which can be suitably determined. Let us learn about the working of graphite
furnace as an atomiser.

Graphite furnace

A graphite furnace consists of a hollow graphite cylinder having a length of

about 5 cm and diameter of about 1 cm. The tube is surrounded by a metal
jacket through which water is circulated and remains separated from the tube
by a gas space where an inert gas such as argon or nitrogen is circulated as
schematically shown in Fig. 2.10. A small amount of analyte sample solution
(1-100 PL) is introduced in the sample cell or holder by inserting the tip of
micropipette through a port in the outer jacket, and into the gas inlet orifice in
the center of the graphite tube. Alternatively, the powered analyte sample (about
10-500 Pg) is introduced directly into the graphite tube.

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Spectroscopic Methods

Fig. 2.10: Schematic diagram of the cross section of an electrically heated graphite
furnace

The nature and design of cuvettes or sample holder is of great importance in

GFAAS. Different types of cuvettes are commercially available. The standard
cuvette made from electrographite is suitable for the determination of volatile
elements such as Pb and Cd. Extended lifetime cuvettes can sustain faster
heating rate and have longer lifetime and are especially useful in the
determination of refractory elements.

The graphite tube is heated by the passage of an electric current to a temperature

capable of evapourating the solvent from the solution. The current is then
increased in such a way that initially the sample is ashed and then ultimately it
is vaporised producing metal atoms. In other words, a heating cycle is followed.
For reproducibility, the temperatures, and the time of the drying, ashing and
atomisation process are carefully selected depending on the metal to be
analyzed.

The radiation from the line source is passed through the central hollow graphite
tube containing the vaporised analyte. The absorption signal produced by this
method is a transient one and lasts for a few seconds. The signal will be obtained
only when the analyte is atomised. This can be recorded on a suitable chart
recorder. This is in contrast with the flame atomisation technique wherein a
steady absorption signal is obtained. Each graphite tube can be used for 100-
200 analyses depending upon the nature of material.

The sensitivity of GFAAS is much higher as compared to the flame AAS and
the detection limits are lower by 2-3 orders of magnitude than that in flame
AAS. This is so because in the furnace a much higher concentration of atomic
vapour can be maintained as compared with flames. Furthermore, in this
method, the dilution of the analyte by the solvent is avoided as the solvent is
evapourated before the atomisation step.

5.4.2 Advantages and Disadvantages of GFAAS

The most significant advantages of this flameless vaporisation method are:

124
z It eliminates the possibility of the interaction of the sample with different Atomic Absorption and
Emission Spectrometry
components of the flame, thereby eliminating anomalous results.

z The longer residence time for the analyte in the path of incident radiation
leads to a greater sensitivity.

z
Nebulisation serves to
As a higher proportion of the analyte sample is converted into vapours,
increase the surface area of the
the sensitivity is further enhanced. solution sample, so that the
solvent evaporation
z It provides an ability to deal with very small sample sizes. This becomes
(desolvation) can proceed
quite important in the context of clinical samples. more rapidly and the resulting
dried solute particles can be
However, it has the following disadvantages too. volatilised better.

z The background absorption effects are more serious.

z Analyte may be lost during ashing especially for the volatile compounds.

z Precision is poorer than in flame AAS. However, furnace auto samplers

have enhanced the precision of furnace AAS.

SAQ 5
In what way is the signal obtained in GFAAS different from that obtained
in flame AAS?
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The five processes occurring

5.5 FLAME ATOMIC EMISSION in the flame can be
SPECTROMETRY (FAES) summarised as follows.
i) MX(soln.)®MX(solid)
ii) MX(solid)!MX
In AES one (vap.)
invariably, starts
Atomic emission spectrometry is a method used for the determination of
iii) MX(vap.) ! M + X which may be
with a sample,
elements which can be easily excited for example, alkali and alkaline iv)
earthM(ground state) liquid,
in a solid, ! or gaseous
metals. This method is based upon the measurement of intensity of radiationM* (excited state)
form, and ends with
v) M* oM. + h υ results, which may
analytical
emitted, in the visible region, when a metal atom is introduced into a flame.
be qualitative, semi-
The wavelength of the radiation (or the colour) emitted tells us what the element quantitative, or quantitative.
Processes (ii) and (iii) may
is, and the intensity of the radiation tells us how much of the element is present.
take place simultaneously and
The International Union of Pure and Applied Chemistry (IUPAC) Committee process (iii) may take place
on Spectroscopic Nomenclature has recommended abbreviation FAES (flame partially if the temperature of
atomic emission spectrometry) for this technique. the flame is too low.

