FLAME PHOTOMETRY

INTRODUCTION :
 Flame photometry (more accurately called Flame Atomic Emission
Spectrometry) is a branch of spectroscopy in which the species examined in the
spectrometer are in the form of atoms.
 A photoelectric flame photometer is an instrument used in inorganic chemical
analysis to determine the concentration of certain metal ions among them sodium,
potassium, calcium and lithium.
 Flame Photometry is based on measurement of intensity of the light emitted
when a metal is introduced into flame –
( i ) The wavelength of colour tells what the element is (qualitative),
( ii ) The colour's intensity tells us how much of the element present (quantitative).
The basic principle upon which Atomic Spectroscopy works is based on the fact that
"Matter absorbs light at the same wavelength at which it emits light".
When a metal salt solution is burned, the metal provides a colored flame and each
metal ion gives a different colored flame.
Flame tests, therefore, can be used to test for the absence or presence of a metal ion.

PRINCIPLE :
Liquid sample containing metal salt solutionintroduced into a flame.
Solvent is vaporized, leaving particles of solid salt.
Salt is vaporized into gaseous stateGaseous molecule dissociate to give neutral
atoms.
The unstable excited atoms emit photonswhile returning to lower energy state.
The measurement of emitted photons forms the basis of flame photometry using
photomultiplier tube detectors.
INTERFERENCE :
In determining the amount of a particular element present, other elements can also affect the

result. i.e. radiation intensity may not accurately represent the sample concentration because

of the pressure of other materials in the sample.

Such interference may be of 3 kinds –

( A ) Spectral interferences, ( B ) Chemical interferences & ( C) Chemical interferences.

( A ) Spectral Interferences :
The first type of interference arises when two elements exhibit spectra, which partially

overlap, and both emit radiation at someparticular wavelength. eg. - the Fe line at 324.73 nm

overlaps with the Cu line at 324.75 nm.

•SOLUTION : It can overcome either by taking measurements at analternative wavelength

which has no overlap, if available, or byremoving the interfering element by extraction.

The second type of spectral interference deals with spectral lines of two or more elements

which are close but their spectra do notoverlap

•SOLUTION : It can be reduced by increasing the resolution of thespectral isolation system.

A third type of spectral interference occurs due to the presence of continuous background

which arises due to high concentration of salts in the sample, especially of alkali and alkaline

earth metals
•SOLUTION : This type of interference can be corrected byusing suitable scanning

technique.
( B ) Chemical Interferences :

The chemical interferences arise out of the reaction between different interferens

and the analyte. These are of different types:

( I ) Cation-Anion Interferences : The presence of certain anions, such as

oxalate, phosphate, sulphate, in a solution may affect the intensity of radiation

emitted by an element, resulting in serious analytical error. For example, calcium

in the presence of phosphate ion forms a stable substance, as Ca (PO) which does

not decompose easily, resulting in the production of lesser atoms.

( II ) Cation-Cation Interference : Due to mutual interferences of cations. These

interferences are neither spectral nor ionicin nature. Eg. aluminum interferes with

calcium and magnesium.

( III ) Oxide Formation Interferences : Interference due to oxide formation. It

arises due to the formation of stable metal oxide if oxygen is present in the flame.
( C ) Ionization Interferences :
 High temperature flame may cause ionzation of some of the metal atoms, e.g.

sodium, Na ↔ Na+ + e-
 The Na+ ion possesses an emission spectrum of its own with frequencies, which

are different from those of atomic spectrum of the Na atom.

INSTUMENTATION :
Typical instrumental

set up for a flame

Photometer.
( A ) Sample Delivery System :

There are three components for introducing liquid sample:

( I ) Nebulizer - it breaks up the liquid into small droplets.

Nebulization the is conversion of a sample to a mist of finely divided droplets using

a jet of compressed gas.

The flow carries the sample into the atomization region.

Types of Nebulizer :

(a)
Pneumatic nebulizer,

(b)
Electro-thermal vaporizers,

(c)Ultrasound nebulizer.

( II ) Aerosol modifier - it removes large droplets from the stream and allow only

smaller droplets than a certain size to pass.

( III ) Flame or Atomizer - it converts the analyte into free atoms.

