FLAME PHOTOMETRY
INTRODUCTION
• Flame photometry is based on measurement of intensity of the light emitted
when a metal is introduced into a flame.
• The wavelength of the colour indicates what element is present whereas the
intensity suggests the quantity of the element.
• In early experiments, the visible colour of the flame was used to confirm the
presence of elements in the sample, particularly alkali metals and alkaline
earth metals.
• Later the whole UV and visible range was utilized using a
spectrophotometer that permitted us to select the wavelengths of radiation
and measure its intensity with considerable accuracy.
• This spectrophotometric technique was found to be highly reliable and
easily used technique for determination of concentrations of Na, K, Ca and
Mg.
INTRODUCTION
• Flame photometry (FP) is also named as flame emission spectroscopy.
• Here the flame is used to provide the energy of excitation of atoms
introduced into the flame.
• FP, coupled with simple read-out devices, provides high sensitivity and
reliability for the determination of elements in the first two columns of the
periodic table.
• These elements are Na, K, Li, Ca, Mg, Sr (strontium) and Ba.
• The measurements of these elements are highly useful in medicine,
agriculture and plant science.
• For some transition elements, such as Cu, Fe and Mn, FP has been
successful but these have limited scope.
• In addition, FP can be applied to non-metals utilizing IR region of the
spectrum.
Colour of the flames for various elements
Element Group Characteristic Flame Color Strong Emission Line (nm)
Lithium (Li) Group I Crimson red 670.8
Sodium (Na) Group I Intense yellow 589.0, 589.6 (D-lines)
Lilac / pale violet (may be
Potassium (K) Group I masked by Na yellow, cobalt 766.5, 770.1
glass filter used)
Rubidium (Rb) Group I Red-violet 780.0, 795.0
Cesium (Cs) Group I Blue-violet 852.1, 894.3
Calcium (Ca) Group II Brick-red / orange-red 422.7
Strontium (Sr) Group II Crimson / bright red 460.7, 407.8
Barium (Ba) Group II Apple green 553.5
Copper (Cu) Transition Blue-green 510.6
Non-meta
Boron (B) (as borates) Bright green 548.3
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LIMITATIONS
• Relatively low energy is available from the flames and therefore FP is
not appliable for only those metal atoms that require large amount of
energy to become excited.
• FP is primarily applicable to alkali metals (Li, Na, K, Rb, Cs) and
alkaline earth metals (Ca, Sr, Ba, Mg).
• FP is not applicable or has been less successful for transition metals
(Fe, Co, Ni, Cu, Zn, Cr, Mn, etc).
• FP does not tells us about the molecular form of the metal in the
original sample.
• It has not been implemented for direct determination of noble
metals, halides or intern gases since these require more energy.
Periodic table
LIMITATIONS: WHY TRANSITION METALS ARE
NOT USED FOR FLAME PHOTOMETRY
• Flame photometry (also called flame atomic emission spectroscopy) is
primarily applicable to alkali metals (Li, Na, K, Rb, Cs) and alkaline earth
metals (Ca, Sr, Ba, Mg) because:
• These metals have low excitation/ionization energies, so their valence
electrons can be easily excited in a flame.
• They emit characteristic radiation (line spectra) in the visible region (e.g.,
Na at 589 nm, K at 766 nm), which can be easily detected.
• In contrast, transition metals (Fe, Co, Ni, Cu, Zn, Cr, Mn, etc) have:
(i) Higher excitation energies.
(ii)More complex spectra (due to partially filled d-orbitals).
(iii)Weak emission in the flame, making detection unreliable.
General Principle OF FLAME PHOTOMETRY
LIQUID SAMPLE CONTAINING EVAPORATION OF DROPLETS
FORMATION OF LIQUID
ELEMENT ASPIRATED INTO A RESULTING IN THE
DROPLETS
FLAME FORMATION OF RESIDUES
FORMATION OF EXCITED
WAVELENGTH AND INTENSITY DECOMPOSITION OF RESIDUE
ATOMS AND EMISSION OF
OF EMITTED RADIATION INTO NEUTRAL ATOMS
RADIATION FROM ATOMS
MEASURED BY FP
General Principle OF FLAME PHOTOMETRY
• When a liquid sample containing a metallic salt solution is introduced into a flame,
the processes involved in flame photometry are complex.
• The solvent containing the sample is vaporised, leaving particles of the solid salt.
• The salt is vaporised or converted into gaseous state.
• A part of the gaseous molecules are progressively dissociated to give free neutral
atoms or radicals.
• These neutral atoms are excited by the thermal energy of the flame.
• The excited atoms, which are unstable, quickly emit photons and return to lower
energy state, eventually reaching the unexcited state.
• The measurement of the emitted photons, i.e., radiation, forms the basis of flame
photometry.
General Principle OF FLAME PHOTOMETRY
• If E2 and E1 are higher and lower energy levels, the radiation emitted
during the jump may be defined as:
E2-E1 = hγ
Where, γ =c/λ
Therefore, E2-E1 = hc/λ
λ = hc/(E2-E1)
• From this equation, one can calculate the wavelength of emitted radiation
that is characteristics of the particular element from which it is emitted.
The wavelength suggests which element is present and intensity indicates is
amount.