In this method a reproducible and representative amount of the sample is

introduced into an atomisation-excitation source where it is converted into
atomic vapours of the analyte in excited state. As the excited state is short
lived, the excited atoms return to the ground state after a very short lifetime
(typically 10 6 to 10- 9s). This is accompanied by the emission of electromagnetic
radiation, normally in the form of light in the UV-VIS region. This radiation is
characteristic of the constituents of the sample. The resolution of the emitted
radiation generates an emission spectrum, whose detailed analysis can be
exploited to obtain qualitative as well as quantitative details of the analyte.
125
Spectroscopic Methods You have learnt about the nature and structure of flame above. Let us learn
about the processes occurring when a solution of the analyte is put into the
flame.

Fate of the Sample in the Flame

In a typical flame atomic emission experiment, a solution containing the

relevant substance to be analysed is aspirated into the burner and dispersed
into the flame as a fine spray. This process is called nebulisation. In the flame,
the solvent evaporates first, leaving finely divided solid particles which move
to hottest region of the flame where gaseous atoms and ions are produced. The
atoms are excited by absorbing energy available from the flame. As the excited
atoms return to a ground state of lower energy, radiation of wavelength,
characteristic of the element, is emitted. The intensity of the emitted radiation
is then measured, which can be related to the concentration of the element
present, which forms the basis of quantitative analysis. The following processes
occur in the flame.

Desolvation: The sample containing metal particles is dehydrated by the heat

of the flame and the solvent is evaporated.

Vapourisation: The heat of the flame vapourises the sample constituents. No

chemical change takes place at this stage.

Atomisation: At this stage the metal ions that were in the solvent are reduced
to metal atoms. For example, Mg2+(aq) + 2e o Mg (g). By heat of the flame
and action of the reducing gas (fuel), molecules and ions of the sample species
are decomposed and reduced to give atoms.

Excitation: The atoms at this stage can absorb energy from the heat of the flame.
The amount of energy absorbed depends on the electrostatic forces of attraction
between the negatively charged electrons and the positively charged nucleus.
This in turn depends upon the number of protons in the nucleus. As electrons
absorb energy, they move to higher energy levels and are in the excited state.

Emission of radiation: Electrons in the

excited state are very unstable and move
back down to the ground state or a lower
energy state quite quickly. As they do so,
they emit the energy in the form of
radiation of characteristic wavelength,
which is measured by a detector. For some
metals this radiation corresponds to
wavelengths of light in the visible region
of the electromagnetic spectrum and is
observed as a characteristic colour of the
flame. As electrons from different energy
levels can emit light as they relax, the Fig. 2.11: Diagrammatic
flame colour observed will be a mixture representation of the processes
occurring in flame obtained from
of all the different wavelengths emitted any hydrogen flame
126
by the different electrons in the metal atom under investigation. Fig. 2.11 gives Atomic Absorption and
Emission Spectrometry
a block diagram representing the processes occurring in the flame.

The number of atoms in the excited state increases very rapidly with increase
in temperature. Therefore, flames with higher temperatures will increase the
number of excited atoms and make the method more sensitive. Higher
temperatures are also required for decomposition of the compound having
high lattice energies into atoms. However, higher temperatures may also cause
ionisation of the atoms that may cause interference in the determination.
Therefore, we need to optimise the temperature of the flame to be used.

5.5.1 Principle of Flame Atomic Emission Spectrometry

As you would have understood by now that the general procedure in flame
photometric determination involves preparation of the sample solution in a
suitable solvent and aspirating it into the flame and measuring the intensity of
the emitted radiation at the characteristic wavelength of the element. From the
radiation intensity measured, the concentration of the element in the sample is
then determined as the energy emitted by the excited atoms in the flame can
be related to the number of atoms contained in the sample.

However, flame photometry is not an absolute method; it is empirical and is

sensitive to experimental conditions. For example, the signal intensity from a
flame is dependent on the flame temperature, the rate of flow of liquid into the
flame, the pressure and rate of flow of fuel gases, and many other variables
which affect the character of the flame or atomisation of the sample. Therefore,
we can obtain reliable results only by performing repeated checks of
reproducibility and the effects of altering conditions. It is therefore, essential
that the relation between the intensity of the emitted radiation and the
concentration of the associated element must be established. In other words,
we need to prepare a calibration curve as shown in Fig. 2.12.

