ATOMIC ABSORPTION AND

ATOMIC EMISSION (FLAME PHOTOMETRY)

SPECTROMETRY
PRINCIPLE OF AAS
• AAS is an analytical technique used to determine the concentration of
metal atoms/ions in a sample.
• The basic principles of AAS can be expressed as follows:
• Firstly, all atoms or ions can absorb light at specific, unique
wavelengths.
• When a sample containing copper (Cu) and nickel (Ni), for example, is
exposed to light at the characteristic wavelength of Cu, then only the
Cu atoms or ions will absorb this light.
• The amount of light absorbed at this wavelength is directly
proportional to the concentration of the absorbing ions or atoms.
INSTRUMENTATION OF ATOMIC ABSORPTION
SPECTROPHOTOMETER
Working principle of AAS
• The sample, either liquid or solid, is atomized in either a flame or a
graphite furnace.
• The free atoms are then exposed to light, typically produced by a
hollow-cathode lamp, and undergo electronic transitions from the
ground state to excited electronic states.
• The light produced by the lamp is emitted from excited atoms of the
same element that is to be determined, therefore the radiation energy
corresponds directly to the wavelength absorbed by the atomized
sample.
• A monochromator is placed between the sample and the detector to
reduce background interference.
• From here, the detector measures the intensity of the beam of light
and converts it to absorption data.
A typical atomic absorption spectrometer consists of four main
components:
• Light source - Hollow cathode lamp
• Atomization system – Flame or Electrothermal atomizer
• Monochromator – Prism or grating
• Detection system - Photomultiplier detector or Photovoltaic cell
LIGHT SOURCE - HOLLOW CATHODE LAMP
Working of hollow cathode lamp
• The hollow cathode is coated with the element we wish to measure.
• The interior is filled with a relatively low pressure (1 Torr) of an inert
gas such as argon or helium.
• A voltage is applied across the anode and cathode.
• The filler gas (e.g., argon) is ionized to Ar+ at the anode.
• The Ar+ ions are drawn toward the cathode and when they strike the
surface, sputter off some of the coated atoms into the gas phase.
• In the sputtering process, some of the atoms are excited and emit the
characteristic lines of radiation of the atoms.
Sample delivery consists of three steps

Nebulization – using nebulizer- Converts sample solution to aerosol

Aerosol modifier – Converts larger droplets to fine droplets
Atomisation can be done using flame or electrothermal atomizer
which converts analyte into free gaseous atoms
Flame atomizer and
nebulizer assembly
Working of flame atomizer
• The aerosol formed by the flow of oxidant, is mixed with fuel and passes
a series of baffles that remove all but the finest solution droplets.
• The baffles cause most of the sample to collect in the bottom of the
mixing chamber where it drains to a waste container.
• The aerosol, oxidant, and fuel are then burned in a slotted burner to
provide a 5- to 10-cm high flame.
• The quiet flame and relatively long-path length minimizes noise and
maximizes absorption.
• Longer path length increases residence time of the atoms in the flame
and maximizes the absorption signal strength These features result in
reproducibility and sensitivity improvements for AAS
• It is mainly used to determine the concentration of metals in solution in
parts per million (ppm) or parts per billion (ppb) ranges
• In a flame atomizer, a solution of the sample is
nebulized by a flow of gaseous oxidant, mixed with a
gaseous fuel, and carried into a flame where
atomization occurs.
• The following processes then occur in the flame.
• Desolvation: Solvent evaporates to produce a finely
divided solid molecular aerosol.
• The aerosol is then volatilized to form gaseous
molecules.
• Dissociation (leads to an atomic gas)
• Ionization (to give cations and electrons)
• Excitation (giving atomic, ionic, and molecular
emission)
Laminar flow burners produce a relatively
quiet flame and a long path length for
maximizing absorption.

These properties tend to enhance

sensitivity and reproducibility in AAS.

The mixing chamber in this type of burner

contains a potentially explosive mixture that
can flash back if the flow rates are too low.

