Atomic Absorption

and emission
spectroscopy
Belay Haile, MSc (Analytical Chemistry),
PhD Scholar (Postharvest Technology),
Arba Minch University, CNS, Chemistry
Department, Arba Minch Ethiopia
February 2021
1
 2

Optical Atomic Spectroscopy

 Optical
Spectrometry
 Absorption
 Emission
 Fluorescence
 3

Cont. …
 AAS
 Higher number of neutral
atom (ground state)
 AES
 Higher number of neutral
atom (Excited state)
 AFS
 Higher number of neutral
atom (Excited state).
 Emission measured at 90°
 4

Atomic Absorption spectroscopy

 Atomic Absorption Spectroscopy is a very common
technique for detecting metals and metalloids in samples.

 It is very reliable and simple to use.

 It can analyze over 62 elements.

 It also measures the concentration of metals in the sample.

 5

Principle of AAS
 The element being determined must be reduced to the
elemental state, vaporized, and imposed in the beam of the
radiation in the source.
 Absorption of EMR (UV-Vis) by neutral atoms in gaseous
state
 Same principle as molecular Electronic spectroscopy but
sample holding, equipment and spectra are different
 There are two basic types of atomic absorption instruments:
single-beam and double-beam.
 6

Single-Beam AAS

A schematic diagram of Single-Beam Atomic Absorption Spectrometer

 7

Single-Beam AAS
 The light source must be electronically modulated or mechanically
chopped to differentiate between the light from the source and the emission
from the sample cell.
 The monochromator disperses the light, and the specific wavelength of
light isolated passes to the detector, which is usually a photomultiplier tube.

 An electrical current is produced depending on the light intensity and

processed by the instrument electronics. The electronics will measure the
amount of light attenuation in the sample cell and convert those readings to
the actual sample concentration.
 With single-beam systems, a short warm-up period is required to allow the
source lamp to stabilize.
 8

Double-Beam AAS

A schematic diagram of Double-Beam Atomic Absorption Spectrometer

 9

Double-Beam AAS
 The light from the source lamp is divided into a sample beam, which is
focused through the sample cell, and a reference beam, which is directed
around the sample cell.

 In a double-beam system, the readout represents the ratio of the sample and
reference beams.

 Therefore, fluctuations in source intensity do not become fluctuations in

instrument readout, and stability is enhanced.

 Generally, analyses can be performed immediately with no lamp warm-up

required
 10

AAS Instrumentation

Schematic diagram of AAS

 11

Light Sources for Atomic Absorption

 Since atoms absorb light at very specific wavelengths, it is
necessary to use a narrow-line source which emits the narrow-line
spectra of the element of interest.

 Narrow-line sources provide high intensity and make atomic

absorption a specific analytical technique.

 The main sources used for atomic absorption are:

1) Hollow cathode lamp (HCL)and
2) Electrodeless discharge lamp (EDL).
 12
HCL
 When voltage (i.e., 300 V) is applied to the
electrodes the HCL emits radiation which is
characteristic of the metal in the cathode.

 If the cathode is made of Fe, an Fe spectrum will

be emitted and the radiation passes through the
flame containing the atomized sample. Then
only Fe atoms will absorb this radiation.

 Itis required to use a different lamp for each

The schematic depiction of a HCL element to be analyzed.

 There are a limited number of commercially

available multielement lamps which contain
cathodes made of more than one element.
 13

EDL
 The benefits:
 Analysing volatile elements
like As, Sb, Bi, Cd, Hg, Rb,
Sn, Te, etc.

o The main disadvantage of

Electrodeless Discharge Lamp electrodeless discharge lamps
is their short life span
 14
14

Chopper:
 It is a rotating wheel interposed between the hollow cathode
lamp and flame.
 Gives pulsating current in the photocell

Nebulization
 A method of forming small droplets from the liquid sample is called Nebulization

Nebulizer:
 formation of suck up liquid samples at controlled rate
 create a fine aerosol spray for introduction into flame.
 Mix the aerosol and fuel and oxidant thoroughly for introduction into flame.
 15

Atomizer:
 Elements to be analyzed
needs to be in atomic sate.
 Atomization is separation
of particles into individual
molecules and breaking
molecules into atoms.
 This is done by exposing the
analyte to high temperatures
in a flame or graphite
furnace
 16

Atomizers

GRAPHITE TUBE ATOMIZER

FLAME ATOMIZER
 Uses a graphite coated furnace to
 To create flame, we need to mix
vaporize the sample.
an oxidant gas and a fuel gas
 ln GFAAS sample, samples are
 in most of the cases air-
deposited in a small graphite 
acetylene flame or nitrous oxide-
coated tube which can then be
acetylene flame is used.
heated to vaporize and atomize
 liquid or dissolved samples are
the analyte.
typically used with flame
 The graphite tubes are heated
atomizer.
using a high power supply
 17

Flame Emission Spectrometry

 Inatomic emission, the processes of excitation and decay are
both involved.
 18

Cont. …
 Inthis technique, formerly called flame photometry, the source of excitation energy is a
flame.