The calibration curve is prepared by measuring the intensity of emission for a

series of solutions of different concentrations prepared by using a standard
solution and plotting a graph
between emission intensity versus
concentration of the ionic species
of the element of interest. The
concentration of the element in the
unknown sample can then be
found out from the standard plot
as is done in visible
spectrophotometry. Further, it is
very important to measure the
emission from the standard and
unknown solutions under
conditions that are as nearly
identical as possible.
Fig. 2.12: Calibration plot: Emission
intensity versus Concentration of the analyte
127
Spectroscopic Methods Let us take up the instrumentation required for flame atomic emission
spectrometry.

5.5.2 Instrumentation for Flame Atomic Emission

Spectrometry
The instrument used in flame emission spectrometry is called flame emission
spectrometer (commonly called flame photometer). Aschematic diagram
showing the layout of various components of a flame photometer is given in
Fig. 2.12. The role of different components is as given below.

Flame atomiser: It converts the sample into excited atomic species and consists
of the following.

z Nebuliser and mixing chamber: It is a means of transporting a

homogeneous solution into the flame at a steady rate.

z Atomiser burner: Here the fuel and oxidant burn to give a flame that can
be maintained in a constant form and at a constant temperature.

Monochromator (or filter): It isolates the light of the wavelength to be

measured from that of extraneous emissions.

Detector: It helps in measuring the intensity of radiation emitted by the flame.

Amplifier and Readout Device: It is used to amplify the signal and provide a
suitable output.

Fig. 2.13: Schematic diagram showing the layout of various components of a flame
photometer

You have learnt about the working of these components in the context of AAS.
The notable differences from FAAS are that the monochromator is placed
after the sample and secondly, we need a lens to direct the emitted radiation to
the monochromator. Let us now take up ICP-AES.

5.6 ICP- ATOMIC EMISSION SPECTROMETRY

The plasma based AES in principle, is similar to the FAES ; the only difference
being that flame is replaced by much more energetic atomization-excitation
128
processes using plasma. In emission work, the argon plasma is frequently Atomic Absorption and
Emission Spectrometry
employed. Let us learn about the plasma and its characteristics.

5.6.1 Plasma and its Characteristics

An ideal atomisation-excitation source should have the following
characteristics.
The sun, lightning, and the
1. It should separate the analyte from its original matrix to minimise aurora borealis are examples
interferences. of plasmas found in nature.
2. It should have appropriate energy to ensure complete atomisation but keep
ionisation to a minimum.
3. It should provide an inert environment, to keep the undesirable molecular
species formation to a minimum.
4. It should have none or negligible background radiation.

As always, it is difficult to attain ideality, however, plasma sources are quite

promising for the purpose of atomisation-excitation job in atomic emission
spectrometry. A plasma source is an electrically neutral, highly ionised gas
that consists of ions and electrons. It is sustained by absorbing energy from an
electric or magnetic field. Three types of power sources have been employed
in argon plasma spectroscopy. One is a powerful radio frequency generator
that powers an induction coil, the magnetic field generated from it help in
establishing the plasma. The second is a dc electrical source capable of
maintaining a current of several amperes between electrodes immersed in the
argon plasma and third one is a microwave frequency generator through which
the argon flows. Accordingly, there are three types of plasma
sourcesnamely,inductively coupled plasma (ICP), Direct current plasma (DCP),
and Microwave induced plasma (MIP). However, we would take up only the
inductively coupled plasma (ICP), as it appears to offer the greatest advantage
in terms of sensitivity and freedom from interference.

5.6.2 Inductively Coupled Plasma

The cost of argon gas
The inductively coupled plasma (ICP) is used is a major
component of the
plasma induced by radiofrequency. The
routine plasma
energy transfer is mediated by an operation cost.
induction in that produces a magnetic
field which is helps in establishing and
sustaining the plasma. The energy of a
high frequency generator is transferred to
a gas, generally argon, flowing at
atmospheric pressure. A typical
inductively coupled plasma source is
called a torch (Fig.2.13).

