Flame photometer

PRESENTED BY- PANKAJ KUMAR

WATER LAB
1
 Introduction

Atomic spectroscopy is thought to be the oldest instrumental method for

the determination of elements. These techniques are introduced in the mid
of 19th Century during which Bunsen and Kirchhoff showed that the
radiation emitted from the flames depends on the characteristic element
present in the flame. The potential of atomic spectroscopy in both the
qualitative as well as quantitative analysis were then well established. The
developments in the instrumentation area led to the widespread
application of atomic spectroscopy. Atomic spectroscopy is an unavoidable
tool in the field of analytical chemistry. It is divided into three types which
are absorption, emission, and luminescence spectroscopy. The different
branches of atomic absorption spectroscopy are (1) Flame photometry or
flame atomic emission spectrometry in which the species is examined in the
form of atoms (2) Atomic absorption spectrophotometry, (AAS), (3)
Inductively coupled plasma-atomic emission spectrometry (ICP-AES).

2
Atomic Spectroscopy Methods

1. Atomic Emission Spectroscopy (Flame Photometry)

2. Atomic Absorption Spectrometry (AAS)

3
1. Atomic Emission Spectroscopy (Flame Photometry)

Flame photometry, a branch of atomic spectroscopy is used for inorganic

chemical analysis for determining the concentration of certain metal ions
such as sodium, potassium, lithium, calcium, Cesium, etc. The basis of
flame photometric working is that, the species of alkali metals (Group 1)
and alkaline earth metals (Group II) metals are dissociated due to the
thermal energy provided by the flame source. Due to this thermal
excitation, some of the atoms are excited to a higher energy level where they
are not stable. The absorbance of light due to the electrons excitation can be
measured by using the direct absorption techniques. The subsequent loss of
energy will result in the movement of excited atoms to the low energy
ground state with emission of some radiations, which can be visualized in
the visible region of the spectrum. The absorbance of light due to the
electrons excitation can be measured by using the direct absorption
techniques while the emitting radiation intensity is measured using the
emission techniques. The wavelength of emitted light is specific for specific
elements.

4
 Parts of a flame photometer
1. Source of flame:
A burner that provides flame and can be maintained in a
constant form and at a constant temperature.
2. Nebuliser and mixing chamber:
Helps to transport the homogeneous solution of the substance
into the flame at a steady rate.
3. Optical system (optical filter):
The optical system comprises three parts: convex mirror, lens and
filter. The convex mirror helps to transmit light emitted from the
atoms and focus the emissions to the lens. The convex lens help to
focus the light on a point called slit. The reflections from the mirror
pass through the slit and reach the filters. This will isolate the
wavelength to be measured from that of any other extraneous
emissions. Hence it acts as interference type color filters.
4. Photo detector:
Detect the emitted light and measure the intensity of radiation
emitted by the flame. That is, the emitted radiation is converted to an
electrical signal with the help of photo detector. The produced
electrical signals are directly proportional to the intensity of light. 5
A schematic representation of flame photometer is shown in figure 1 ,
6
 Mechanism of working:
The working of the flame photometer involves a series of steps which is
discussed in the following sections.
Nebulisation : The solution of the substance to be analyzed is first aspirated
into the burner, which is then dispersed into the flame as fine spray
particles.

A brief overview of the process:

1. The solvent is first evaporated leaving fine divided solid particles.

2. This solid particles move towards the flame, where the gaseous atoms
and ions are produced.
3. The ions absorb the energy from the flame and excited to high energy
levels.
4. When the atoms return to the ground state radiation of the
characteristic element is emitted.
5. The intensity of emitted light is related to the concentration of the
element.
7
Brief overview of the process

8
 Events occurring in the flame:

Flame photometry employs a variety of fuels mainly air, oxygen or nitrous

oxide (N2O) as oxidant. The temperature of the flame depends on fuel-
oxidant ratio.

The various processes in the flame are discussed below:

Desolvation : The metal particles in the flame are dehydrated by the flame
and hence the solvent is evaporated.

Vapourisation : The metal particles in the sample are dehydrated. This also
led to the evaporation of the solvent.

Atomization: Reduction of metal ions in the solvent to metal atoms by the

flame heat.

