Atomic

Emission
Spectroscopy
Dr. Khawaja Ali Zakir
Background:
• Emission Spectrum:
• The collection of spectral lines produced by an excited atom is
called emission spectrum and will be characteristic of that atom.
• Spectrum:
• A spectrum is a band of different colors produced by radiations or
light.
• It is a range of characteristic wavelengths of radiations emitted or
absorbed by an atom or a molecule.
Types of emission spectrum:
• There are three types of emission spectrum;
1. Line emission spectrum
2. Band emission spectrum
3. Continuous emission spectrum
 • It is consisting of sharply defined and often
widely and irregularly spaced individual
line of a single wavelength.
Line Emission • Line spectrum contains only a few
wavelengths.
Spectrum • They are also called atomic spectrum.
 • It consists of group of lines each of
which has single wavelength that
Band emission becomes closely spaced as they
approach the end of band. ,
spectrum • They are also called molecular
spectrum.
 • The continuous spectrum has no gaps,
breaks or sharp lines in a given range of
Continuous wavelengths.
emission • Continuous spectrum contains all the
wavelengths of a given range.
spectrum • Example of this type of spectrum is a
rainbow.
Atomic Emission Spectroscopy:
• Definition
• When we study the emission of energy by the atoms in the flame, we
call this technique as Atomic Emission Spectroscopy AES.
• Objective:
• Atomic Emission Spectroscopy (AES) is an analytical technique that
measures the concentrations of elements in samples.
• Basis:
• It makes use of the emission of light by these elements, to measure
their concentration.
Principle:
Principle:
• In atomic emission the sample is atomized, and the analyte atoms are
excited to higher energy levels. The analyte concentration is
determined from the amount of emission.
• 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.
• The change in energy can be calculated as,
• Δ𝐸 = 𝐸1 − 𝐸0
• Δ𝐸 = ℎ𝑣
𝑐
•𝜆=
𝑣
• So, the equation will be;
ℎ𝑐
• Δ𝐸 =
𝑣
Instrumentation
Instrumentation:
• The instrumentation of atomic emission spectroscopy is the same as
that of atomic absorption, but without the presence of a radiation
source.
• Atomic emission spectrometer has four principal components;
1. Nebulizer
2. Atomizer (flame, graphite furnace)
3. A Monochromator
4. A detector and read out device
1. Nebulizer
1. Nebulizer:
• The function of the nebulizer is to convert the sample solution into small droplets
having the uniformed diameter and transfer this aerosol to the flame in an efficient
manner.
• Types of nebulizer
1. Pneumatic nebulization:
• They are most widely used. A jet of compressed air nebulizes the solution
when sample is sucked through the capillary tube.
2. Ultrasonic nebulizer:
• They generate homogenous aerosol of fie droplets less than 5 um and has high
efficiency The basic principle involves the use of high frequency sound waves.
2. Atomizer
2. Atomizer:
• The major energy sources in Atomic Emission spectroscopy are;
• Graphite furnace:
• This technique should be used only when the sample size is small.
The substance sample is dried at 200°C for 60 sec. Then it is
burned at 1200°C for 30 sec. to burn all sample. And then finally
the atomization is brought about by heating at 2700°C for 60 sec.
• A flame:
• The flame (1700°C - 3150°C) is most useful for elements with
relatively low excitation energies like sodium, potassium and
calcium.
3. Monochromator
Monochromator
• This is an important part in an Atomic Emission spectrometer.
• It is used to separate out all of the thousands of lines. Without a good
monochromator, detection limits are severely compromised.
• A monochromator, in atomic emission spectroscopy, is simply a
wavelength selector.
• It is used to select the specific wavelength of light which is emitted by
the sample, and to exclude other wavelengths.
• The selection of the specific emitted radiation allows the
determination of the selected element in the presence of others.
Detectors
Detector:
• The selected wavelength 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.
