CHEM F313: Instrumental Methods of Analysis

Lecture 28
Flame Photometry & Atomic Absorption Spectroscopy
10/19/2023
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Outline
 Last Class

 Thermal Methods of Analysis

 Today’s Class

 Flame Photometry & Atomic

Absorption Spectroscopy
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Discoverer

• In 1860 Robert Bunsen and

Gustav Kirchhoff discovered two
alkali metals, cesium and
rubidium, with the aid of the
spectroscope they had invented
the year before.
• These discoveries inaugurated a
new era in the means used to
find new elements.

Gaustav Kirchhoff & Robert Bunsen

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 Discoverer
Classification of Atomic Spectroscopic Methods
• Flame
• Electrothermal (or furnace) method
• Inductively coupled argon plasma
• Direct current argon plasma
• Electric arc
Once in the vapour phase, the atoms of the elements interact with
radiation and provide information about themselves. The interaction of
radiation and matter can manifest itself in terms of absorption,
emission or fluorescence emission.
Atomic Absorption Spectrometry (AAS)
Atomic Emission Spectrometry (AES)
Atomic Fluorescence Spectrometry (AFS)
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 Discoverer
Atomic Absorption Spectrometry (AAS):

• The atomic vapours containing free atoms of an element in the

ground state are subjected to a UV-VIS radiation source emitting a
characteristic frequency of the element present in atomic vapours.
• The radiation is absorbed and the intensity of the radiation is
attenuated.
• The absorbed radiation causes excitation of electrons from the
ground state to an excited level.
• The extent of absorption is a quantitative measure of the
concentration of the atomic vapours of the element in the ground
state.
• It is an electronic excitation and the energy of transitions lies in the
to UV-VIS region of the electromagnetic spectrum.
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 Discoverer
Atomic Emission Spectrometry (AES):

• A sample is normally excited by the thermal energy of a flame, argon

plasma or an electrical discharge.
• As the excited state is short lived, the excited atoms return back to
the ground state after a very short lifetime (typically 10-6 to 10-9 s).
• This is accompanied by the emission of electromagnetic radiation,
normally in the form of light in the UV - VIS region.
• The wavelength of the emitted radiation and its intensity provide the
qualitative and quantitative information about the analyte.
• The AES employing flame as a means of excitation is called flame
photometry or flame emission spectroscopy (FES).
• It is used for the routine determination of metals, mainly of alkali
and alkaline earth metals, though other metals can also be analysed.
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Discoverer

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What is Flame Photometry?
• What is it?
 The measurement of the emitted light intensity when a metal is
introduced into the flame.
 Emission wavelength provides information about the element
 The intensity of the flame provides the concentration
• General facts
 Branches of Atomic Absorption Spectroscopy & Flame emission
spectroscopy
 Important in analytical chemistry
 Flame photometer can be used to determine the concentration of
certain metal ions like sodium, potassium, lithium, calcium and
cesium etc.
 IUPAC name is Flame Atomic Emission Spectroscopy (FAES)
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Kirchoff’s Expt: Interpretation of
Flame Photometry
• White light impinged on a slit dispersed by a prism, a continuous
spectrum is obtained
• If the white light is replaced by a burner onto which NaCl is
sprinkled, an emission of Na is obtained: yellow doublet
• The optical radiation emitted from flames is characteristic of the
elements present in the flame gases or the ones introduced into
the burning flame by different means.
• It was also demonstrated during the same time that the intensities
of the radiation, characteristic of different elements, present in the
spectra, were dependent on the amount of elemental species
present.
• The potential of atomic spectroscopy both as qualitative as well as
quantitative analysis was established.
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Principle of Flame Photometry
• The compounds of the alkali and alkaline earth metals (Group II)
dissociate into atoms when introduced into the flame.
• Some of these atoms get excited to higher energy levels. But these
atoms are not stable at higher level

• Hence, these atoms emit

radiations when returning Emitted
Element wavelength Flame color
back to the ground state.
Na 589 nm Yellow
• These radiations generally lie
in the visible region of the K 766 nm Violet
spectrum. Ba 554 nm Lime green
• Each of the alkali and alkaline Ca 622 nm Orange
earth metals has a specific Li 670 nm Red
wavelength.
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Principle of Flame Photometry
• Relation with the concentration,
 For certain concentration ranges, the intensity of the emission is
directly proportional to the number of atoms returning to the
ground state.
 And the light emitted is in turn proportional to the concentration of
the sample.

