Atomic Absorption and emission

spectroscopy

By Minaleshew A

1 Copyright © 2022 by Minaleshewa A ( PhD), BDU

Atomic Absorption Spectroscopy:

• Developed by Alan Walsh in early 1950s.

2 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Introduction
 Atomic absorption is the absorption of light by free atoms.
 An atomic absorption spectrophotometer is an instrument
that uses this principle to analyze the concentration of
metals in solution.
 The substances in a solution are suctioned into an excited
phase where they undergo vaporization, and are broken
down into small fragmented atoms by high temperature

3 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 BASIC PRINCIPLE

ATOMIC ABSORPTION SPECTROSCOPY (AAS) is an
analytical technique that measures the concentrations of
elements or identify its identity
 Applicable to many metals and few non metals

 It makes use of the absorption of light by these elements in

order to measure their concentration
 Atomic-absorption spectroscopy quantifies the absorption
of ground state atoms in the gaseous state .
The atoms absorb ultraviolet or visible light and make
transitions to higher electronic energy levels . The analyte
concentration is determined from the amount of
absorption.
4 Copyright © 2022 by Minaleshewa A ( PhD), BDU
Theory of Operation
• When atoms are subjected to
heat or some form of EMR, one
or more electrons jump to a
higher energy level, leaving a
vacancy in the inner shell
• We say the electron is excited

• As this happens, energy is

absorbed

5 Copyright © 2022 by Minaleshewa A ( PhD), BDU

Theory of Operation, continued

•When the excited electron in the

outer orbital returns to the lower
energy level of the inner, vacant
orbital, energy is released in the
form of a photon

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 -
-
 The solvent of the solution is evaporated and all materials
present in the sample are vaporised and dissociated to atoms at
the very high temperature.


7 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Atomic Spectroscopy
High
Sample Vapour
Temperature
Measure absorbance or emission of the atomic vapour.

atomization: process of converting sample to gaseous atoms

8 Fig. Atomization
Copyright © 2022 by Minaleshewa A ( PhD), BDU
9 Copyright © 2022 by Minaleshewa A ( PhD), BDU
  Basic steps of Atomic Absorption :
a) nebulization – solution sample, get into fine droplets by
spraying the solution through thin nozzle
b) desolvation - heat droplets to evaporate off solvent just
leaving analyte
c) volatilization – convert analyte into gas phase
d) dissociation – break-up molecules in gas phase into
atoms.
e) ionization – cause the atoms to become charged
f) excitation – with light, heat, etc. for spectra
measurement
10 Copyright © 2022 by Minaleshewa A ( PhD), BDU
  The gaseous atoms absorb ultraviolet or visible light and
make transitions to higher electronic energy levels . The
analyte concentration is determined from the amount of
absorption of light.

 The sample is atomised at a very high temperature (2500-

3000 ºC) and the free atoms have line spectrum
 There are no vibration or rotation energy levels that would
widen the lines to brands in the spectrum (like it happens in
the case of UV-Vis

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 Instrumentation for AAS

Light source
atomizer monochromator
(hollow cathode Lamp )

readout device Detector

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 1 – Light Source

The light source is usually a hollow cathode lamp of

the element that is being measured . It contains a
tungsten anode and a hollow cylindrical cathode made
of the element to be determined. These are sealed in a
glass tube filled with an inert gas (neon or argon ) .
Each element has its own unique lamp which must be
used for that analysis .

13 Copyright © 2022 by Minaleshewa A ( PhD), BDU

Multielement lamps are available
 How it works
Applying a potential difference between the anode
and the cathode leads to the ionization of some gas
atoms .

These gaseous ions bombard the cathode and eject

metal atoms from the cathode in a process called
sputtering. Some sputtered atoms are in excited
states and emit radiation characteristic of the metal
as they fall back to the ground state .

14 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 2 – Atomizer
Elements to be analyzed needs to be in atomic sate
The process of converting an analyte in solid, liquid,
or solution form to a free gaseous atom is called
atomization.
Atomization is usually performed by:
Flames- uses flame as atomizer
Furnaces- uses electrically heated furnance
Plasmas-uses ionized argon gas

15 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Flame Atomization

Sample solutions are usually introduced into a nebuliser by being

sucked up a capillary tube . In the nebuliser the sample is
16 Copyright © dispersed
2022 into tiny
by Minaleshewa droplets
A ( PhD), BDU , which can be readily broken down in

the flame.
 Flame Atomisation
Degree of atomisation is temperature dependent.

