Flame Photometry

Flame Photometer technology is an inherently simple and reliable methodology which has been
applied to a range of products encompassing many fields of applications.
The aim of this section is to introduce the reader to the simple technique of low temperature
flame photometry and to discuss in some detail some of the many and varied applications in
which the technique can be utilized.
Introduction:
The estimation of the alkali metals by flame photometry is by far its most important application
in routine chemical analysis. For this widespread requirement, low temperature flame
photometry provides the most reliable and convenient procedure available.
This technique has considerable appeal in the clinical chemistry field as it provides a rapid and
reliable means of estimating sodium, potassium and lithium in body fluids.
However the estimation of the alkali and alkaline earth metals is commonly required in a sample
matrix which does not lend itself to simple and direct analysis involving only a dilution step, e.g.
sodium in fuel oil. The information that follows therefore aims to guide the user towards making
successful determinations in a wide variety of sample media by giving in detail a large selection
of procedures using flame photometry from which other methodologies may be appended with
relative ease.
Principles of Flame Photometry:
The basis of low temperature flame photometry is the same as that of the simple quantitative
analytical flame test. This exploits the fact that compounds of the alkali and alkaline earth metals
are thermally dissociated into atoms at the temperature of a Bunsen burner flame and that some
of these atoms produced are further excited to a higher energy level. When these 'excited' atoms
return to the ground state, they emit radiation, which for the elements of thesettwo groups lies
mainly in the visible region of the electromagnetic spectrum.
The wavelength of the light emitted from the flame is characteristic of the particular element.

The intensity of this light is, in most cases, proportional to the absolute quantity of the species
present in the flame at any moment, i.e. the number of atoms returning to the ground state is
proportional to the number of atoms excited, i.e. the concentration of the sample. N.B. This
relationship applies only at low concentrations.
The emitted radiation is isolated by an optical filter and then converted to an electrical signal by
the photo detector

A simple flame photometer consists of the following basic components:

1. A flame that can be maintained in a constant form and at a constant temperature:- "The
Burner"
2. A means of transporting an homogeneous solution into the flame at a steady rate:-
"Nebuliser and mixing chamber"
3. A means of isolating light of the wavelength to be measured from that of extraneous
emissions:- "Simple colour filters" (interference type)
4. A means of measuring the intensity of radiation emitted by the flame:- "Photo Detector
Burner:
This is a part which produces excited atoms. Here the sample solution is sprayed into fuel and
oxidant combination. A homogenous flame of stable intensity is produced.
There are different types of burners like Total consumption burner, Laminar flow and Mecker
burner.
Fuel and oxidants:
Fuel and oxidant are required to produce the flame such that the sample converts to neutral atoms
and get excited by heat energy.
The temperature of flame should be stable and also ideal. If the temperature is high,
the elements in sample convert into ions instead of neutral atoms. If it is too low, atoms may not
go to excited state. So a combination of fuel and oxidants is used such that there is desired
temperature.
The following combination of fuel and oxidants are commonly used.

Fuel Oxidant Temperature of Flame

Propane + Air 2100 Degree C

Propane + Oxygen 2800 Degree C

Hydrogen + Air 1900 Degree C

Hydrogen + Oxygen 2800 Degree C

Acetylene + Air 2200 Degree C

Acetylene + Oxygen 3000 Degree C

Monochromators:
Filters and monochromators are needed to isolate the light of specific wavelength from
remaining light of the flame. For this simple filters are sufficient as we study only few elements
like Ca, Na, K and Li. So a filter wheel with filter for each element is taken. When a particular
element is analyzed, the particular filter is used so that it filters all other wavelengths.
Detector:
 Flame photometric detector is similar to that used in spectrophotometry. The emitted radiation is
in the visible region, i.e., 400nm to 700nm. Further, the radiation is specific for each element, so
simple detectors are sufficient for the purpose of photovoltaic cells, phototubes, etc.
Recorders and display:
These are he devises to read out the recording from detectors.
Flame photometer uses/ Applications:
1. For qualitative analysis of samples by comparison of spectral emission wavelengths with that
of standards.
2. For quantitative analysis to determine the concentration of group IA and IIA elements. For
example,
a) Concentration of calcium in hard water.
b) Concentration of Sodium, potassium in Urine
c) Concentration of calcium and other elements in bio-glass and ceramic materials.

Flame photometry limitations:

Unlike other spectroscopy methods, flame photometry finds little use in research and analysis.
This is due to
1. Limited number of elements that can be analyzed.
2. The sample requires to be introduced as a solution into fine droplets. Many metallic salts,
soil, plant and other compounds are insoluble in common solvents. Hence, they can’t be
analyzed by this method.
3. Since the sample is volatilized, if a small amount of sample is present, it is tough to
analyze by this method. As some of it gets wasted by vaporization.
4. Further, during solubilization with solvents, other impurities might mix up with the
sample and may lead to errors in the spectra observed.
lame photometry more properly called flame atomic emission spectrometry is a relatively old
instrumental analysis method. Its origins date back to Bunsen’s flame-color tests for the qualitative
identification of select metallic elements. Probably the most common example of the atomic emission
effect is fireworks. As an analytical method, atomic emission is a fast, simple, and sensitive method for
the determination of trace metal ions in solution. Flame photometry is good only for elements that are
easily excited and do not require very high temperatures (Na, K, Li, Ca are the most widely determined
atoms by this technique).

Figure 1: Energy level diagram for atomic sodium (Only few lines are shown)

Detection limits can be quite low. “Good” elements typically have detection limits between about 1
ng/ml and 1 µg/ml.

The method is suitable for many metallic elements, especially for those metals that are easily excited to
higher energy levels at the relatively cool temperatures of some flames.

Metalloids and nonmetals generally do not produce isolated neutral atoms in a flame, but mostly as
polyatomic radicals and ions. Therefore, nonmetallic elements are not suitable for determination by
flame emission spectroscopy, except for a very few and under very specialized conditions.

Flame photometry is a highly empirical, rather than an absolute, method of analysis such as gravimetric
tests. That is, you must calibrate the method carefully and frequently. Many different experimental
variables affect the intensity of light emitted from the flame and that finding its way to the detector.
Therefore, careful and frequent calibration is required for good results. The instrument is called a
“single-channel” photometer because it can determine only one element at a time and has a single
direct-reading output.

Instrumentation
 A flame photometer instrument is extremely simple where the sample in solution is aspirated through
an aspirator or nebulizer into the flame which is usually a propane / air fuel or, even, a purified natural
gas/air mixture. The sample matrix evaporates followed by atomization of the sample. Atoms present
in the high temperature zone of the flame are excited to higher energy levels by absorbing energy from
the flame. As excited atoms return to the ground state they emit radiation in definite wavelength
depending on the energy level from which each atom drop. This gives rise to a line spectrum. However,
in flame photometry a pre-selected filter (depending on the atom in question) is used and it is the
intensity of the emission line that is practically measured and is related to the original concentration of
the sample in solution. The detector is usually a phototube or a photomultiphier tube depending on the
quality of the instrument. A schematic diagram of a simple flame photometer is shown is shown in
Figure 2.