• The processing of electrical signal is fulfilled by a signal amplifier.
• The signal could be displayed for readout, or further fed into a data
station for printout by the requested format.
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 emission of each known solution is measured and
then a calibration curve of concentration vs. emission is plotted.
• The sample solution is fed into the instrument, and the emission of the
element in this solution is measured.
• The unknown concentration of the element is then calculated from the
calibration curve.
Difference Between Atomic Absorption and
Atomic Emission Spectroscopy
Difference
Atomic Absorption Spectroscopy
1. An absorption spectrum can be defined
as a spectrum obtained by transmitting
electromagnetic radiation through a
substance.
2. An absorption spectrum is produced
when atom absorb energy.
3. Absorption spectra show dark lines or
gaps
4. An atom obtains a higher energy level
when an absorption spectrum is given
by that atom
Atomic Emission Spectroscopy
Emission spectrum can be defined as a
spectrum of the electromagnetic
radiation emitted by a substance.
An emission spectrum is produced when
atoms release energy.
Emission spectra show colored lines.
An emission spectrum is given when an
excited atom obtains a lower energy
level.
Excitation Source:
Excitation Source:
1. Flame
2. Inductively coupled plasma
3. Spark and arc
Flame photometer:
• There are two types of Flame Photometers that are used invariably in
Flame Emission Spectroscopy (FES), namely:
(a) Simple Flame Photometer
(b) Internal Standard Flame Photometer
Simple flame photometer:
• In general, Flame Photometers are designed and intended mainly for
carrying out the assay of elements like: Sodium, Potassium, Calcium,
and Lithium that possess the ability to give out an easily excited flame
spectrum having sufficient intensity for rapid detection by a photocell.
Instrumentation:
A = Inlet for compressed Air
B = Drain outlet (to maintain constant pressure head in the mixing Chamber)
C = Liquid sample (sucked into the Nebulizer)
D = Inlet for Fuel-Gas to the Laminar-Flow-Burner
E = Nebulizer to atomize the liquid sample
F = Mixing Chamber for Fuel Gas, Compressed Air, and Atomized Liquid Sample
G = Burner
H = Flame
I = Convex lens
J = Optical filter to transmit only a strong-line of the element
K = detector
L = Amplifier to amplify the feeble electrical impulse and a built-in direct read-out device
Procedure:
1. The compressed and filtered air (A) is first introduced into a Nebulizer (E) which
creates a negative pressure (suction) enabling the liquid sample (C) to gain entry
into the atomizer (E).
2. Thus, it mixes with the stream of air as a fine droplet (mist) which goes into the
burner (G).
3. The fuel gas (D) introduced into the mixing chambers (F) at a given pressure gets
in touch with the air and the mixture is ignited.
4. Consequently, the radiation from the resulting flame (H) is made to pass through a
convex lens (I) and ultimately through an optical filter (J) that allows specifically
the radiation characteristic of the element under examination to pass through the
photocell (K).
5. Finally, the output from the photocell is adequately amplified (L) and
subsequently measured on an appropriate sensitive digital-read-out device.
1. Nebulizer
2.Atomizer:
• Write detail of nebulizer and atomizer as discussed in atomic emission
spectroscopy
3. Burner
• The function of the burner is to maintain stable flame which is sufficiently
energetic to vaporize the aerosol and excite the neutral atoms to emit their
characteristic spectra.
• Types of burner
I. Total combustion burner:
• The sample solution, the fuel and the oxidizing gas are passed through
different passages, and they meet at the base of the flame.
II. Premix-burner:
• The sample is aspirated into large chamber by means of stream of oxidant.
Here the mist of sample, oxidant and fuel supply are mixed and then forced to
the burner.
 Difference between Total Combustion
burner and Premix Burner
Total Combustion Burner Premix Burner