The most common ICP torch in use today

has evolved over decades of
Fig. 2.13: A schematic section
diagram of an ICP torch
129
Spectroscopic Methods development. It consists of a quartz tube whose upper part is surrounded by a
radiofrequency work coil. The torch assembly is designed to deliver gases so
that stable argon plasma is formed at the open end through which the sample
aerosol can be injected. Let us learn about the different components of the ICP
torch and their functions.
Quartz tube: The body of the torch consists of three concentric quartz tubes;
the diameter of the largest tube being about 2.5 cm. The tube has three separate
gas inlets. The argon gas enters the plasma through the outer channel with a
tangential flow pattern at a rate of 8 – 20 L min-1. The gas traveling up the
central channel is called auxiliary gas and also has a tangential flow pattern.
The innermost third inlet is connected to the nebuliser from which the gas
enters the plasma along with the sample in a laminar flow.
Radio Frequency Power Generators: The majority of radiofrequency (rf)
power generators are crystal controlled radiofrequency generators. These are
designed to operate within the industrial frequency bands of 27.12 or 40.68
MHz, although plasma generators have been described operating at between 5
to 100 MHz. The radio frequency at which the torch operates is an important
parameter in sustaining plasma operation. At the lower frequency range, it is
necessary to deliver large power up to 30 kW to sustain the plasma. At a
frequency of 27.12 MHz, the generators are normally designed with maximum
power ratings of between 2 and 5 kW, and are often used routinely to deliver
about 1 kW to the plasma. The radiofrequency power supply is so controlled
that it ensures a constant power transfer to the induction coil.
Work coil: The work coil consists of a water-cooled induction coil that is
powered by a radio frequency generator. The copper induction coil is wrapped
two or three times around the ICP torch and has water flowing through it for
cooling purposes. The lines of force, generated by the magnetic field, are
directed along the axis of the solenoid inside the tube and take the form of an
ellipse on the outside.
Argon gas supply: The conventional argon plasma torch uses between 13
and 20 liters of argon per minute, mainly to ensure that the outer quartz glass
tubing adjacent to the plasma is adequately cooled. Such a high consumption
of argon gas is met by installing a liquid argon supply Dewar flask rather than
relying on conventional compressed gas cylinders.
Mechanism of plasma formation
The ionisation of the argon gas flowing through the crystal tube inside the
solenoid is initiated by a spark from a Tesla coil. The resulting ions and the
electrons are subjected to the fluctuating magnetic field produced by the
induction coil. This makes them flow in the closed annular paths within the
coils. The induced or eddy currents are thus produced. These electrons rapidly
acquire enough energy from the oscillatory field generated by the induction
coil and sustain a high degree of ionisation. This leads to the formation of ring
shaped toroidal plasma. The spacing between coil and torch, the distance
between individual copper coils and the concentricity of both coil and torch
130 are important parameters in the formation of stable plasma.
Appearance of ICP plasma Atomic Absorption and
Emission Spectrometry
The typical plasma has a very intense, brilliant white, nontransparent core
The plasma is self maintai-
topped by a flame like tail as shown in Fig.10.3 (a). The analytical zone has a ning and continuous.
temperature of 5000-8000 K and is approximately 1 cm above the coils. It
offers the best optical viewing area for maximum sensitivity. Fig.10.3 (b) shows
the variation of temperature throughout the plasma. The plasma emits a
continuum of background radiation that extends from the visible into the
ultraviolet region. The radiation originates from electrons, Ar and Ar+ ions, as
well as various atomic and molecular species in the matrix and their
recombination products. In the region 10 to 30 mm above the core, the
continuum fades, and the plasma is optically transparent. The spectral
observations are generally made at a height of 15 to 20 mm above the induction
coil. Here the background radiation is remarkably free of argon lines and is
well suited for analysis.

(a) (b)
Fig. 2.14: (a) An ICP torch (b) A schematic diagram showing the temperature profile
of a typical ICP torch

Choice of Argon as Plasma Gas

Argon is commonly used as the plasma gas because it being an inert gas, does
not form stable compounds with analyte [Link], there would be
lesser chemical interference in the event of atomisation in the plasma. Further,
as its emission spectrum is relatively simple, and optically transparent in the
UV-visible region it does not cause spectral interference in emission
spectrometry.

In addition, as the first ionisation energy of argon is quite high (15.75) eV, it
has the capacity to atomise, ionise and excite most of the elements of the
periodic table which in turn permits the determination of almost all elements
that can be excited to emit lines in the UV-visible region.
131
Spectroscopic Methods
SAQ

Enlist different components of ICP torch and give their function in one
line each.
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5.6.3 Instrumentation for ICP-AES

A schematic layout of an ICP-AES spectrometer is given in Fig.2.15. The
sample in the solution form is nebulised and injected into the plasma source
with the help of a suitable nebuliser. The emitted radiation is passed through
monochromator and after dispersion it is detected by a photodetector and sent
to the processing unit for the processing and generating suitable output.

Fig. 2.15: A schematic layout of different components of an ICP-AES

spectrometer

Two general arrangements of instrumentation viz., sequential spectrometers

and simultaneous spectrometersare widely used in ICP-AES. The basic
principle or the set-up is similar for these. However, these differ on the type of
dispersion method, or the monochromator assembly used to disperse or resolve
the large number of emission lines emerging out of the plasma and the detector
device. Here, we would take up only the sequential spectrometer.

