INTRODUCTION

• Flame emission spectroscopy is so named

because of the use of a flame to provide the
energy of excitation to atoms introduced into
the flame.

9/22/2017 KMCH College of Pharmacy 2

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)
3
– The colour's intensity tells us how much of the element
• The basic principle upon which Atomic Spectroscopy
works is based on the fact that "Matter absorbs
light at the same wavelength at which it emits
light".
• Atoms of elements  subjected to hot flame 
specific quantum of thermal energy absorbed by
orbital electrons  become unstable at high energy
level  release energy as photons of particular
wavelength  change back to ground state.
• When a metal salt solution is burned, the metal
provides a colored flame and each metal ion gives a
different colored flame.
• Flame tests, therefore, can be used to test for the
4
absence or presence of a metal ion
BASIC CONCEPT:
• Liquid sample contaning metal salt
solution is introduced into a
flame,
• Solvent is first vaporized, leaving
particles of solid salt which is then
vaporised into gaseous state
• Gaseous molecule dissociate to
give neutral atoms which can be
excited (made unstable) by thermal
energy of flame
• The unstable excited atoms emit
photons while returning to lower
energy state
• The measurement of emitted
photons forms the basis of flame
5
photometry.
 PRINCIPLE

9/22/2017 KMCH College of Pharmacy 6

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.

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.

9/22/2017 KMCH College of Pharmacy 7

 INSTRUMENTATIO
N
The basic components for flame photometer are as follows

 Burner(source)

 Atomizer

 Monochromators

 Detector

 Read out device

9/22/2017 KMCH College of Pharmacy 8
INSTRUMENTATION:

THE FLAME PHOTOMETER

Schematic Representation of the Flame Photometer

Major Components:
1. Sample Delivery
System
2. Source
3. Monochromato
r
4. Detector
Sample Delivery System:
There are three components for introducing
liquid sample:
• Nebulizer – it breaks up the liquid into small
droplets.
– Nebulization the is conversion of a sample to a mist of
finely divided droplets using a jet of compressed gas.
– The flow carries the sample into the atomization
region.
– Pneumatic Nebulizers: (most common)
• Aerosol modifier – it removes large droplets from the
stream and allow only smaller droplets than a certain
size to pass
• Flame or Atomizer – it converts the analyte into free 11
Source:
• A Burner used to spray the sample solution into
fine droplets.
• Several burners and fuel+oxidant
combinations have been used to produce
analytical flame including: Premixed, Mecker,
Total consumption, Lundergarh, Shielded burner,
and Nitrous oxide- acetylene flames
• Pre-mixed Burner:
– widely used because uniformity in flame
intensity
– In this energy type of burner , aspirated sample , fuel
and oxidant are thoroughly mixed before reaching the
burner opening. 12
 BURNERS
The FLAME used in the flame photometer should possess following
functions:

 The flame should have ability to evaporate the liquid droplets from
the sample solution in the formation of solid residue

 The flame should decompose the compounds in the solid residue

resulting in the formation of atoms.

 The flame must have the capacity to excite the atoms formed and
cause them to emit radiant energy.

9/22/2017 KMCH College of Pharmacy 13

 TYPES OF
BURNERS
 Mecker Burner
 Total Consumption Burner
 Laminar Flow (premix) Burner
 Lundergraph Burner.
 Shielded Burner
 Nitrous Oxide –Acytelene Flame.

9/22/2017 KMCH College of Pharmacy 14

 MECKER BURNER

 This burner employed natural gas and

oxygen.
 Produces relatively low temp.
and
 low
Thisexcitation energies.
are best used ALKALI
for metals only.
 Nowadays it is not used.

9/22/2017 KMCH College of Pharmacy

 Total consumption burner

 In this burner the fuel

oxidant are hydrogen and
oxygen gas respectively. and
 In this the sample solution is
aspirated through a capillary by
the high pressure. fuel and
oxidant are burnt at the tip of
the burner.
 The name “total consumption
burner” is used because all the
sample that enters the capillary
will enter the flame regardless
of the droplet size.

9/22/2017 KMCH College of Pharmacy

Advantage
 Design is simple and entire sample is consumed.

Disadvantage
 Uniform and homogeneous flame is not obtained. Since
droplet size vary, leading to fluctuations in the flame
intensity.