Non-Explosive Explosive

All aspirated sample reaches the flame 10% sample reached the flame

Rate of sample totally depends on viscosity of Depends moderately on viscosity

sample
Little reproducibility (not uniform droplet) Better reproducibility (uniform droplets reaches
burner)

Produce noisy operation or produce noisy Not noisy

background in detector
Types of flame
• Based on burner flames are of two types
• Diffusion Flame:
• Characteristic of the total combustion burners. The fuel and oxidant
gasses reaches the flame through different parts and mix at the base
of the flame.
• Pre-mixed burner:
• Characteristic of pre-mixed burner in which the oxidant gas and
fuel gas along with the sample are introduced to the burner and the
flame produced is known as the pre-mixed burner.
Types of Flame:
Hydrocarbon Flame Hydrogen Flame Reducing and oxidizing
flame
Temperature Range 2000K-3400K 2300K 3060K-3333K
Example Acetylene air flame Hydrogen air flame Acetylene + Oxygen
Acetylene Natrium oxide flame
Characteristics High Temperature Decreased spectral Excessive fuel produces
Efficient Excitation interference reducing flame
Decrease Chemical Less efficient excitation Excessive oxidant
interference Increased chemical produces oxidizing flame
interference
Disadvantages Acetylene nitrous oxide Excessive dissociation of No disadvantage
has high burning velocity oxide strongly require
and cannot be used safely high temperature.
in premixed burner. This requirement cannot
be satisfied by the
hydrogen flame
Regions of flame
• Flame exhibit a well-defined structure consisting of different regions:
i) Pre-heating region:
• is a region which is 1 mm thick and mixed gases are heated and ignited here.
ii) Primary reaction region:
• (blue zone) the zone where chemical excitation of the atoms takes place.
iii) Inter Conal zone/region:
• the zone which is present above the lip of the blue zone, and it is the hottest zone
where the emission of photon takes place.
iv) Secondary reaction zone:
• in which combustion takes place and molecules exist in stable condition.
• In diffusion flame only inter conal region and secondary reaction zones are
present. But all four regions are present in the pre-mixed flame.
5. Slits:
• Entrance and exit slits
i. Entrance slit: - Cuts out most of the radiation from the surrounding -
Allows only the radiation from the flame to enter into the
monochromator
ii. Exit slit: - Placed after the monochromator - Allows only the selected
wavelength to pass through the photodetector.
6. Monochromators:
• It is a means of isolating light of the wavelength to be measured from that
of extraneous emissions.
• When kept between the flame and detector, the radiation of the desired
wavelength from the flame will be entering the detector and be measured.
• Remaining will be absorbed by the monochromator and not measured Either
prisms or diffraction gratings.
• 1. Prism: Quartz material is used for making prism, as quartz is transparent
over entire region
• 2. Grating: it employs a grating which is essentially a series of parallel
straight lines cut into a plane surface.
7. Detectors:
• There are two types of detectors that are used most frequently in
emission spectroscopy, namely:
(a) Photographic Detectors-used for qualitative analysis, and
(b) Photomultiplier Detectors-used for quantitative analysis.
Interferences:
• The disturbances which affects the detection of the analyte in flame
photometer is called interference.
1. Spectral interference
2. Chemical interference
3. Physical interference
4. Self interference
Limitation of Flame Emission Photometry:
1-The number of excited atoms in flame is very small. It is the alkaline
and alkaline earth metals that can be practically determined.
2- It needs perfect control of flame temperature.
3- Interference by other elements is not easy to be eliminated.
4- Heavy and transition metals , the number of absorption and emission
lines is enormous, and the spectra are complex.
 APPLICATIONS OF FLAME EMISSION
SPECTROSCOPY
1. It has been used for the analysis of a number of elements, for
instance: Na, K, Zn, Cu, Ca, Mg, Ni and Fe present in various tissues of
human beings.
2. Changes in trace-metal concentrations have been studied at length
with regard to the ageing process.
3. Assay of sodium, potassium and calcium in blood serum and water.
4. The technique of flame emission spectroscopy is used to determine
the concentration of Ba, K, and Na ions.
5. Detection of ions in heavy water.
6. Detection of body electrolyte.