Sequential Spectrometers

These instruments use a moveable grating monochromator to select

wavelengths in sequential order and use a single photomultiplier tube to detect
them.

132
 Atomic Absorption and
Emission Spectrometry

Fig. 2.16: A schematic diagram showing the optical diagram of a sequential ICP
optical emission spectrometer

A schematic diagram of a sequential spectrometer is shown in Fig. 2.16. The

monochromator is programmed to make measurements in turn or sequentially
at a pre-programmed series of peaks and background wavelengths to cover
the elements of interest. For this purpose, the grating of the monochromator is
rotated in a controlled manner to sequentially focus a predetermined wavelength
on the exit slit. Alternatively, the grating is kept fixed and the slit and the
photomultiplier detector are moved to detect the desired wavelengths. As only
a few components are used these instruments are economical. However, longer
analysis times, poorer accuracy and precision are the major disadvantages of
sequential instruments. In addition to these, the reproducibility of wavelength
selection is another area of concern.

5.7 INTERFERENCES IN ATOMIC ABSORPTION

AND EMISSION SPECTROMETRY
As mentioned above, the success of the quantitative determination depends
on how accurately the intensity of the radiation represents the concentration
of the analyte. It has been found that number of factors besides the analyte,
affect the intensity of the radiation. The contributions of these factors are known
as interferences and are found to influence the outcome of the analytical
procedure. These interferences need to be addressed to put the technique to
analytical use. We may define an interference to be a chemical, physical, or
spectral effect that may cause the analyte signal to be altered in intensity.
Accordingly, there are three types of interferences viz., spectral, chemical,
and physical interferences.

Let us first learn about these in the contexts of flame AAS and GFAAS.
Absorption due to molecular
5.7.1 Interferences in FAAS and GFAAS species and scattering are
more problematic with
The spectral Interferences in FAAS and GFAAS refer to the presence of electrothermal atomization.
another atomic absorption line or a molecular absorption band close to the
133
Spectroscopic Methods spectral line of the analyte element being monitored. It qualifies to be an
interference if it is not resolved by the monochromator. Most probable spectral
interferences are the ones of the molecular emissions from oxides of other
elements in the [Link] source of spectral interference is the light
scattering or absorption by solid particles, unvaporised solvent droplets or
molecular species in the flame. This problem is significant at wavelengths
less than 300 nm when solutions of high salt content are aspirated. A yet another
source of spectral interference is the background emission from the flame.

The chemical interferences include interferences due to ionisation, formation

of low volatility compounds, dissociation, etc. During atomisation in the flame,
several reactions occur resulting in the formation of analyte compounds which
decrease atomic population in the cell. Most important chemical interference
is due to anions and formation of compounds of low volatility from the analyte
element. For example, the absorbance due to Ca is decreased in presence of
phosphate because of the formation of calcium phosphate having low volatility.

Specific strategies are available for addressing these interferences. For example,
the interference due to phosphate can be eliminated by using Sr or La as
releasing agents that react preferentially with phosphate and avoids its reaction
with the analyte element i.e., calcium.

The physical interferencesare independent of the analyte type and have nearly
the same effect on emission or absorption spectrum with a given type of
atomiser. These may be due to variations in the gas flow rates, changes in the
solution viscosity affecting its rate of aspiration into the flame which may
finally change the atomic concentration in the flame. Some instruments offer
the capability of using internal standards that can partially compensate for
changes in physical parameters including flame temperature.

5.7.2 Interferences in FAES

In FAES one type of spectral interferences arise when two elements exhibit
spectra, which partially overlap, and both emit radiation at same wavelength.
The detector cannot distinguish between the sources of radiation and records
the total signal, thus resulting in incorrect answer. Such interference can be
overcome either by taking measurements at an alternative wavelength which
has no overlap, if available, or by removing the interfering element by
extraction. The second type of spectral interference deals with spectral lines
of two or more elements which are close, but their spectra do not overlap. This
type of interference can be reduced by increasing the resolution of the spectral
isolation system. A third type of spectral interference occurs due to the presence
of continuous background which arises due to high concentration of salts in
the sample, especially of alkali and alkaline earth metals. Some organic solvents
also produce a continuous background. This type of interference can be
corrected by using suitable scanning technique.

In FAES ionisation interferencecould be observed due to ionisation of some

of the metal atoms by the flame, e.g., in case of sodium the Na+ ion formed has
its own emission spectrum with frequencies, which are different from those of
134
atomic spectrum of the Na atom. This interference can be eliminated by adding Atomic Absorption and
Emission Spectrometry
a large quantity of a potassium salt to the standards as well as sample solutions.
The addition of potassium salt suppresses the ionisation of sodium, as the
potassium atom itself undergoes ionisation due to low ionisation energy.