N* and N0 = Number of atoms in excited state and

ground state, respectively,
ΔE = Energy difference between ground and excited
state (in J),
g* and g0 = Statistical factors that depend on the
degeneracies of the levels involved,
k = Boltzmann constant (= 1.28 × 10-23 J k -1), and
T = Absolute temperature
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Principle of Flame Photometry
The intensity of the emitted radiation (P) is proportional to the number
of excited atoms N*

Thus, the intensity of the emitted light will be directly proportional

to the concentration of the element introduced into the flame.
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 Parts of Flame Photometer
• Source of Flame: A Burner in the flame photometer is the source of
flame. It can be maintained in at a constant temperature. The
temperature of the flame is one of the critical factors in flame
photometry.
Temperature (°C)
Fuel-Oxidant mixture
Natural gas-Air 1700
Propane-Air 1800
Hydrogen-Air 2000
Hydrogen-Oxygen 2650
Acetylene-Air 2300
Acetylene-Oxygen 3200
Acetylene-Nitrous oxide 2700
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 Parts of Flame Photometer
• Nabulizer: Nebuliser is used to send homogeneous solution into the
flame at a balanced rate.
• Optical system: The optical system consists of convex mirror and
convex lens. The convex mirror reflects the light emitted from the
atoms. Convex mirror also helps to focus the emissions to the lens.
The lens helps to focus the light on a point or slit.
• Simple color filters: The reflections from the mirror pass through the
slit and reach the filters. Filters will isolate the wavelength to be
measured.
• Photo detector: The intensity of radiation emitted by the flame is
measured by photo detector. Here the emitted radiation is
converted to an electrical signal with the help of photo detector.
These electrical signals are directly proportional to the intensity of
light.
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Flame Photometry: Set Up

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Flame Photometry: Set Up

Diagram describing the process of atomization

for continuous atomizers.

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Mirror used in Flame photometry

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Overview of Flame Photometry

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 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.
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 Working procedure
• 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.
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 Processes in Flame Photometry
• 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 heat of the flame vaporizes the sample
constituents. No chemical change takes place at this stage.
• 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.
For example, Mg2+ (aq) + 2e →Mg (g)
• Excitation: The atoms at this stage are able to absorb energy from
the heat of the flame. The electrostatic force of attraction between
the electrons and nucleus of the atom helps them to absorb a
particular amount of energy.
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 Processes in Flame Photometry
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.

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 Determination of Concentration
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.
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Flame Emission Color

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 Flame Emission Spectroscopy vs
Atomic Absorption Spectroscopy
• In Flame Photometry, a thermal device used to elevate the
temperature consists of a burner fed with a gaseous combustible
mixture; In atomic absorption spectroscopy, a small electric oven
that contains a graphite rod resistor heated by the Joule effect.
• In Flame photometry, an aqueous solution of the sample is
nebulized into the flame where atomization takes place; In the latter,
the sample is deposited on the graphite rod
• In Flame photometry, the radiation intensity emitted by a small
fraction of the atoms that have passed into the excited state by the
elevated temperature is measured; In atomic absorption
spectroscopy (AAS), the optical absorption of atoms in their ground
state is measured when the sample is irradiated with the appropriate
source
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Conclusions
 Flame Photometry & Atomic
Absorption Spectroscopy

Next Class
 Flame Photometry & Atomic
Absorption Spectroscopy

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