Flame Photometry Ankit

Flame Photometry
By-
Ankit Sharma
Assistant Professor (Pharmaceutical Analysis and Quality Assurance)
Laureate Institute of Pharmacy, Kathog, Jawalamukhi Distt. Kangra (H.P.)
Atomic Spectroscopy
• The process of excitation and decay to ground state is involved
in the two techniques of atomic spectroscopy.
• We measure the energy absorbed or emitted and use it for
quantification process
• Principle: Flame photometry is based upon those particles that
are electronically excited in the medium.
• Flame: is the source of excitation energy.

• Uses:
• Flame photometry is used mainly for the determination of
alkali metals and easily excited elements (Na, K, Li, Ca, etc.)
particularly in biological fluids and tissues.
Emitted
Element wavelength Flame color
Sodium 589 nm Yellow
Potassium 766 nm Violet
Barium 554 nm Lime green
Calcium 622 nm Orange
Lithium 670 nm Red
Flame Photometry:
Events occur in FES
Solution of metal Ground state atoms
salt M+X- (NaCl) Na°
Solvent evaporation Emission and
return to G° Emission
Solid aerosol of Excited atoms

metal salt M+X- Na*
Volatilization or Evaporation Thermal
Excitation
Gaseous metal Dissociation Free atoms (Gas)

salt Na°
Scheibe-Lomakin equation
Scheibe-Lomakin equation describes intensity of light
emitted with the help of following formula:
I = k × cn
Where:
I = Intensity of emitted light
c = Concentration of the element
k = Proportionality constant
At the linear part of the calibration curve n~1,
then I = k × c.
In other words, the intensity of emitted light is directly
related to the concentration of the sample.
Flame Photometry
Flame Photometry
Functions of Flame
1. To convert the constituents of liquid sample into the vapor state.
2. To decompose the constituents into atoms or simple molecules:
M+ + e- (from flame) -> M + hn
3. To electronically excite a fraction of the resulting atomic or molecular
species
M -> M*
Max. temp.
Oxidant - Fuel
(oC)
Air - propane 1725
Air - acetylene 2400
The flame is composed of :
Oxygen - acetylene 3100
a fuel gas and oxidant gas
Nitrous oxide-acetylene 3000
Air-hydrogen 2000
Oxygen-hydrogen 2700
Factors influence intensity
1- The concentration of the analyte in solution
2- The rate at which excited atoms are formed in
the flame.
3- The rate at which the sample is introduced into
the flame.
4- Temperature of the flame.
5- Composition of the flame.
6- The ratio of fuel to oxidant in the flame.
7- Solvent used to dissolve the sample.
Factors influence intensity
 Viscosity: Reduced Automisation - decrease intensity
 Presence of Acid: disturb Dissociation equilibrium
 Other metals
 The flame temperature is the most important factor.
 Increase in flame temperature causes an increase in

emission intensity. This is controlled by composition
of the flame.
 High temperature flames should not be used for

elements that ionized easily e.g. Na, K, Li or Ce.
However, high temperature flames are generally
favored for transition elements and alkaline earth
metals.
 Effect of the solvent used to dissolve the sample:
 If the solvent is water the process is slow and if it is
organic solvent the process is fast and emission
intensity is increased.
 It is therefore very important that calibration curves be

prepared using the same solvent.
 The stochiometric ratio of fuel to oxidant in the flame

must be used, in which both fuel to oxidant are totally
consumed.
Flame Photometry
The nebulizer-burner system
To convert the test sample into gaseous atoms
Nebulizer produce an aerosol of the test solution

Burner in which the mixing between fuel and oxidant
Flame Photometry
Types of burner system
1. Pre-mix or laminar flow burner
Advantages
Flame
1. Homogenous flame Fuel in
2. Suitable for AAS and AES as the Burner
pathway could be increased
Oxidant in
Disadvantages
Suffers from explosion hazards
Sample
Aspirator Mixing
Drain
air baffles
Flame Photometry
2. Total consumption burner
3 concentric tubes, the sample, fuel and
oxidant only mix at the tip of burner
Used mainly for FES
Oxidant
Fuel
Advantages
Sample
1. Simple to manufacture
2. Allows a total representative sample to
reach the flame
3. Free from explosion hazards Oxidant
Fuel
Disadvantages
1. Aspiration rate varies with different solvents
2. Suitable only for AES
Flame Photometry
Non Flame Atomizers
For example: Electrically heated graphite tube
Sample evaporation→ time and temp. controlled drying and ashing
Advantages
1. small samples are analysed
2. 1000-fold more sensitive than flame
3. Oven is adaptable to determination of solid samples
Disadvantages
1. Low accuracy 2. Low precision