Vary flame temperature by fuel/oxidant mixture.

Fue l Ox ida nt Te mpe ra ture (K)

Acetylene Air 2,400 - 2,700
Acetylene Nitrous Oxide 2,900 - 3,100
Acetylene Oxygen 3,300 - 3,400
Hydrogen Air 2,300 - 2,400
Hydrogen Oxygen 2,800 - 3,000
Cyanogen Oxygen 4,800
17 Copyright © 2022 by Minaleshewa A ( PhD), BDU
  A significant disadvantage to flame atomizers is that the
efficiency of atomization may be quite poor. This may occur
for two reasons.
 First, the majority of the aerosol mist produced during
nebulization consists of droplets that are too large to be carried
to the flame by the combustion gases. Consequently, as much
as 95% of the sample never reaches the flame.
 the large volume of combustion gases significantly dilutes the
sample
 ppm concentration (part per million, that is mg kg-1 or mg/L
in case of dilute solutions

18 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Graphite furnace/electrothermal atomizer
 A significant improvement in sensitivity is achieved by
using resistive heating in place of a flame.
 A typical electrothermal atomizer, also known as a
graphite furnace, consists of a cylindrical graphite tube
approximately 1–3 cm in length, and 3–8 mm in diameter
 The assembly also allows for the passage of a continuous
stream of inert gas, protecting the graphite tube from
oxidation, and removing the gaseous products produced
during atomization. A power supply is used to pass a
current through the graphite tube, resulting in resistive
heating.

19 Copyright © 2022 by Minaleshewa A ( PhD), BDU

  Improved sensitivity over flame sources. (Hence) less sample
is required.
 Measuremnts could be done at ppb level (part per billion, ppb
= 10-3 ppm, that is μg kg-1 or μg L-1

20 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Inductively Coupled Plasmas
Enables much higher temperatures to be achieved.
Uses Argon gas to generate the plasma.
Temps ~ 6,000-10,000 K.
Used for emission expts ( ICP-OES) rather than
absorption expts due to the higher sensitivity and
elevated temperatures.
Atoms are generated in excited states and
spontaneously emit light.

21 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 3. Monochromator:
Isolates photons of various wavelengths that pass through
the flame or furnace.
Similar to the monochromator in UV-VIS spectroscopy in
that it uses slits, lenses, mirrors and gratings/prisms.

4. Detector:
The light selected by the monochromator is directed onto a
detector that is typically a photomultiplier tube , whose
function is to convert the light signal into an electrical
signal proportional to the light intensity.
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 Application of Atomic Absorption
Spectrometry
1. Qualitative detection How?
2. For the quantitative determination of more than 60
metals or metalloid elements

23 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Calibration Curve
A calibration curve is used to determine the
unknown concentration of an element in a solution.
The instrument is calibrated using several solutions
of known concentrations. The absorbance of each
known solution is measured and then a calibration
curve of concentration vs absorbance is plotted.

The sample solution is fed into the instrument, and

the absorbance of the element in this solution is
measured .The unknown concentration of the
element is then calculated from the calibration
curve either by extrapolation or using line equation
( Y= mx +b)
24 Copyright © 2022 by Minaleshewa A ( PhD), BDU
25 Copyright © 2022 by Minaleshewa A ( PhD), BDU
 Atomic emission spectroscopy

26 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Atomic Emission
Spectroscopy

Atomic emission spectroscopy is also an analytical

technique that is used to measure the
concentrations of elements in samples .

It uses quantitative measurement of the emission

from excited atoms to determine analyte
concentration .

27 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 The analyte atoms are promoted to a higher energy level
by the sufficient energy that is provided by the high
temperature of the atomization sources .

The excited atoms decay back to lower levels by emitting

light . Emissions are passed through monochromators or
filters prior to detection by photomultiplier tubes.

