FLAME PHOTOMETRY

Fire Light Measurement

Dr.J.Radhika - 04.11.16
Introduction
• A photoelectric flame photometer is a device used in
inorganic chemical analysis to determine the
concentration of certain metal ions such as sodium,
potassium, calcium and lithium.

• Group 1 and Group 2 metals are sensitive to Flame

Photometry due to their low excitation energies.

• The flame photometry is a method which employs

flame for the analysis of the substance. The sample
gets excited and the absorption or emission of
specific wavelengths by excited atoms is studied.
 Principle
When a liquid sample containing the metallic salt is introduced
into the flame the following events occur:

• The solvent is vaporized. The particles of the solid salt

are left in the flame.
• The salt is vaporized and converted into its gaseous
state.
• The gaseous molecules are dissociated to give out
neutral atoms.
• The neutral atoms are excited by the thermal energy of
the flame.
• The excited atoms are unstable and emits photons and
return to the lower energy state.
• The measurement of the emitted photons form the basis
of flame photometry.
E2 and E1 represent the higher and lower energy
levels the radiation emitted

E2 –E1 = hν
Where h is planck’s constant and ν the frequency
of the radiation
ν = c/λ

E2 –E1= hc /λ or λ = hc / E2 –E1
 Instrumentation

The basic components of a flame photometer are

• Nebulizers or atomizers

• The Flame/Burners

• Monochromators

• Photocells
 Block Diagram

Nebuliser Flame Filter Recorder

Compressed air

Detector

Sample
Process Involved in Flame Photometry

Vaporisation in flame Molecules

Aspiration
+- -+ - N Thermal dissociation in flame
+
Aerosol
-+--+- flame
+- +
Ions in
Solution

Ground state atoms

Heat energy absorbed

Excited state atoms
 Nebulizers or Atomizers
The analysis uses liquid samples which must be converted into
a fine spray before being introduced into the flame.

• The process of breaking the large droplets of the liquid

sample into a fine spray in called nebulization.
• A forced stream of air passes over the capillary tube
dipping in the test solution which leads to a drop in
pressure in the capillary tube.
• This leads to the suction of the sample through the
capillary.
• The flow of air breaks the solution into a mist of fine
droplets.
• To eliminate the large droplets a cloud chamber is placed
between the flame and the nebulizer where they condense
and are removed from the drain.
Nebulizers or Atomizers

Fuel
Cloud
Chamber

Fuel
Cloud
Chamber

Sample Drain
Compressed Impact
air Bead
Sample
Compressed Drain

Simple Nebuliser air

Improved Nebuliser
Nebulizers or Atomizers

• Large droplets are removed through the

drain the there is a loss of about 90% of the
introduced sample.
• To solve this problem an improvement in the
basic design has been carried out by
introducing an impact bead.
• The large droplets collide with the impact
bead and are broken into smaller droplets
which reduces the droplet size further and
the sample loss.
Flame
Various gas mixtures are being used to produce flame

Fuels Gas(oxidant) Temperatureº C Elements

Acetylene Air 2400 Ca,Mg,Fe

Acetylene Nitrous oxide 2800 Ti, V

Acetylene Oxygen 3140 Mg

Propane Air 2000 Ca

Natural Gas Air 1500 Na, K

 Flame
The flame must possess the following functions:

• It should evaporate the liquid present in

the sample.
• A solid residue must be left behind
• The flame should decompose the
compounds resulting in the formation of
atoms.
• It should excite the atoms formed
• It should emit radiant energy.
Flame

The temperature of the flame is responsible for

the events in the flame. The temperature is
regulated by the

• Type of fuel and oxidant ratio

• Type of solvent used

• Amount of solvent entering the flame

Burners

Mecker Burner

• Use Natural gas and oxygen

• Produce low temperatures
• Used for the study of alkali metals
• Flame not homogenous and no proper
results were obtained
 Burners- Total Consumption Burners

• Use hydrogen and

oxygen as fuel and
oxidant respectively.
• The liquid sample is
drawn into the flame
• All the sample that
enters the flame gets
atomized and excited.
• The flame produced is Fuel

noisy and turbulent. Oxidant

Sample Inlet
 Burners- Pre Mix or Laminar Flow Burners

 The sample, fuel and

oxidant are Flame
thoroughly mixed Fuel
before reaching the
flame. Burner

 The flame is
nonturbulent, Oxidant

noiseless and stable.