• A portion of neutral atoms or radicals may combine to form gaseous
compounds decreasing the population of neutral atoms and its intensity.
• It constitutes the chemical interference in flame photometry.
General Principle OF FLAME PHOTOMETRY
• The fraction of atoms that are thermally excited is governed by
Boltzmann distribution:
N*/N0 = Ae-∆E/kT
• Where N* = number of excited atoms, N0 = number of atoms
remaining in the ground state, A = Constant for a particular element,
∆E = difference in energies of the two levels, k = Boltzmann’s
constant, T = Temperature.
• Therefore, the fraction of atoms excited depends on the temperature
of the flame.
FLAME TEMPERATURES
Fuel Oxidant Flame temperature (0C)
H2 O2 2800
H2 Air 2100
H2 Ar 1600
Acetylene O2 3000
Acetylene Air 2200
Acetylene N2O 3000
Propane O2 2800
Propane Air 1900
• The temperature of the fuel is controlled by the type pf fuel and oxidant used.
• Flames have only limited amount of energy available as compared to emission spectrographs or plasma emission
torches (6000–10,000 K).
• For this flames are most useful when for the detection of alkali metals and alkaline earth metals.
• These are not useful for transition metals and most of the other metals of periodic table. For these, emission
spectrographs or plasma emission torches are used.
• On the contrary, emission spectrographs or plasma emission torches may be used for group I and II metals. However,
it increases the risk of ionization due to low ionization potential of these elements.
• Ionization results in loss of atoms due to generation of ions and create a complete change of energy levels and
therefore may reduce the intensity of entire emission spectra.
• Therefore, in practice emission spectrographs or plasma emission torches have limited use for the analyses of the
group I and II metals.
Instrumentation/Components of FP
•Burner
•Filter/Monochromator
•Detector
•Read out device
BURNERS
• There are different burners available, which are used to spray the
sample solution into fine droplets, mix with fuel and oxidant, so that a
homogenous flame of stable intensity is obtained.
• The most common ones are Mecker burner, total consumption burner
and Laminar flow (premix).
• Mecker burner: It was used earlier and employed natural gas and
oxygen. Produces relatively low temperatures and low excitation
energy (applicable to alkali metals only). The flames are not
homogenous leading to different concentrations of excited atoms in
oxidizing regions and reducing regions.
BURNERS
• Total consumption burner: The
sample solution is aspirated
through a capillary by the high
pressure of fuel and oxidant and
burnt at the tip of the burner.
• Merit: The design is simple and the
entire sample is consumed.
• Demerit: An uniform and
homogenous flame is not
obtained.
• Laminar flow (premix) burner: It is
the most widely used mainly because
of uniformity in flame intensity.
• Sample solution, fuel and oxidant
are mixed before they reach the
burner tip.
• Only few droplets of uniform size
reaches the flame and remaining are
drained through an outlet at the
bottom.
Filter/monochromator
• In simple FP, the monochromator is a prism. In extensive models, the
grating monochromators are used.
• In FP, the wavelength as well as intensity of the radiation emitted by the
element has to be monitored. Hence a filter monochromator is to be used.
• The grating monochromator employs a grating which is essentially a series
of parallel straight lines cut into a plane surface.
• Typically, a simple flame photometer contains a filter wheel (containing
several filters for either Ca, Li, Na or K) and when a particular element has
to be analysed, the specific filter is selected.
Detector: Photomultiplier tube
• The radiation emitted by the elements is mostly in the
visible region.
• Hence conventional detectors like photo voltaic cell or photo
tube is used as detector.
• In a FP, photomultiplier tube is most commonly used.
• The principle employed in this detector is that multiplication
of photoelectrons by secondary emission of electrons.
• This is achieved by using a photo cathode and a series of
anodes (dyanodes), upto 10 and each is maintained at
75-100V higher than the preceding one.
• At each stage, the electron emission is multiplied by a factor
of 4 or 5 due to secondary
8
emission of electrons and hence
an overall factor of 10 is achieved.
• The multiplied electrons are collected at the anode,
producing a measurable electrical current or pulse
proportional to the incoming light intensity.
• PMT can detect very week signals, even 200 times weaker
than that could be done using photovoltaic cell.
Read out device: The signal from the detector is a shown as a response in the digital read out device.
Overall technique of Flame Photometry
• Typically a flame photometer contains a burner, where the solution to be analysed is sprayed into fine droplets after mixing with
fuel and oxidant.
• A compressor, compresses the air or oxygen and fuel, at a pressure of about 0.5 Kg/cm2.
• This high pressure is required to spray the sample solution to fine droplets. When the sprayed droplets are ignited, the solvent is
evaporated by the thermal energy of the flame, leaving behind behind fine residue that is converted to neutral atoms.
• The neutral atoms are excited by thermal energy to excited atoms that are unstable and hence loose energy in the form of
radiation and returns to the ground state.
• The wavelength as well as intensity of the light radiation emitted is detected by using a filter and a photometric detector.
• A conclave mirror is used to focus the light onto a filter wheel (containing Na, K, Li, Ca filters), in which the desired position can
be selected based on the element to be measured.
• This light passes through a slit and falls on the detector.
• The detector response is shown in the digital display device (% flame intensity).