The chemical interferences arise due to the reaction between different

interfering species and the analyte. For example, the presence of certain anions,
such as oxalate, phosphate, sulphate, and aluminate, in a solution may affect
the intensity of radiation emitted by an element. This type of interference is
called cation-anion interference and result in decrease in the signal intensity.
In some cases, the formation of stable metal oxide due to the oxygen is present
in the flame, results in reduced signal intensity. The alkaline earth metals are
subject to this type of interference. This type of interference can be eliminated
by either using very high flame temperature to dissociate the oxides or by
using oxygen-deficient environment to produce excited atoms.

5.7.3 Interferences in ICP-AES

In case of ICP-AES the interferences may occur in any stage of the operation,
starting from the sample preparation stage to the plasma operating conditions.
The spectral interferences in ICP-AES may be caused by either the overlap
of a spectral line from another element or unresolved overlap of molecular
band spectra. For example, Cu emission at 515.323 nm is likely to show an
overlapping with the emission from Ar at 515.139 nm. These spectral
interferences can be minimised either by using a high-resolution dispersion
system or by using more than one analytical line for the detection of a single
element. In addition, background emission from the source and stray light
from the line emission of high concentration elements, may also contribute.
Background emission and stray light can usually be compensated for by
subtracting the background emission determined by measurements adjacent
to the analyte wavelength peak.

Thephysical interferences are associated with the processes of sample

nebulisation and transport. The differences in the physical properties of the
sample and calibration solutions lead to variations in the aerosol droplet size.
This may influence the efficiency of the nebuliser and the sample introduction.
The physical interferences can be reduced by diluting the sample. The use of
an internal standard also proves to be [Link] chemical interferences
include molecular compound formation, ionisation effects, and solute
vaporisation effects. These effects are generally not very significant in ICP-
AES. If present, these can be minimised by carefully controlling the operating
conditions such as incident power, observation position, matrix matching, etc.

5.8 ENVIRONMENTAL APPLICATIONS OF

ATOMIC ABSORPTION AND EMISSION
SPECTROMETRY
Air, soil, and water are three components of environment where determination
of toxic contaminant is of extreme importance. Analysis of particulate matter
135
Spectroscopic Methods in air from industrial establishments is the most representative study of
environmental samples by atomic spectrometry. Let us take up some
representative environmental applications of AAS and AES.

Applications of Atomic Absorption Spectrometry

i) Analysis of airborne particulate matter

In the analysis of airborne particulate matter, the choice of sample collection

location and collection procedure is very important. For example, samples
may be collected from surrounding areas of a factory emitting harmful
gases affecting workers health adversely or a residential colony located
near industrial establishment where toxic pollutants may travel and thus
affect public. A measured volume of air is collected on a cellulose acetate
membrane filter using air sampler. Weighed amount of particulate matter
is scratched out of the filter paper or the filter paper itself may be dry
ashed in a low temperature furnace to avoid loss of volatile elements. The
particulate matter or ash is then dissolved using acid digestion method
and heating on hot plate. The final solution is prepared in dilute HCl and
making up final volume to a fixed volume. Appropriate hollow cathode
lamps are selected depending on the elements to be determined and
respective standard solutions are prepared. Calibration plots should be
drawn for each element to be determined and the test solution is aspirated.
Thus, concentration of desired elements in air dust particulate matter may
be determined. Results are usually reported in terms of µg/m3 of air.

ii) Mercury in air/water

Metallic mercury is important as it forms amalgam with other metals. Its

alloy with silver was earlier used by dentists for dental filling though it is
no longer so because of toxicological effects known since many
[Link] in air is collected by bubbling air through an acidic KMnO4
solution where volatile elemental mercury is trapped by oxidising it to
Hg2+. The excess permanganate is reduced with hydroxylamine, and the
collected mercury (or mercury in a water sample) is then reduced to the
element by SnCl2.

As elemental mercury has appreciable vapour pressure at room temperature,

and by bubbling argon through the solution, mercury vapour is swept into
a quartz ended cell where its atomic absorption is measured at 253.6 nm
using mercury line. A calibration curve should be prepared before the
sample is run. The measured absorbance is corrected for the blanks and
the amount of mercury is determined from the calibration curve.