 Note that the laminar-flow burner is

equipped with pressure relief vents for this
reason.
Common fuels used are propane, hydrogen and acetylene
Common oxidants used are air, oxygen and nitrous oxide
Depending upon the element to be analysed, fuel and oxidants can
be selected
Copper, lead, zinc and cadmium – Low temp – Propane & air or
Acetylene & air
Alkaline earth metals form oxides – High temperature flame for
decomposition
Al, Be and rare earths – Stable oxides – acetylene & oxygen and
acetylene & nitrous oxide
Sequence of Steps involved in Flame Atomization Process
Performance Characteristics of Flame Atomizers
In terms of reproducible behavior, flame atomization appears to be superior
to all other methods for liquid sample introduction.
ADVANTAGES:
1. Uniform dropsize
2. Homogeneous flame
3. Quiet flame and a long path length
DISADVANTAGES:
1. A large portion of the sample flows down the drain , ~90% of sample is lost
2. The residence time of individual atoms in the optical path in the flame is brief
(~10-4s)
3. Flash back, if Velocity of burning > Velocity of flow
4. Measure one metal at a time and as different lamps are required for each
element, the lamp must be changed each time we want to analyze for
something different.
 ELECTROTHERMAL ATOMIZATION ASSEMBLY WITH GRAPHITE FURNACE
(No nebulizer unit as like flame atomization assembly)