9
Excitation:
The electrostatic force of attraction between the electrons and
nucleus of the atom helps them to absorb a particular amount of energy.
The atoms then jump to the exited energy state.

Emission process:
Since the higher energy state is unstable the atoms jump back to the
stable low energy state with the emission of energy in the form of
radiation of characteristic wavelength, which is measured by the photo
detector. That is the intensity of emitted light is directly related to the
concentration of the sample.The comparison of emission intensities of
unknown samples to either that of standard solutions (plotting
calibration curve), or to those of an internal standard (standard addition
method), helps in the quantitative analysis of the analyte metal in the
sample solution.

10
The
flame emissions of the alkali and alkaline earth metals in terms of the emission
wavelength and the characteristic color produced by each element is shown in
Below Emitted wavelength
Name of the element Observed colour of the flame
range (nm)

Potassium (K) 766

Violet

Lithium (Li) 670

Red

Calcium (Ca) 622

Orange

Sodium (Na) 589

Yellow

Barium (Ba) 554

Lime green
11
Flame photometer
To determine the concentration of alkali and
alkaline earth metals in various samples

12
 Atomic Spectroscopy
To understand the relationship of these techniques to each other, It is
important to understand the atom itself and the atomic process
involved in each technique.

Ground state atom (stable or

normal orbital configuration) Excited state atom

3
Excited Excited
states states 3

Spectral resonance line

(The strongest line)
3
Ground Ground
state state Light energy 13
 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

14
 Atomic Emission Spectroscopy (AES)
(Flame Photometry)
Principle: Flame photometry is based upon those particles that
are electronically excited in the medium.

Flame : is the source of excitation energy. (low energy source).

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

15
 Flame Photometry
Events occur in FES
Solution of metal Ground state atoms
salt (NaCl) Na°
Solvent evaporation Emission and
return to G°

Solid aerosol of Excited atoms

metal salt (NaCl) Na*
Volatilization or decomposition Excitation

Gaseous metal Atomization Free atoms

salt (NaCl) Na°
16
 Flame Photometry
Instrument
components Monochromator

Flame Detector

Flame Structure Secondary

combustion zone
Interzonal region
Primary
combustion zone

Fuel- oxidant mixture

17
 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
Oxidant - Fuel Max. temp. (oC)
M -> M*
AIR- LPG 1200-1500

The flame is composed of : AIR- ACETYLENE 2400

a fuel gas and oxidant gas
N2O- ACETYLENE 3200

18
 Flame Photometry
Factors affecting intensity of flame emission :
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.

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 Ca.
19
 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

Types of burner system

Flame
1. Pre-mix or laminar flow burner Fuel in
Burner

Oxidant in
1. Homogenous flame
2. Suitable for AAS and AES as
the pathway could be increased
Sample

Aspirator Mixing
Drain
air baffles
20
 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 (short bath)

Oxidant
Fuel

Sample
1. Simple to manufacture
2. Allows a total representative sample
to reach the flame
3. Free from explosion hazards Oxidant

Fuel

21
 Flame Photometry
Monochromators Filter

Detectors Photomultipliers Tube

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.
22
 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 23
 Flame Photometry
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.
24
 Flame Photometry
Application of flame photometry in pharmaceutical analysis
1. Metals are major constituents of several pharmaceuticals such as dialysis
solutions, lithium carbonate tablets, antacids and multivitamin - mineral
tablets.
2. The elements Na, K, Li, Mg, Ca, Al and Zn are among the most common
elements subjected to pharmaceutical analysis using flame emission
technique.

3. 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.

Advantages and disadvantages

1. Flame emission is the simplest and least expensive technique.

2. The analysis may be carried out without prior separation as other

components such as dextrose, do not interfere. 25
Relationship Between Atomic Absorption and Flame
Emission Spectroscopy
Atomic Absorption Flame Emission
1. Measures the radiation 1. Measures the radiation
absorbed by the unexcited emitted by the excited atoms
atoms

2. Depends only on the 2. Depends only on the

number of unexcited atoms number of excited atoms

3. Absorption intensity is 3. Emission intensity is greatly

NOT affected by the affected by the temperature
temperature of the flame variation of the flame

26
Thanks

27