( B ) Source :
 A Burner used to spray the sample solution into fine droplets.
 Several burners and fuel + oxidant combinations have been used to produce
analytical flame including - Premixed, Mecker, Total consumption, Lundergarh,
Shielded burner and Nitrous oxide- acetylene flames.

( I ) Pre-mixed Burner : In this type of burner

the sample and fuel-oxidant are thoroughly
mixed before aspiration and reaching to the
flame. The advantage of this type of burner is
uniformity of flame produced. However, it has
a disadvantage that heavy loss of mixture up to
95% occurs during the process.
( II ) Mecker Burner : This was the first type of
burner used in flame photometry. It generally works
with aid of natural gas and oxygen as the fuel and
oxidant. The temperature produced in the flame is very
low and results low excitation energy. Hence, it is not
used widely.

( III ) Total Consumption Burner : Due to high

pressure of fuel (hydrogen) and oxidant (oxygen) the
sample solution is aspirated through a capillary and
burned at the tip of burner. It has advantage over others
as the entire consumption of sample takes place during
the during the process of measurement. But it produces
non-uniform flame and turbulent.
( IV ) Lundergraph Burner : In this particular
burner the sample and aid are mixed in a chamber
and the mixed composition is sent to a fuel nozzle
where it is atomised here the sample reaches to
the flame is only about 5% of the total content.

( V ) Shielded Burner : In this burner the

flame is shielded from the ambient atmosphere
by a stream of inert gas ceiling is required to
get better analytical sensitivity during the
measurement process following results are
obtained with sale did.
( VI ) Nitrous Oxide-Acetylene Burner :
These flames are superior to other flames for
effectively producing free atoms. Metals
with very reflective oxides such as
aluminium and titanium are analysed by this
burner. However, it has a drawback that high
temperature reduces its usefulness for the
determination of alkali metals as they easily
ionised. Also it produces intense background
emission which makes measurement of metal
emission difficult.
( C ) Monochromator :
 Prism : Quartz material is used for making prism, as quartz is transparent over
entire region.
 Grating : It employs a grating which is essentially a series of parallel straight lines
cut into a plane surface.

( D ) Filters :
 In some elements, the emission spectrum contains a few lines. In such cases wide
wavelength ranges will be allowed to enter the detector causing any serious error.
 In such situation, an optical filter may be used in place of slit and monochromator
system.
( E ) Detectors :
The radiation coming from the optical system is allowed to fall on the detector
which measure the intensity of radiation following on it.
Photomultiplier tubes
Photo emissive cell
Photo voltaic cell

( F ) Read-out Device :
 It is capable of displaying the absorption spectrum as wellabsorbance at specific
wavelength.
 Nowadays the instruments have microprocessor controlled electronics that
provides outputs compatible with theprinters and computers.
 Thereby minimizing the possibility of operator error intransferring data.
APPLICATION :

( A ) Qualitative Analysis :
 Generally alkali and alkaline earth metal can be estimated by flame photometry.
 As characteristic wavelength is emitted by the element hence detector recognizes
that wavelength and atom is detected.
 Manual method of detection is via flame characteristic color e.g. Na produce
yellow.
( B ) Quantitative Analysis :
Many alkali and alkaline metals amount can be detected by the flame photometry
by –
 Method of standard addition,
 Method of internal standard.
( C ) Other Application :
 To estimate Na, K, Ca, Li in serum, body fluid, CSF and urine.
 Determination of sodium and potassium in soil
 Determination of metals such as Mn and Cu.
 It is also used for the analysis of plant materials and industrial cements.
REFERENCE :
1. Deewan SK. Organic spectroscopy (N.M.R., I.R., Mass and UV).New Delhi:CBS
Publishers and Distributors Pvt. Ltd.; 2010.
 
2. William K. Organic Spectroscopy. Macmillan: Macmillan Chemistry Text; 1991.
 
3. Verma RM, Analytical Chemistry:Theory and Practice. Third Edition. New Delhi:
CBS Publishers and Distributors Pvt. Ltd.; 2006.
 
4. Ravi Sankar S., Text Book of Pharmaceutical Analysis, Fifth Edition.
Tirunelveli:Rx Publications: 2018.