 The sample is introduced into the flame in the form of a solution, and so the technique is
very easy to quantify.

Processes occurring in flame

 19
Flames
 Most flame spectrometers use a premix burner,
as shown in the Figure

 Sample solution is drawn into the pneumatic

nebulizer by the rapid flow of oxidant (usually
air) past the tip of the sample capillary.

 Liquid breaks into a fine mist as it leaves the

capillary.

 The spray is directed against a glass bead, upon

which the droplets break into smaller particles.
Figure of Premix burner
 20
Cont. …
 The formation of small droplets is termed nebulization.

 A fine suspension of liquid (or solid) particles in a gas is called an aerosol.

 The nebulizer creates an aerosol from the liquid sample.

 The mist, oxidant, and fuel flow past baffles that promote further mixing and
block large droplets of liquid.

 Excess liquid collects at the bottom of the spray chamber and flows out
to a drain.

 Aerosol reaching the flame contains only about 5% of the initial sample.
 21
Cont. …

 The most common fuel-oxidizer combination is acetylene and air, which produces
a flame temperature of 2400–2 700 K

 Ifa hotter flame is required to atomize high-boiling elements (called refractory

elements), acetylene and nitrous oxide are usually used.

Maximum flame temperatures

 22

Emission vs. Absorption

Atomic Absorption Spectroscopy Flame emission Spectroscopy
 Amount of light  Amount of light emitted
absorbed by ground state by the excited atom is
atom is measured measured
 Absorption intensity does  Absorption intensity is
not depend upon greatly influenced by
temperature temperature variation
 Beers law is obeyed over
 Beer’s law is not obeyed
wide range of
concentration
 23

Advantages of AAS: Disadvantages of AAS:

 Separatelamp for each element to be

 Technique is specific
because the atom of determined is required
particular element can
 Technique cannot be used successfully
only absorb radiation of
for estimation of element like Mo, Si
their own characteristic
etc because these element give rise to
wavelength oxide in the flame

 Is independent of flame  Predominant anion affect the signal to

temperature negotiable degree
 24

Interferences in AAS:
 Spectral Interferences: include
 Absorption from other closely absorbing atomic species, usually not
a problem because of the extremely narrow band-width used

 Absorption and scattering by molecular species, usually problematic

at lower atomising temperatures

 Scattering by non-volatile salt particles and oxides

 Background emission (which can be electronically filtered)

 25

Non-spectral Interferences:
Could be specific or non-specific
A) Non-specific interferences:
 affect the nebulization by altering the viscosity, surface tension, or
density of the analyte solution and consequently the sample flow
rate
 Some contaminants also decrease the desolvation and atomization
efficiency by lowering the atomizer temperature
B) Specific interferences:
 are also called chemical interferences because they are more
analyte dependent
 26

Chemical interferences
 Solute volatilization interference: refers to the situation when the contaminant forms
non-volatile species with the analyte.

 Dissociation interferences: affects the degree of dissociation of the analyte. Analytes

that form oxides and hydroxides are esp susceptible to dissociation interferences

 Ionization interferences: occurs when the presence of an easily ionized element, such
as K, affects the degree of ionization of the analyte which leads to changes in the
analyte signal.

 Excitation interferences: occur when the analyte atoms are excited in the atomizer
with a subsequent emission at the absorption wavelength . This is more pronounced at
higher temperatures.
 27

Calibration Curve
o A calibration curve is used to determine the unknown concentration of an element in a
solution.

o The instrument is calibrated using several solutions of known concentrations.

o The absorbance of each known solution is measured and then a calibration curve of
concentration vs absorbance is plotted.

o The sample solution is fed into the instrument, and the absorbance of the
element in this solution is measured.

o The unknown concentration of the element is then calculated from the calibration curve.
 28

Application of AAS
 Qualitative and quantitative analysis

 Environmental studies: drinking water, ocean water, soil.

 Determination of metallic elements in biological system

 Determination of metallic element in food industry

 Determination of Ca, Mg, Na, K in serum

 Determination of lead in petrol