2. More ionic interferences due to very high temp.
Flame Photometry
To select given emission line and isolate it

Monochromators from other lines- Interference filter and
grating
Detectors Barrier layer cell

Analytical technique
1. Choice of the wavelength: of max. sensitivity and min. spectral interferences
2. Sample preparation:
a. It is very important to obtain the sample in a form of solution, where the spectral
and chemical interferences are absent
b. Demineralized dist. Water and very pure reagents are to be used because of the
high sensitivity of the technique.
c. Because of the instability of the very dil. Solution, it is advisable to dilute the
soln just before use.
d. Several elements can be determined in blood, urine, cerebrospinal fluid and other
biological fluids by direct aspiration of the sample after dilution with water.
Flame Photometry
Chemical interferences: can often be overcome
by simple dilution with a suitable reagent solution e.g.
serum is diluted by EDTA solution for the
determination of calcium in order to prevent
interference from phosphate.
3. Standard curves
Absorbance,
Intensity
Deviations from
linearity may occur
A
Concentration, c
3. Qualitative analysis
Flame photometry are useful mostly for the detection of
elements in group I and II of the periodic table. The
presence of certain elements can be detected by the
use of a filter or monochromator.
4. Quantitative analysis
To perform quantitative analysis, the sample is

introduced into the flame and the intensity of
radiation is measured. The concentration of the
emitting substance is then calculated from a
calibration curve or using standard addition method.
Methods
• Standard Addition Method
• Internal standard method
• Simultaneous multi element analysis
Advantages:
 Flame emission is the simplest and least expensive technique.
 The analysis may be carried out without prior separation as

other components such as dextrose, do not interfere.
 It is quick, convenient, selective and sensitive analysis.
 It is both and qualitative and quantitative in nature.
 Even very low concentrations (parts per million/ppm to parts
per billion/ppb range) of metals in the sample can be
determined.
 This method compensates for any unexpected interfering
material present in the sample solution.
Disadvantages:
 The accurate concentration of the metal ion in the solution cannot be
measured.
 It cannot directly detect and determine the presence of inert gases.
 Though this technique measures the total metal content present in the
sample, it does not provide the information about the molecular structure
of the metal present in the sample.
 Only liquid samples may be used. Also sample preparation becomes
lengthy in some cases.
 Flame photometry cannot be used for the direct determination of each and
every metal atom. A number of metal atoms cannot be analysed by this
method. The elements such as carbon, hydrogen and halides cannot be
detected due to their non-radiating nature.
Applications:
 Metals are major constituents of several pharmaceuticals such as
dialysis solutions, lithium carbonate tablets, antacids and
multivitamin - mineral tablets.
 The elements Na, K, Li, Mg, Ca, Al and Zn are among the most
common elements subjected to pharmaceutical analysis using
flame emission technique.
 Sodium and potassium levels in biological fluids are difficult to

analyze by titrimetric or colorimetric techniques. Their analysis is
very important for control of infusion and dialysis solutions which
must be carefully monitored to maintain proper electrolyte balance.
Applications:
 The presence of some group II elements is critical for soil
health. We can determine the presence of various alkali and
alkaline earth metals in soil sample by conducting flame test and
then the soil can be supplied with specific fertiliser.
 Soft drinks, fruit juices and alcoholic beverages can also be

analysed by using flame photometry to determine the
concentrations of various metals and elements.
Interference
• Spectral interference: overlap, total signal, high temperature,
numerous spectrum.
• High salt concentration of salt may lead to continuous

background
• Ionisation interference:
• Cation-Anion interference: calcium +phosphate= stable
• Cation-cation interaction: sodium, potassium, decrease
• Oxide Formation: stable

Flame Photometry Ankit

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Flame Photometry

• Flame: is the source of excitation energy.

Solid aerosol of Excited atoms

Gaseous metal Dissociation Free atoms (Gas)

 Increase in flame temperature causes an increase in

 High temperature flames should not be used for

 It is therefore very important that calibration curves be

 The stochiometric ratio of fuel to oxidant in the flame

The nebulizer-burner system

To convert the test sample into gaseous atoms

Nebulizer produce an aerosol of the test solution

1. Pre-mix or laminar flow burner

1. Low accuracy 2. Low precision

To select given emission line and isolate it

Detectors Barrier layer cell

To perform quantitative analysis, the sample is

 The analysis may be carried out without prior separation as

 Sodium and potassium levels in biological fluids are difficult to

 Soft drinks, fruit juices and alcoholic beverages can also be

• High salt concentration of salt may lead to continuous

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