13

9/22/2017 KMCH College of Pharmacy

 LAMINAR FLOW BURNER

9/22/2017 KMCH College of Pharmacy

 LAMINAR FLOW (PREMIX) BURNER.

 In this type of the burner, aspirated sample, fuel and oxidant are
thoroughly mixed before reaching the burner opening and then
entering the flame.
 Important feature of this is that only a small portion (about 5%) of the
sample reaches the flame in the form of small droplets and is easily
decompose.
ADVANTAGES:
 Premix burner is non-turbulent ,noiseless and stable.
 Easy decomposition which leads to high atomization.
 Can handle solution up to several % without clogging.
DEMERITS
 When it contains 2 solvents, the more vol. will evaporate and lesser
will remain undissociated.
9/22/2017 KMCH College of Pharmacy 19
 MONOCHROMATORS AND FILTERS
 In simple flame photometers, the monochromators is the prism.
 QUARTZ is the material most commonly used for making prisms
because quartz is transparent over entire region .
 FILTERS: the filter is made up of such material which
is
transparent over a narrow spectral range.
 When a filter is kept between the flame detector, the radiation of
the desired wavelength from the flame will be entering the
detector and be measured. The remaining undesired wavelength
will be absorbed by the filter and not measured.
 In flame photometry, the wavelength as well as intensity of
radiation emitted by the element has to be monitored. Hence a
filter or monochromatoreKMCH
9/22/2017 is College
used. of Pharmacy 20
 DETECTORS

 Photovoltic cell

 Phototubes

 photomultiplier tubes.

9/22/2017 KMCH College of Pharmacy 21

 APPLICATION
S
 FES has found wide application in agricultural and
environmental analysis, industrial analyses of ferrous metals and
alloys as well as glasses and ceramic materials, and clinical
analyses of body fluids.

 FES can be easily automated to handle a large number of

samples. Array detectors interfaced to a microcomputer system
permit simultaneous analyses of several elements in a single
sample

 They are also used to determine the metals present in Chemicals,

Soil, Cements, Plant materials, Water, Air pollutants and
Oceanography

9/22/2017 KMCH College of Pharmacy 22

 INTERFERENCES

 Matrix interference

 Chemical interference

 Ionization interference

 Spectral Interferences

9/22/2017 KMCH College of Pharmacy 23

 Matrix interference

 When a sample is more viscous or has different surface tension

than the standard it can result in differences in sample uptake rate
due to changes in nebulization efficiency.

 Such interferences are minimized by matching as closely

as
possible the matrix composition of standard and sample.

9/22/2017 KMCH College of Pharmacy 24

 Chemical interference
 If a sample contains a species which forms a thermally stable
compound with the analyte that is not completely decomposed by
the energy available in the flame then chemical interference
exists.
 Refractory elements (Ti, W, Zr, Mo and Al) may combine with
oxygen to form thermally stable oxides.
 Analysis of such elements can be carried out at higher flame
temperatures using nitrous oxide – acetylene flame instead of air-
acetylene to provide higher dissociation energy.
 Alternately an excess of another element or compound can be
added e.g. Ca in presence of phosphate produces stable calcium
phosphate which reduces absorption due to Ca ion.
 If an excess of lanthanum is added it forms a thermally stable
compound with phosphate and calcium absorption is not affected.
9/22/2017 KMCH College of Pharmacy 25
 Ionization interference
 Ionization interference is more common in hot flames. The
dissociation process does not stop at formation of ground state
atoms.
 Excess energy of the flame can lead to excitation of ground state
atoms to ionic state by loss of electrons thereby resulting in
depletion of ground state atoms.
 In cooler flames such interference is encountered with easily
ionized elements such as alkali metals and alkaline earths.
 Ionisation interference is eliminated by adding an excess of an
element which is easily ionized thereby creating a large number
of free electrons in the flame and suppressing ionization of the
analyte.
 Salts of such elements as K, Rb and Cs are commonly used as
ionization suppressants.
9/22/2017 KMCH College of Pharmacy 26
APPLICATIONS:

• To estimate sodium, potassium, calcium, lithium etc.

level in sample of serum, urine, CSF and other body
fluids.
• Flame photometry is useful for the determination of
alkali and alkaline earth metals.
• Used in determination of lead in petrol.
• Used in the study of equilibrium constants involving
in ion exchange resins.
• Used in determination of calcium and magnesium in
cement.

27