Flame Photometry

Instrumentation and Application

Presented By-
Vishal Singh
Group-1
 Contents
• Introduction
• Principle
• Instrumentation
• Applications
• Limitations
• References
 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.
– The wavelength of colour tells what the element is
(qualitative)
– The colour's intensity tells us how much of the element
present
(quantitative)
 Principle

Steps involved
• Desolvation
• Vaporisation
• Atomization
• Excitation
• Emission process
 Instrumentation
Basic components of flame photometer are –
• Nebuliser
• Flame
• Monochromator
• Detector
• Read out device
 Nebuliser
• This is the component of sample delivery system which breaks up the
bigger liquid droplet to smaller liquid droplets.
• The process of conversion of sample to a fine mist of finely divided
droplets using a jet of compressed gas is known as Nebulization.
• The solution to be nebulised is drawn up a capillary tube by the
Venturi action of a jet of air blowing across the top of the capillary; a
gas flow at high pressure is necessary in order to produce a fine
aerosol.
Types of Nebuliser:
• Pneumatic nebulizers

• Electro thermal vaporizer

• Ultrasound nebulizer
Types of pneumatic nebulizer
• Concentric Tubes Nebulizer
• Cross Flow Nebulizer
• Babington Nebulizer
• Fritted Disk Nebulizer

Concentric tubes
• The liquid sample is sucked through a
capillary tube by a high pressure jet of
gas flowing around the tip of the
capillary.
• The high velocity breaks the sample into
a mist and carries it to the atomization
region.
 Cross Flow
• The jet stream flows right
angles to the capillary tip.

• It uses a high speed stream

of gas perpendicular to the
tip of the sample capillary
 Babington
• The jet is pumped through a
small orifice in a sphere on
which a thin film of sample
flows
• In this type of nebulizer the
sample solution flows freely
over small aperture, rather than
passing through a fine capillary
Fritted or Porous Disk
• The sample is pumped into a fritted
disk through which the gas jet is
flowing and this gives fine aerosol
than others
• High efficiencies can be obtained by
introducing the sample at
predetermined location of the fritted
surface
ELECTRO-THERMAL VAPORZERS
An electro thermal
vaporizer contains an
evaporator in a closed
chamber through which an
inert gas carries the
vaporized sample into the
atomizer.
ULTRASONIC NEBULIZERS
• The sample is pumped onto the
surface of a vibrating
piezoelectric crystal.
• The resulting mist is denser and
more homogeneous than
pneumatic nebulizers
 BURNERS
Several kinds of burners are used to convert the fine droplets of sample
solution into neutral atom ,which further due to the high heat or
temperature of flame are excited hence emit radiation of characteristic
wavelength and colour.
Types of burner used:
• Mekker or Mecker burner
• Total consumption burner
• Premix burner
• Lundergarph’s burner
• Shielded burner
• Nitrous oxide – Acetylene burner
MECKER OR MEKKER BURNER
• This was the primitive type of burner used
in flame photometry and was used earlier.
• It generally works with aid of natural gas
and oxygen as fuel and oxidant.
• The temperature so produced in the flame
was relatively low, resulting in low
excitation energy.
• Now a days it is not used but it was best
suited for alkali metal.
 TOTAL CONSUMPTION BURNER
• Due to the high pressure of fuel and
oxidant the sample solution is aspirated
through capillary and burnt at the tip of
burner
• Hydrogen and oxygen are generally
employed as fuel and oxidant.
• The advantage over other is the entire
consumption of sample,
• It’s disadvantage is the production of non
uniform flame and turbulent.
Premix or Laminar Flow Burner
• In this burner the sample , fuel
oxidant are thoroughly mixed
before aspiration and reaching to
flame.
• The main advantage of it is the
uniformity of flame produced.
• The main disadvantage is the
heavy loss of mix up to 95%.
 LUNDENGARPH’S BURNER
• A small sample liquid droplets vaporized and
move to base of flame in the form of cloud.
• Large droplets condensed at side and then
drained off.

SHIELDED BURNER
• In this flame was shielded from the ambient
atmosphere by a stream of inert gas.
• Shielding is done to get better analytical
sensitivity.
• Following results are obtained with shielded
burner
 NITROUS OXIDE-ACETYLENE
FLAME
• These flames were superior to other flames for
effectively producing free atoms
• E.g.-metals with very reflective oxides such as
aluminium and titanium.
The drawback of it is:
• the high temperature reduces its usefulness for
the determination of alkali metals as they are
easily ionized
• Intense background emission, which makes the
measurement of metal emission very difficult
 STRUCTURE OF FLAME
As seen in the figure, the flame may be
divided into the following regions or
zones
1. Preheating zones
2. Primary reaction zone or inner zone
3. Interconal zone
4. Secondary reaction zone
LIST OF FUEL AND OXIDANT USED
 MONOCHROMATORS
• The main function of the monochromator is to convert
polychromatic light into the monochromatic one.
• The two types of monochromator generally used are as
under:
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
 DETECTORS

