Flame Emission Spectroscopy And

Atomic Absorption Spectroscopy

Presented By: Facilitated To:

Sachin.J.Gaddimath Dr. B.S.Kittur
M.Pharm 1st year HOD &
PROFESSOR
Dept. of Pharmaceutics Dept. of ph.
Chemistry
HSKCOP, BAGALKOT HSKCOP,
Contents
Flame Emission Spectroscopy and Atomic
Absorption Spectroscopy:
Principle
Instrumentation
Interferences
Applications
Principle:
Desolvation: The metal particles in the flame are
dehydrated by the flame and hence the solvent is
evaporated.
Vaporisation: The metal particles in the flame are
dehydrated. This also led to the evaporation of the
solvent.
Atomisation: Reduction of metal ions in the
solvent to metal atoms by the flame heat.
Excitation: The electrostatic force of attraction
between the electrons and nucleus of the atom
helps them to absorb a particular amount of energy.
The atoms then jump to the exited energy state.
 Emission process: Since the higher energy state
is unstable the atoms jump back to the stable low
energy state with the emission of energy in the
form of radiation of characteristics wavelength,
which is measured by the photo detector
Instrumentation:
The basic components of Flame Emission
Spectroscopy are:
Burners
Atomiser
Monochromators
Detector
Burners:
1.The flame should have ability to evaporate the
liquid droplets from the sample solution in the
formation of solid residue.
2. The flame should decompose the compounds in
the solid residue resulting in the formation of atoms.
3. The flame must have the capacity to excite the
atoms formed and cause them to emit radiant
energy
FLAMES IN FES
Name of the element Wavelength range(nm) Colour observed in the
emitted flame

Potassium(K) 766 Violet

Lithium(Li) 670 Red

Calcium(Ca) 622 Orange

Sodium(Na) 589 Yellow

Barium(Ba) 554 Lime green

Types of burners:
1. Mecker burner.
2. Total consumption burner.
3. Laminar flow burner.
4. Lundergraph burner.
5. Shielded burner.
6. Nitrous oxide- Acytelene flame.
Mecker burner:

1. This burner employed natural gas and oxygen.

2. Produces relatively low temperature and low excitation
energies.
3. These are best used for alkali metals only.
Total consumption burner:
1. In this burner the fuel and oxidant used
are hydrogen and oxygen gas.

2.In this sample, solution is aspirated

through a capillary by the high pressure.
the fuel and oxidant are burnt at the tip of
burner.