 Easy decomposition
and efficient
atomization
 Smaller number of
atoms reach the Sample
 Mirrors Slits

• The radiation from the • Entrance and exit slits

flame is emitted in all are present
directions • Entrance slit allows the
• To increase the radiations from the
radiations reaching the flame to enter the
detector a concave monochromator.
mirror is used. • Exit slit is between the
• It is set behind the monochromator and the
burner to reflect the detector.
radiations. • It allows only the
selected wavelength
• The focal point lies at
range from the radiation
the entrance of the
traveling from the
monochromator.
monochromator to the
detector.
 Wave Length Selectors - Monochromators
Monochromator resolves the polychromatic radiation into its
individual wavelength and isolates these wavelengths into
very narrow bands.

Prism
Focusing Sample
lens holder
Entrance
slit

Collimating
lens

Source

Exit slit
Components of a Monochromator
• Entrance Slit- allows polychromatic light from the source
• Collimating Lens- collimates (converts into parallel
beam) the polychromatic light on a dispersion device.

• Wavelength selector- Prism or grating

• Focusing Lens
• Exit slit
The entire assembly is mounted in a light tight box so
that it does not absorb light from the environment.
The band width of the radiation emerging from the
monochromator depends mostly upon the dispersing
element used and the slit widths.
Prism

• A prism disperses polychromatic light

from the source into its constituent
wavelength.
• It diffracts different wavelengths to
varying extent
• Shorter wavelengths are diffracted the
most.
 Prism
The degree of dispersion by the prism depends on

• The apical angle of the prism – usually 60°

• The materials with which it is made of
Visible region – simple glass prisms
UV region – fused silica or quartz
IR region – ionic crystalline materials-
NaCl, KBr, CsBr, and the mixed
crystalline material- KRS-5.
 Grating Gratings are used in UV, Visible and IR spectrophotometers

Gratings possess a highly reflective

aluminium surface with large number of 400-800
300
grooves which are parallel and equally
spaced.
The grooves are called as lines. 500-1000

A grating may have 600-2000 lines per

mm on the surface. 600-1200

It resolves the light into its component i

wavelength.
Monochromators usually consists of both
prism and grating.
The advantage of the grating is that its
resolving power is much better than that
of the prism.
 Photovoltaic or barrier layer cells

Cathode (-)

silver
selenium

Steel back plate

Anode (+)
 Photovoltaic or barrier layer cells

• These cells employ semiconductor materials.

• Semiconductors are crystalline and the bonding

electrons between the crystals are knocked of by the
incident radiation.

• Cadmium sulphide, silicon and selenium are used as

semiconductors in photocells.

• Photocells have a long life and are inexpensive and

reliable. They are widely used in colorimeters.
Photovoltaic or barrier layer cells
• Selenium based photocells are most common.

• A photocell consists of a thin coating of selenium over a

thin transparent silver film on a steel base.
• The electrons move from the selenium layer to the silver
film and not in the reverse direction.
• The silver film acts as the collecting electrode for the
electrons liberated from the selenium by the incident
radiation.
• The steel plate acts as the anode.
• The electrons are attracted towards the anode.
• The current flowing between the electrodes is measured
using a microammeter.
 Applications

• Flame photometry is used in various

industries like chemicals , soils,
agriculture, pharmaceuticals, glass and
ceramics, in plant materials and water,
oceanography, and in biological and
microbiological laboratories.
 Applications

It is used in determination of potassium, sodium,

magnesium and calcium in biological fluids like serum,
plasma, urine etc,
Analysis of industrial water, natural water for determining
elements responsible for hard water (magnesium, barium,
calcium etc.)
Soil samples are routinely analysed mainly for sodium,
potassium, calcium and magnesium
Some important elements which are commonly
determined by this method are aluminium, barium, calcium,
chromium, copper, iron, lead , magnesium, potassium, zinc,
manganese, and strontium.
 Applications

Glass industry- used in determining of sodium, potassium,

boron, lithium etc.
Cement industry - used in estimation of sodium, potassium,
calcium, magnesium, manganese, as well as lithium.
Extensively used in estimation of alkali-alkaline earth metals
as well as other metals present in metallurgical products,
catalysts, alloys etc.
In determination of certain metals like lead, manganese, in
petroleum products like gasoline, lubricating oils and organic
solvents.
Analysis of ash is routinely carried out in various industries
for estimating alkali and alkaline earth metals as their oxides.