• Photomultiplier tube

• Photo emissive cell

• Photo voltaic cell

 PHOTOMULTPLIER TUBE
• The intensity of the light is fairly low, so a photomultiplier tube (PMT) is
used to boost the signal intensity.
• A detector (a special type of transducer) is used to generate voltage from
the impingement of electrons generated by the photomultiplier tube.
 PHOTOVOLTAIC CELL
• It has a thin metallic layer coated with silver or gold act as
electrode , also has metal base plate which act as another
electrode.
• Two layers are separated by semiconductor layer of
selenium, when light radiation falls on selenium layer.
• This creates potential difference between the two electrode
and cause flow of current.
 Read-out Device
• It is capable of displaying the absorption spectrum as well as
absorbance at specific wavelength
• Nowadays the instruments have microprocessor controlled
electronics that provides outputs compatible with the
printers and computers.
• Thereby minimizing the possibility of operator error in
transferring data.
 APPLICATIONS
• 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 colour e.g. Na produces yellow colour.
• QUANTITATIVE ANALYSIS :
Many alkali and alkaline metals amount can
be detected by the flame photometry by:
1. Method of standard addition.
2. Method of internal standard.
Elements and their Characteristic Wavelength of
Emission and Detection Limit
Element Wavelength Detection
(nm) limit
Al 396 0.5
Ba 455 3
Ca 423 0.07
Cu 325 0.6
Fe 372 2.5
Pb 406 14
Li 461 0.067
Mg 285 1
Ni 355 1.6
Hg 254 2.5
 OTHER APPLICATIONS
• Determination of concentration of Na in extracellular fluid (in cases
of Hypernatremia or Hyponatremia and K in intracellular fluid (in case
of hypo and hyperkalemia).
• In soil analysis.
• Review of sodium, potassium or calcium content in the
construction and cement industries.
• Concentration determinations of sodium and potassium in fertilizer
production and in process control.
 INTERFERNCES DURING
QUANTITAIVE ESTIMATION
Following types of interferences generally occur during
quantitative estimation
1. SPECTRAL INTERFERENCE
2. CHEMICAL INTERFERENCES
3. IONIZATION INTERFERENCES
 SPECTRAL INTERFERENCES
• The first type of interference arises when two elements exhibit spectra,
which partially overlap, and both emit radiation at some particular
wavelength.
e.g. - 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 an
alternative wavelength which has no overlap, if available, or by removing
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 not overlap
SOLUTION: It can be reduced by increasing the resolution of the spectral
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 by using suitable
scanning technique.
 CHEMICAL INTERFERENCE
The production of ground-state gaseous atoms which is the basis of
flame spectroscopy may be inhibited by two main forms of chemical
interference: (a) by stable compound formation, or (b) by ionization.
1. Stable compound formation:
This leads to incomplete dissociation of the substance to be analysed
when placed in the flame, or it may arise from the formation within the
flame of refractory compounds which fail to dissociate into the
constituent atoms. Examples of these types of behavior are shown by
(1) the determination of calcium in the presence of sulphate or
phosphate, and (2) the formation of stable refractory oxides of
titanium, vanadium, and aluminum. Chemical interferences can usually
be overcome in one of the following ways.
1. Increase in flame temperature often leads to the formation of free gaseous atoms,
and for example aluminium oxide is more readily dissociated in an acetylene-nitrous
oxide flame than it is in an acetylene-air flame. A calcium-aluminium interference
arising from the formation of calcium aluminate can also be overcome by working at
the higher temperature of an acetylene-nitrous oxide flame
2. Extraction of the analyte or of the interfering element(s) is an obvious method of
overcoming the effect of 'interferences'. It is frequently sufficient to perform a simple
solvent extraction to remove the major portion of an interfering substance so that, at
the concentration at which it then exists in the solution, the interference becomes
negligible. If necessary, repeated solvent extraction will reduce the effect of the
interference even further and, equally, a quantitative solvent extraction procedure may
be carried out so as to isolate the substance to be determined from interfering
substances.
2. IONIZATION INTERFERENCES:
High temperature flame may cause ionization 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.
• Solution: The ionization of the element to be determined may also be reduced by
the addition of an excess of an ionization suppressant; this is usually a solution
containing a cation having a lower ionization potential than that of the analyte.

LIMITATIONS
• The temperature is not high enough to excite transition metals,
therefore the method is selective towards detection of alkali and
alkaline earth metals.
• The relatively low energy available from the flame leads to relatively
low intensity of the radiation from the metal atoms.
• The low temperature renders to interference and the stability of the
flame and aspiration conditions.
• Interference by other elements is not easy to be eliminated.
 References
• Vogel’s Textbook of quantitative chemical analysis, FIFTH EDITION, By- G. H. Jeffery, J.
Bassett, J. Mendham, R C. Denney
• https://gpatindia.com/flame-photometry-principle-instrumentation-application-mcq-for-g
pat-gate-csir-net-jrf/
• Quantitative Chemical Analysis, 8th edition, D.C. Harris.
• Fundamentals of Analytical Chemistry, 9th edition, Douglas A. Skoog, D.M. West, F.J. Holler,
S. R. Crouch.
• http://
www.gju.edu.jo/sites/default/files/water_wastewater_unit_operation_spring_2015_part_
b.pdf.pdf
• Powell, F. J. N. The Determination of Calcium in Biological Fluids by Flame Photometry. J.
Clin. Pathol. 1953, 6 (4), 286–289. https://doi.org/10.1136/jcp.6.4.286.
• Myers, A. T.; Dyal, R. S.; Borland, J. W. The Flame Photometer in Soil and Plant Analysis. Soil
Sci. Soc. Am. J. 1948, 12 (C), 127–130.
https://doi.org/10.2136/sssaj1948.036159950012000C0027x.
Thank You