3.The name “total consumption burner” is

used becoz all the sample that enters the
capillary will enter into flame of the droplet
size.
 CONSUMPTION BURNER
Advantage:
This design is very simple and the whole/entire sample is
consumed by this process.
Disadvantage:
Uniform & homogenous flame is not obtained. Since the
droplet size vary, leading to fluctuations in the flame
intensity.
 Laminar flow burner:
In this type of burner, aspirated sample, fuel and
oxidant are thoroughly mixed before reaching the
burner opening and then entering the flame.
Important feature of this is that only a small portion
(about 5%) of the sample reaches the flame in the
form of small droplets and is easily decompose.
Advantages:
Burner is non-turbulent, noiseless, stable.
Easy decomposition which leads to high
atomisation.
It can handle the solution up to several %
without clogging.
Disadvantages:
When it contains 2 solvents, more volume will
evaporate and lesser will remain
undissociated.
Monochromators and filters:
 In simple FES, monochromators is the prism.
 QUARTZ is the material most commonly used
for making prisms becoz quartz is transparent
over entire region.
Filters:
 It is made up of such material which is
transparent over a narrow spectral range.
 When a filter is kept between flame detector, the
radiation of the desired wavelength from the
flame will be entering the detector and be
measured. The remaining undesired wavelength
will be absorbed by the filter and not measured.
In FES, the wavelength as well as intensity of
radiation emitted by the element has to be
monitored. Hence a filter or monochromator is
used.
DETECTORS:
 Photovoltic cell
Phototubes
Photomultiplier tubes
Applications:
FES has found wide application in agricultural
and environmental analysis, industrial analysis of
ferrous metals and alloys as well as glasses,
ceramic materials, and clinical analysis of body
fluids.
FES can be easily automated to handle a large
number of samples. Array detectors interfaced to
a microcomputer system permit simultaneous
analyses of several elements in a single sample.
They are also used to determine the metals
present in chemicals, soil, cements, plant
materials, water, air pollutants.
Used in clinical laboratory to determine
concentrations of sodium and potassium in
biological fluids like serum, urine.
INTERFERENCES:
 Matrix Interference
Chemical Interference
Ionization Interference
Spectral Interference
Matrix Interference:
 When a sample is more viscous or has
different surface tension than the standard, it
can result in differences in sample uptake
rate due to changes in nebulisation efficiency.
 Such interferences are minimized by
matching as closely as possible the matrix
composition of standard sample.
Chemical interference:
If a sample contains a species which forms a
thermally stable compound with the analyte that is
not completely decomposed by the energy available
in the flame then chemical interference exists.
Refractory elements(Ti, W, Mo and Al) may combine
with oxygen to form thermally stable oxides.
Analysis of such elements can be carried out at
higher flame temperatures using nitrous oxide-
acetylene flame instead of air acetylene to provide
higher dissociation energy.
Alternately an excess of another element or
compound can be added e.g Ca in presence of
phosphate produces stable calcium phosphate
which reduces absorption due to Ca ion.
If an excess of lanthanum is added it forms a
thermally stable compound with phosphate and
calcium absorption is not affected.
Ionization Interference:
 It is more common in hot flames. The
dissociation process does not stop at
formation of ground state atoms.
 Excess energy of flame can lead to excitation
of ground state atoms to ionic state by loss of
electrons thereby resulting in depletion of
ground state atoms.
In cooler flames such interference is
encountered with easily ionized elements
such as alkali metals, alkaline earths.
Salts of such elements as K, RB, and Cs are
commonly used as ionization suppressants.
Atomic Absorption Spectroscopy
AAS is a technique for determining the concentration
of a particular metal element in a sample. And it can
be used to analyse the concentration over a 62
different metals in a solution.
Principle:
The principle of Atomic Absorption Spectroscopy is
based on the free atoms (gas) generated in an
atomiser which can absorb radiation at specific
frequency.
It quantifies the absorption of ground state atoms in
the gaseous state.
This absorbs UV or visible light and make
transitions to higher electronic energy levels. The
analyte concentration is determined from the
amount of absorption.
Concentration measurements are usually
determined from a working curve after calibrating
the instrument with standards of known
concentration.
It is very common technique for detecting metals
and metalloids in environment samples.
INSTRUMENTATION:
Light Source:
Hollow cathode lamp are the most common
radiation source in AAS.
It contains a tungsten anode and a hollow
cylindrical cathode.
These are sealed in a glass tube filled with an
inert gas(mainly neon or argon).
Each elements has its own unique lamp which
must be used for that analysis.
Nebulizer:
Nebulizer suck up liquid samples at controlled rate.
Creates a fine aerosol spray for introduction into the
flame.
Mix the aerosol, fuel and oxidant thoroughly for
introduction into flame.
Atomizer:
Elements to be analysed needs to in atomic state
and this is done by means of atomizer.
Atomization is a separation of particles into
individual molecules and breaking molecules into
atoms.
This is done by exposing the analyte to high
temperature in flame or graphite furnace.
The atomizers most commonly used nowadays
are(spectroscopic) flames and electro thermal
(graphite tube) atomizers.
Types of Atomizers:
Flame atomization:
Nebulizer suck up in liquid sample at controlled rate and
creates a fine aerosol spray for introduction into flame.
To creat flame, we need to mix an oxidant gas and a fuel
gas.
In most of the cases air-acetylene flame or nitrous oxide
acetylene flame is used.
Liquids or dissolved samples are typically used with
flame atomizer.
Elecrto Thermal Atomization:
It uses a graphite coated furnace to vaporize the
sample.
Samples are deposited in a small graphite coated
tube which then heated to vaporize and atomize the
analyte.
The graphite tubes are heated using a high current
power supply.
Steps used in electro thermal atomization:
Drying, Pyrolysis, Atomization, Cleaning
Monochromators:
It is used to separate out all of the thousand of lines.
It is used to select the specific wavelength of light
which is absorbed by the sample and to remove
other wavelengths.
The selection of the specific light allows the
determination of the selected element in the
Detector and Amplifier:
The light selected by the monochromator is
directed onto a detector whose function
converts the light signal into an electrical
signal.
Photomultiplier tube detector is mainly used.
The processing of electrical signal is fulfilled
by a signal amplifier.
The amplified signal is then displayed on read
out system or fed into a data station for
printout by the requested format.
Calibration Curve:
It is used to determine the unknown
concentration of an element in a sample.
The instrument is calibrated using several
solutions of known concentrations.
The absorbance of each solution is measured
& then calibration curve of concentration vs
absorbance is plotted.
The sample solution is fed into instrument &
the abs of the element in the solution is
measured.
The unknown concentration of element is
then calculated from the calibration curve.
Interferences in AAS:
Analyte interference:
It changes the magnitude of the analyte signal
itself. Such interferences are usually not spectral
in nature but rather physical or chemical effects.
Physical interference:
It can alter the aspiration, nebulisation,
desolvation, and volatilization processes.
Substances in the sample that change the
solution viscosity.(EX- It can alter the flow rate
and efficiency of the nebulisation process.)
Combustible constituents, such as organic
solvents, can change the atomiser temperature
and thus affects the atomization efficiency
indirectly.
Chemical interference:
They occur in the conversion of solid or
molten particle after desolvation into free
atoms or elementary ions.
Constituents that influences the volatilization
of analyte particle causes this type of
interferences and are often called solute
volatilization interferences.
For example, can alter in some flames the
presence of phosphate in the sample can alter
the atomic concentration of calcium in the
flame owing to the formation of relately non-
volatile complexes.
 Such effects can sometimes be eliminated or
moderated by the use of higher temperatures.
Spectral interference:
The elements that absorb at analyte
wavelength are rare in atomic absorption.
Molecular constituents and radiation
scattering can cause interference.
These are often corrected by background
correction scheme.
In some case, if the source of interference is
known, an excess of the interferent can be
added to both the sample and the standards.
The added substance is sometimes called as
radiation buffer.
Applications:
Determination of even small amounts of
metals(lead, mercury, calcium, magnesium)
Environmental studies: drinking water, ocean
water, soil.
Food industry
Pharmaceutical industry.
Presence of metals as an impurity or in alloys
could be done easily.
It is used in qualitative & quantitative
analysis of different drug compounds
To detect heavy metals elements in the herbal
drugs and synthetic drugs.
To estimate lead in petroleum products.
Reference:
Analytical chemistry by Gary D Christian
Principles of instrumental analysis Skoog
Instrumental method of analysis by Willard
Merritt
Spectroscopy by B K Sharma
Instrumental method of analysis by Gurdeep
chatwal
www.google.com
THANK YOU