Insulator →

Electrical connector →
• It is a small, hollow graphite tube about 2 Inches long by ¼ inch in diameter with a hole in the
top.
• Graphite furnaces are used for atomic absorbance measurements.
• Radiation from the source shines through the tube to the detector.
• A small volume of sample (typically 0.50.5 to 10μl10μl) is introduced through the hole into the
tube either through the use of a micropipette or a spray system.
• The entire furnace system is maintained under an argon atmosphere.
• After introduction of the sample into the furnace, a three step heating process is followed.
• The first step (heating to about 100oC) evaporates the solvent.
• The second (heating to about 800oC) ashes the sample to a metal power or metal oxide.
• The third (heating to between 2,000-3,000oC) atomizes the sample.
• The first two steps are on the order of seconds to a minute. The third step occurs over a few
milliseconds to seconds.
• The atomization step essentially creates gas phase atoms in the furnace and the absorbance is
measured during this time,
• Gas phase atoms only occurs over a second or so before the sample is swept from the furnace.
• The area under the curve is integrated and related back to the concentration through the use
of a standard curve.
• Enhanced sensitivity due to entire sample is atomized in a short period,
• The average residence time of the atoms in the optical path is a second
or more.
• A few microliters of sample are first evaporated at a low temperature
and then ashed at a somewhat higher temperature in an electrically
heated graphite tube or in a graphite cup.
• Then the current is rapidly increased to several hundred amperes,
which caused the temperature to soar to perhaps 2000oC to 3000oC;
atomization of the sample occurs in a period of a few milliseconds to
seconds.
• The absorption or fluorescence of the atomic vapor is then measured
in the region immediately above the heated surface.
• Pyrolytic coating of graphite tubes
• -reducing the natural porosity of the graphite tube minimizes some
sample matrix effects and poor reproducibility associated with
graphite furnace atomization.
• -During atomization, part of the analyte and matrix apparently diffuse
into the surface of the tube, which slows the atomization process,
thus giving smaller analyte signals.
• -To overcome this effect, most graphite surfaces are coated with a
thin layer of pyrolytic carbon, which seals the pores of the graphite
tube.
Monochromator
Prism
• Prism is a homogeneous solid transparent and refracting
medium bounded by two plane surfaces inclined at an
angle.
• The commonly used prism has two triangular faces that are
parallel to each other and three rectangular surfaces.
• They are made from glass (borosilicates) or other
transparent material cut with precise angles. Two of the
three rectangular faces are polished and are called
refracting surfaces.
• The angle between these two rectangular faces is called the
refractive angle of the prism.
• Prisms are made in different shapes depending on the
application. Triangle is the traditional shape of the prism.
• The triangular prism separates the white light into
constituent colours when it is passed through the prism.
Working of Prism
• When light travels from one medium to another, there is a change in the speed of light.
• This change in the speed of light causes the light to get refracted and enter the new medium
with a different angle.
• The angle at which the light hits the surface of the medium and the ratio of refractive indices
determines the degree of bending of the refracted light. There will be a change in
the refractive index of many materials (e.g. glass) when lights of different wavelengths are
used.
• This is the reason for each colour or different wavelengths making up the white light to be
refracted at different angles.
• When a narrow beam of white light is incident on a prism, the emerging light is found to
consist of seven prominent colours in the order of violet, indigo, blue, green, yellow, orange
and red.
• The violet colour with the shortest wavelength is bent the most and the longest wavelength
red is bent the least. This phenomenon of splitting white light into constituent colours is called
dispersion.
• Prism is sometimes used as a reflector of light rather than dispersion. If the light rays that
enter the prism hits the surface at an angle greater than the critical angle, there will be total
internal reflection.
Monochromator
Grating
• Grating monochromators disperse ultraviolet, visible,
and infrared light
• Grating consists of a hard, optically flat, surface that
has a large number of parallel and closely spaced
grooves.
• A grating for the ultraviolet and visible region typically
has 300–2000 grooves/mm, however 1200–1400
grooves/mm is most common.
• For the infrared region, gratings usually have 10–200
grooves/mm.
• A diffraction grating is able to disperse a beam of
various wavelengths into a spectrum of associated
lines because of the principle of diffraction:
Prism vs Grating
• Prisms and gratings are the two most common types of dispersive optics.
The major difference between these two elements is that the dispersion of
prisms is non-linear while gratings offer linear dispersion.
• The dispersion of prisms is efficient over a wide range of wavelengths and
the throughput of a prism is usually pretty high (>90%).
• However, they refract light in a wavelength-dependent manner, resulting in
the non-linear dispersion and accordingly the wavelength-dependent
resolution.
• Diffraction gratings, on the other hand, can spread light linearly or equally
into the chosen detector, which can improve resolution when used at their
intended wavelength and may allow for easier implementation into some
systems.
Burners
Total consumption burner
• In total-consumption burner, the fuel and oxidant (support) gases are mixed and
combust at the tip of the burner.
• The fuel (usually acetylene), oxidant (usually air) and sample all meet at the base
of flame. The sample is drawn up into the flame by the ‘Venturi Effect’, by the
support gas.
• The gas creates a partial vacuum above the capillary barrel, causing the sample
to be forced up the capillary. It is broken into a fine spray at the tip where the
gases are turbulently mixed and burned. This is the usual process of
‘nebulisation’.
• The burner is called total consumption because the entire aspirated sample
enters the flame or in other words the sample solution is directly aspirated into
the flame. All desolvation, atomization, and excitation occurs in the flame.
• However, the total consumption burner can be used to aspirate viscous and ‘high
solids’ samples with more ease, such as undiluted serum and urine. Also, this
burner can be used for most types of flames, both low- and high-burning velocity
flames.
• The Venturi Effect is the reduction in fluid pressure that results when a fluid
flows through a constricted section of pipe
Burners
Premixed burner or laminar flow burner
Premix burner system really consists of two key components, the burner
head or nozzle, and the gas-air mixing device that feeds it.
The fuel and support gases are mixed in a chamber before they enter the
burner head (through a slot) where they combust.
The sample solution is again aspirated through a capillary by the ‘Venturi
effect’ using the support gas for the aspiration.
 Large droplets of the sample condense and drain out of the chamber. The
remaining fine droplets mix with the gases and enter the flame. As much as
90% of the droplets condense out, leaving only 10% to enter the flame.
The 90% of the sample that does not reach the flame will travels back
through the mixing chamber and out as waste drain.
• The premix burners are generally limited
to relatively low-burning velocity flames.
• The most outstanding disadvantage of the
premix burner is that only low burning-
velocity flames can be used.
• A burning velocity which is higher than
the rate of flow gases leaving the burner
will cause the flame to travel down into
the burner resulting in an explosion
commonly known as flashback.
• Because of this limitation it is somewhat
difficult to use high burning-velocity
gases, which includes oxygen-based
flames.
 Total Consumption burner Premixed burner
The fuel and oxidant (support) gases are mixed and The fuel and support gases are mixed in a chamber
combust at the tip of the burner. before they enter the burner head (through a slot)
The sample is drawn up into the flame by the ‘Venturi where they combust.
Effect’, by the support gas. The sample solution is again aspirated through a
capillary by the ‘Venturi effect’using the support gas

The sample that enters the flame is lesser because the The sample that enters the flame is greater, because
droplets are larger. the droplets are finer.
Shorter path length Longer path length
The resulting drops are relatively large which will No fluctuation because of finer droplets
vaporize partially, leaving solid particles in the light
path. This may result fluctuation of flame
temperature and light scattering, which is registered
as an absorbance may cause false measurements to
be detected.