28 Copyright © 2022 by Minaleshewa A ( PhD), BDU

Atomic Emission Spectroscopy (AES) – similar to AA with flame now being used for
atomization and excitation of the sample for
light production
1) Atomic Processes

heat

Degree of Excitation Depends on Boltzmann Distribution:

N1 and No – are the number of atoms in excited and ground states

k – Boltzmann constant (1.28x10-23 J/K)
T – temperature
E – energy difference between ground and excited states
P1 and Po – number of states having equal energy at each quantum level
Increase Temperature  increase in N1/No (more excited atoms)

Copyright
© I2022
(emission) N1, soAsignal
by Minaleshewa ( PhD),increases with increase in temperature
29 BDU
 The instrumentation of atomic emission spectroscopy is
the same as that of atomic absorption ,but without the
presence of a radiation source .

In atomic Emission the sample is atomized and the

analyte atoms are excited to higher energy levels all in
the atomizer .

30 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 Schematic Diagram of an Atomic
Emission spectrometer

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 Most of atomic emission spectroscopic techniques varies
by the sources of atomization techniques.
Flame
Plasma
Photons

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 The source of energy in Atomic Emission could be a flame
like the one used in atomic absorption ,or an inductively
coupled plasma ( ICP ) .

- The flame ( 1700 – 3150 oC ) is most useful for elements

with relatively low excitation energies like sodium
potassium and calcium .

- The ICP ( 6000 – 8000 oC) has a very high

temperature and is useful for elements of high excitation
energies .

33 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 a) Flame Source:
- The flame ( 1700 – 3150 oC ) is most useful for elements with relatively low excitation
energies like sodium and potassium.

- used mostly for alkali metals

 easily excited even at low temperatures
-
Advantages
- cheap

Disadvantage
- not high enough temperature to extend to many other elements

34 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 b) Plasma (inductively coupled plasma - ICP)
- plasma – electrically conducting gaseous mixture (cations & electrons) ( Ar, Ar+
and e-)
- temperature much higher than flame (( 6000 – 8000 oC)
- possibility of doing multiple element analysis
-useful for elements of high excitation energies .

Inductively Coupled Plasma (ICP) Emission Spectroscopy ( ICP-OES)

- involves use of high temperature plasma for sample atomization/excitation
- higher fraction of atoms exist in the excited state, giving rise to an increase
in emission signal and allowing more types of atoms to be detected

Advantages
- uniform response
- multi-element analysis, rapid

35 Copyright © 2022 by Minaleshewa A ( PhD), BDU

36 Copyright © 2022 by Minaleshewa A ( PhD), BDU
37 Copyright © 2022 by Minaleshewa A ( PhD), BDU
 Comparison Between Atomic
Absorption and Emission Spectroscopy
Absorption Emission

- Measure trace metal - Measure trace metal

concentrations in concentrations in
complex matrices . complex matrices .

- Atomic absorption - Atomic emission depends

depends upon the upon the number of
number of ground state excited atoms .
atoms .

38 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 - It measures the - It measures the
radiation absorbed by radiation emitted by
the ground state atoms. the excited atoms .
- Presence of a light
source ( HCL ) . - Absence of the light
source .
- The temperature in
the atomizer is adjusted - The temperature in the
to atomize the analyte atomizer is big enough
atoms in the ground to atomize the analyte
state only. atoms and excite them to
a higher energy level.

39 Copyright © 2022 by Minaleshewa A ( PhD), BDU

 3
AAS APPLICATIONS
There are many applications for atomic absorption:
- Clinical analysis : Analyzing metals in biological
fluids such as blood and urine.
- Environmental analysis : Monitoring our
environment – e g finding out the levels of various
elements in rivers, seawater, drinking water, air, and
petrol.

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 - Pharmaceuticals. In some pharmaceutical
manufacturing processes, minute quantities of a
catalyst used in the process (usually a metal) are
sometimes present in the final product. By using
AAS the amount of catalyst present can be
determined.
- Industry : Many raw materials are examined and
AAS is widely used to check that the major elements
are present and that toxic impurities are lower than
specified – e g in concrete, where calcium is a major
constituent, the lead level should be low because it is
toxic.

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 - Mining: By using AAS the amount of metals such as
gold in rocks can be determined to see whether it is
worth mining the rocks to extract the gold .

- Trace elements in food analysis

- Trace element analysis of cosmetics
- Trace element analysis of hair

42 Copyright © 2022 by Minaleshewa A ( PhD), BDU