Similarly, the water sample from tap, river, or other sources can be analysed.
Tap water should contain around 1 ppb or less mercury. In such
determinations the water samples and the standards should be run in a
similar manner. As in the case of air samples, the correction should be
made for the reagent blank as its magnitude will generally govern the
detection limit of the procedure. Extreme care must be taken to minimise
136
 reagent and glassware contamination. From the calibration graph the Atomic Absorption and
Emission Spectrometry
quantity and concentration of mercury in the sample is determined.

iii) Trace element contamination in soil

To determine toxic contaminants in soil samples, the representative samples

are collected from surface of the soil, and at some depth. These are then
passed through a sieve to make it uniform sample and is stored in separate
containers to avoid cross contamination. To determine all the contaminants,
the sample is prepared by treating a weighed amount of soil with 1:1 nitric
acid and making appropriate solution. Metal contents such as Ni, Cu, Zn,
Cd, Pb, etc. are then determined by using appropriate hollow cathode lamp
and air-acetylene flame. It is essential that the standard solutions for each
element are prepared in appropriate concentration range and their respective
calibration plots are obtained.

Applications of Atomic Emission Spectrometry

Emission spectroscopy is widely used for qualitative as well as quantitative

analysis because of high sensitivity and the possible simultaneous excitation
of many elements, notably metals and metalloids. AES is especially suited for
rapid survey analysis of the elemental contents in small samples at level of
10µg/g or less. It is essential to construct an analytical curve with known
standards. The internal standard method improves the precision of analysis.

ICP-AES is used widely for determining trace metals in environmental samples

such as drinking water, industrial waste water and ground water supplies and
so also for determining trace metals in petroleum products, biological materials,
foodstuffs geological samples and industrial quality control. The simultaneous
multielemental determinations make it possible to form correlations and to
reach conclusions that are impossible with single element determinations. The
excellent sensitivity and wide working range for many elements together with
the low level of interferences make ICP-AES a nearly ideal method. Let us
take up the analysis of trace elements in airborne particulate matter by AES as
a representative example of environmental applications of AES.

i) Trace elements in airborne particulate matter

AES has been used extensively for the determination of trace elements in
atmospheric particulates, especially large-scale survey studies where
simultaneous multielement analysis is required. Airborne particulate matter
is routinely collected by drawing a measured volume of air through filter
material such as fiberglass, asbestos, cellulose paper, porous plastic, or
graphite in the form of discs or electrodes. However, for the determination
of trace elements, the chemical composition of filter is important. For
example glass filters show high concentrations of Ba, Sr, Rb, Zn, Ni, Fe,
Ca, As and other elements. The composition of filter materials is particularly
significant in sampling relatively clean atmospheres because of the low
particulate levels collected in reasonable sampling time. The particulates
are collected, dried, and weighed; then spectroscopic buffer is added along
137
Spectroscopic Methods with internal standards. The sample so prepared is then suitably determined.
The detection limits between 0.1 and 5 ng can be obtained for up to 14
elements.

5.9 SUMMARY
Flame atomic absorption spectrophotometry (FAAS) concerns the absorption
of radiation by the atomised analyte element in the ground state. The atomisation
is achieved by the thermal energy of the flame. The wavelength(s) of the
radiation absorbed, and the extent of the absorption form the basis of the
qualitative and quantitative determinations respectively. As it is not an absolute
method of analysis, the routine analytical methodology for quantitative
determinations using AAS is based on calibration method. Besides this the
internal standard method and standard addition methods are also employed.

A typical flame atomic absorption spectrophotometer consists of a source

delivering the characteristic resonant radiation of the analyte, an atom reservoir
into which the analyte is introduced and atomised, a monochromator, a detector
and a readout device. In a typical flame atomic absorption spectrophotometric
determination, the radiation from a hollow cathode lamp is made to fall on the
sample of the analyte aspirated into the flame, where a part of it is absorbed.
The transmitted radiation is then dispersed by a monochromator and sent to
the detector. The detector output is suitably processed and is displayed by
appropriate readout device. Like, UV-VIS spectrophotometers the atomic
absorption spectrophotometers are also of two typesviz., single beam atomic
absorption spectrophotometers and double beam atomic absorption
spectrophotometers

Three types of interferences viz., spectral, chemical and physical interferences

are encountered in FAAS. These need to be suitably addressed to put the
technique to analytical use. Sample preparation is a crucial step in the AAS
determination. Though in principle, the sample in solid, liquid or in the gas
phase can be analysed by flame AAS but in practice the sample is taken in the
solution form. The solution of the solids is generally prepared by wet dissolution
method using a suitable acid.