The resulting flame is turbulent and non-homogenous Usually produces an approximately laminar
(streamline) flame
Combustion with the total-consumption burner is Combustion with the premix burners is very quiet
noisy
Detectors
• Photomultiplier detector
Detectors
• Photomultiplier detector
• The working principle of the photomultiplier tube is that photons will dislodge
electrons by striking the photocathode. These electrons will then strike a
chain of dynodes, which dislodges more electrons, increasing the electric
signal that is proportional to the initial electromagnetic radiation in the
sample. This is all caused by the photoelectric effect.
• Photomultiplier tubes have three primary components, photocathodes,
dynodes and anode. The photocathode is a photoemissive surface that the
photons strike, which releases electrons equivalent to the number of photons
that hit it. The electrons hit the dynodes which releases even more electrons,
amplifying the electric signal.
• A total of 106–107 electrons per photon eventually reach the anode,
generating an electrical current
• Commonly used photocathode materials: Ag-O-Cs, Bialkali compounds (Sb-
Rb-Cs), multialkali compounds (Na-K-Sb-Cs), GaAs etc.
Detectors
• Photovoltaic cell
• A photovoltaic (PV) cell, also known as a solar cell, is an electronic component that
generates electricity when exposed to photons, or particles of light. This conversion is
called the photovoltaic effect, which was discovered in 1839 by French physicist Edmond
Becquerel
• A photovoltaic cell is made of semiconductor materials that absorb the photons emitted
by the sun and generate a flow of electrons.
• When the photons strike a semiconductor material like silicon , they release the
electrons from its atoms, leaving behind a vacant space. The stray electrons move
around randomly looking for another “hole” to fill.
• To produce an electric current, however, the electrons need to flow in the same
direction.
• This is achieved using two types of silicon. The silicon layer that is exposed to the sun is
doped with atoms of phosphorus, which has one more electron than silicon, while the
other side is doped with atoms of boron , which has one less electron.
• The resulting sandwich works much like a
battery: the layer that has surplus electrons
becomes the negative terminal (n) and the
side that has a deficit of electrons becomes
the positive terminal (p). An electric field is
created at the junction between the two
layers.
• When the electrons are excited by the
photons, they are swept to the n-side by an
electric field, while the holes drift to the p-
side. The electrons and holes are directed to
the electrical contacts applied to both sides
before flowing to the external circuit in the
form of electrical energy. This produces
direct current. An anti-reflective coating is
added to the top of the cell to
minimize photon loss due to surface
reflection.
FLAME PHOTOMETRY OR ATOMIC EMISSION SPECTROMETRY
Scheibe-Lomakin equation describes intensity of light emitted with the
help of following formula:
• I = k × cn
• Where:
I = Intensity of emitted light
c = Concentration of the element
k = Proportionality constant
• At the linear part of the calibration curve n~1,
• then I = k × c. In other words, the intensity of emitted light is directly
related to the concentration of the sample.
• The oxidants in flame photometer are mainly air, oxygen or nitrous oxide. The
temperature of the flame depends on the ratio of fuel and oxidant.
• The processes occurring during flame photometer analysis are summarized below:
• Desolvation: Desolvation involves drying a sample in a solution. The metal particles
in the solvent are dehydrated by the flame and thus solvent is evaporated.
• Vaporization: The metal particles in the sample are also dehydrated. This also led
to the evaporation of the solvent.
• Atomization: Atomization is the separation of all atoms in a chemical substance.
The metal ions in the sample are reduced to metal atoms by the flame.
• 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 higher energy state when excited.
• Emission: Since the higher energy state is unstable the atoms jump back to the
ground state or low energy state to gain stability. This jumping of atoms emits
radiation with characteristic wavelength. The radiation is measured by the photo
detector.
Working operation
• The principle of operation of the flame photometer is simple. The liquid is sprayed with a
non-shiny flame in the form of a fine colored mist depending on the characteristic emissions
of the elements, for example, sodium (Na), potassium (K), calcium (Ca) and lithium ( Li).
• The flame is detected by a photodetector which observes the flame through a very narrow
band optical filter which only lets through the wavelength (nm) according to the
characteristic emission of the chosen element.
• The output of the photodetector is fed into electronic modules which provide digital
readings of the desired element concentration. The method must be calibrated with known
concentrations of the solution, before testing the unknown liquid sample.
• Compressed air is supplied to an atomizer in a metering system using a compressor, resulting
in an airflow at the end of an atomizer, which draws sample fluid from the mixing chamber
and in the mixing mixing chamber. Liquid Petroleum Gas (LPG) is also used at controlled
pressure in the mixing chamber; here the atomized sample and gas are delivered to the
burner and ignited.
• Light from the flame is emitted by the optical lenses and transmitted to the flame
photometer detector through a selected filter. Electronically analyzed detector data and
sample solution results are displayed correctly.
Working procedure
• Both the standard stock solution and sample solution are prepared in fresh distilled water.
• The flame of the photometer is calibrated by adjusting the air and gas. Then the flame is allowed
to stabilize for about 5 min.
• Now the instrument is switched on and the lids of the filter chamber are opened to insert
appropriate colour filters.
• The readings of the galvanometer are adjusted to zero by spraying distilled water into the flame.
• The sensitivity is adjusted by spraying the most concentrated standard working solution into the
flame. Now the full scale deflection of the galvanometer is recorded.
• Again distilled water is sprayed into the flame to attain constant readings of galvanometer. Then
the galvanometer is readjusted to zero.
• Now each of the standard working solutions is sprayed into the flame for three times and the
readings of galvanometer are recorded. After each spray, the apparatus must be thoroughly
washed.
• Finally sample solution is sprayed into the flame for three times and the readings of
galvanometer are recorded. After each spray, the apparatus must be thoroughly washed.
• Calculate the mean of the galvanometer reading.
• Plot the graph of concentration against the galvanometer reading to find out the concentration
of the element in the sample.
• Atomizer : Flame atomizer
• Monochromator – Prism or grating
• Detector – Photomultiplier or photovoltaic detector
• Burner – Total consumption and premixed burner
• Total consumption burner is used in flame photometry and is not useful
for atomic absorption. The reason for this is that the resulting flame is
turbulent and non-homogenous because it combines the function of
nebulizer and burner.
• The detection limit is (informally) the lowest concentration of the
analyte that can be reliably detected
• LOD's may also be calculated based on the standard deviation of the
response (Sy) of the curve and the slope of the calibration curve (S) at
levels approximating the LOD according to the formula: LOD = 3.3(Sy/S).
Applications of flame photometer
• Flame photometer can be applied both for quantitative and qualitative
analysis of elements. The radiations emitted by the flame photometer are
characteristic to particular metal. Hence with the help of Flame photometer
we can detect the presence of any specific element in the given sample.
• The presence of some group II elements is critical for soil health. We can
determine the presence of various alkali and alkaline earth metals in soil
sample by conducting flame test and then the soil can be supplied with
specific fertiliser.
• The concentrations of Na+ and K+ ions are very important in the human
body for conducting various metabolic functions. Their concentrations can
be determined by diluting and aspirating blood serum sample into the
flame.
• Soft drinks, fruit juices and alcoholic beverages can also be analysed by
using flame photometry to determine the concentrations of various metals
and elements.
Advantages of flame photometer
• The method of analysis is very simple and economical.
• It is quick, convenient, selective and sensitive analysis.
• It is both and qualitative and quantitative in nature.
• Even very low concentrations (parts per million/ppm to parts per
billion/ppb range) of metals in the sample can be determined.
• This method compensates for any unexpected interfering material
present in the sample solution.
• This method can be used to estimate elements which are rarely
analysed.
•
Disadvantages of flame photometer
• In spite of many advantages, this analysis technique has quite a few
disadvantages:
• The accurate concentration of the metal ion in the solution cannot be
measured.
• It cannot directly detect and determine the presence of inert gases.
• Though this technique measures the total metal content present in the
sample, it does not provide the information about the molecular structure of
the metal present in the sample.
• Only liquid samples may be used. Also sample preparation becomes lengthy in
some cases.
• Flame photometry cannot be used for the direct determination of each and
every metal atom. A number of metal atoms cannot be analysed by this
method. The elements such as carbon, hydrogen and halides cannot be
detected due to their non-radiating nature.
Reference Books

Instrumental Methods of Analysis by Willard Merritt, Dean Settle

Instrumental methods of chemical analysis – V. K. Ahluwalia
Refer any book with the topic as Instrumental methods of analysis