The accuracy, precision and detection limits of flame AAS depend on how the
analyte sample is introduced into the atomiser. We need to transfer a
reproducible and representative portion of a sample into an atomiser which
depends on the physical and chemical state of the analyte and the sample matrix.
The sample introduction is achieved with the help of a nebuliser. The commonly
used nebulisation methods are pneumatic nebulisation.

Flame atomic absorption spectrophotometry (FAAS) is now a routinely and

widely employed technique for trace and ultra-trace analysis of complex
matrices of geological, biological, environmental, pharmaceutical, and other
kind of samples. The atomic absorption methods using flame are rapid and
precise and are applicable to about 67 elements.

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 Atomic Absorption and
5.10 TERMINAL QUESTIONS Emission Spectrometry

1. Explain the origin of flame atomic absorption spectrum. What information

can be obtained from the spectrum?

2. Give a description about the commonly used flame in flame spectrometry.

3. List the main parts of FAAS instrument and give the function of each one
of them.

4. Describe hollow cathode lamp and explain the principle of its working.

5. Describe the calibration method used in FAAS.

Self Assessment Questions

1. The characteristics of an atomic spectral line are as under

z position of the signal

z intensity of the signal

z line width

2. The laminar flow flame has the following four zones:

a) Preheating zone

b) Primary reaction zone or inner zone

c) Interconal zone

d) Secondary reaction zone

Of these, the tip of the inner zone is used in flame based atomic spectroscopic
methods

3. The calibration plot method provides a simple method to determine the

concentration of the analyte in flame atomic absorption spectrophotometry.

4. The atomic absorption spectrophotometers generally use line sources. Two

commonly used line sources are hollow-cathode lamp (HCL) and
electrodeless discharge lamps (EDL).

5. Double beam atomic absorption spectrophotometers are better than a single

beam spectrophotometer because these correct the fluctuations in the
intensity of radiation coming from the radiation source and for changes in
the sensitivity of the detector.

6. a) Phosphate interferes in the quantitative determination of calcium as

it forms calcium phosphate having low volatility which decreases
atomic population in the cell.

b) The interference of phosphate in the determination of Ca can be

removed by using a releasing agent like Sr or La. These act by reacting
preferentiallywith the phosphate.
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Spectroscopic Methods Terminal Questions

1. The flame atomic absorption spectrum is obtained by the absorption of

UV-VIS radiation by the atomic vapours containing free atoms of an
element in the ground state. The absorbed radiation causes excitation of
electrons from the ground state to an excited state.

The wavelength of the absorbed radiation provides the information about

the element and the intensity of the signal gives the quantitative measure
of the concentration of the element.

2. In flame spectrometry premix or laminar flame is commonly used. Such a

flame may be divided into four zones. The first or the innermost region of
the flame is the preheating zone where the fuel-oxidant mixture is heated
to its ignition temperature by thermal conduction from the primary reaction
zone. The second zone or inner zone is about 0.1 mm thick and is visible
due to its blue green light. This region is not used for flame photometry.
The maximum temperature is achieved just above the tip of this zone and
is used for flame based atomic spectroscopic methods.

Immediately above the inner zone lies the third orinterconal zone which
can extend up to considerable height. The outermost fourth zone is the
secondary reaction zone in which the products of the fuel combustion are
burnt to stable molecular species by the surrounding air.

3. The components of a typical flame atomic absorption spectrophotometer

and their functions are as under.

A. Radiation source: it provides the characteristic spectrum of the element

to be determined.

B. Atom reservoir (flame): it converts a small portion of the sample into

free neutral ground state atoms.

C. Monochromator: it selects a given emission line from the emissions

of the radiation source.

D. Detector: it detects and amplifies the unabsorbed radiation and converts

into an electrical signal.

E. Readout device: it provides the spectral output on the basis of inputs

from the detector.

4. It consists of a sealed cylindrical glass tube with a quartz window at one

end and a hollowed cylindrical cathode along with an anode wire made of
tungsten. The cathode is made of the element to be analysed and the lamp
is filled with an inert gas under vacuum.

When a voltage of ~300 V is applied between the two electrodes, a low-

pressure glow discharge is produced that is confined to the inside of the
cathode material. The gaseous cations accelerate towards the cathode and

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 bombard it to vapourise the atoms its surface. These metal atoms are excited Atomic Absorption and
Emission Spectrometry
by collisions with electrons and ions and emit characteristic emission lines.

5. In this method, a series of solutions of different known concentrations of

the analyte are aspirated into the flame and absorbance for each solution
is measured. Then a calibration plot is prepared between the absorbance
and concentration. The concentration of the element in the unknown sample
can then be found out from this calibration plot.

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