FLAM

PHOTOMETR
E
1
Y
 CONTENT
S:
• INTRODUCTION
• HISTORY
•ELECTRON ORBITAL AN D EN ERGY
STATE
• PRINCIPLE
• INTRUMENTATION
• SAMPLE INTRODUCTION
• BURNERS AND FLAME
• MIRRORS
• MONOCHROMATORS
• DETECTORS
• APPLICATIONS
2
• INTERFERENCES
• LIMITATIONS
 INTRODUCTI
 Flame ON or Flame
photometry Emission
Atomic spectroscopy.

 I t is type of emission spectroscopy where atomic emission

is measured using spectrophotometer.

 When metallic species is introduced into flame the metal

salt is burnt emitting certain colored wavelength and this
instrument is based on measurement of intensity of color.

 Each metal gives characteristic color and the intensity of

color depicts the amount or quantity of metal present.
3
 HISTORY
 T h e history of spectroscopy starts with the use of the
lens by Aristophanes about 423 B.C.; and the studies of
mirrors by Euclid (300 B.C.) and Hero (100 B.C.).

 I n the later 1800, scientists such as Kirchhoff, Bunsen,

Angstrom, Rowland, Michelson and Balmer studied the
composition of the sun based on their emissions at
different wavelengths.

 I n February of 23rd 1955 Murray Nelson A. filed a patent

for invention of Flame Photometry which was granted in
year 1958

4
 ORBITALS OF
o
ELECTRON
Electrons of atoms reside in concentric spheres known
energy “ shells ” in which they orbit the nucleus of an
atom .

o Each shell is assigned a principal quantum number,

n.

o The value n is integer , 1,2,3, etc.

o This number determines the relative energy of the orbital

and relates the distance from the shell to the nucleus the
lower the number, the lower the energy of the electron
and the closer it is to the nucleus .

o Electron can be further distinguished according to there

location in atomic orbital, specifi ed region in space that
depend on there energies
5
 ENERGY STATE OF
ELECTRON
 A l l the electrons are in there respective lowest
energy state referred as the ground state or the
state of lowest energy.

 A s a certain energy is provided to the atom, an

electron from its residence ground state shell to the
higher energy state shell called as excited state ..

 A s the excited state electrons are in shell with

greater ‘n’ ,hence have more energy and less
stability.
6
 ENERGY LEvEL OF
ELECTRON E
2

E ∆E= E2-
E1= h

E
∆E = h 1

∆E =

hc/λ

7 (v=c/λ)
 BOLTzMANN LAw
 The fraction of free atom that are thermally exited
is governed by a Boltzmann Distribution

 N*/N= ∆e- ∆EkT/

 N* =is the number of exited atom

 N = is the number of atom
 remaining in the ground state
 ∆E = is the difference in energies levels
 k = The Boltzmann
 constant T = the
8 tempeature
 PRINCIPL
E
• Liquid sample containing metal salt solution
introduced into a flame:
• Solvent is vaporized , leaving
particles of solid salt
Excited state E1
• Salt is vaporized into gaseous state Emission
• Gaseous molecule dissociate to give
neutral atoms
• The unstable excited atoms emit photons
while returning to lower energy state.
• The measurement of emitted photons
forms the basis of flame photometry using e
Ground state E0
• photomultiplier tube detectors.

9
 TABLE SHOwING
CHARECTERSTIC wAvELENGTH
AND COLOUR
ELEMENT WAVELENGHT OF
OR COLOR EMISSION
METAL
SODIU 589
M YELLOW
POTTASSI 76 VIOLE
UM 6 T
CALCIU 66 ORAN
M 2 GE

LITHIU 67 RE
M 0 D
LIME
BARIU 55 GREE
1
0
M 4 N
 INSTRUMENTATI
 SAMPLE ON
DELIEVERY
SYSTEM

 BURNER AND
FLAME OR SOURCE

 MONOCHROMATOR

 DETECTOR

11
 DIAGRAMMATIC
REPRESENTATION

12
 SAPMLE INTRODUCTION
TYPES AND
TECHNIQUES

13
 SAMPLE DELIVERY OR
NEBULIZATION
 This is the part of sample delivery system
in which liquid droplets of comparatively
larger size are broken or converted to smaller
size.

 The process of conversion of sample into

a mist of very fine droplets through the
aid of jets of compressed gas is called
 pneumatic
srez i luben
nebulization
▪ Electro-thermal
Types of nebulizers:
vaporizers
14 ▪ Ultrasoundsrezi lu
b
en
 PEBNEUMATIC
NEBULIZERS:

15
16
17
 ELECTRO-THERMAL
VAPORZERS
 Electro-thermal Vaporizers
(ETV)-
An electro thermal vaporizer
contains an evaporator in a
closed chamber through
which an inert gas carries the
vaporized sample into the
atomizer.

18
 ULTRASONIC
NEBULIZERS
 Ultrasonic Nebulizer-The
sample is pumped onto the
surface of a vibrating
piezoelectric crystal.
 The resulting mist is denser
and more homogeneous than
pneumatic nebulizers

19
 BURNERS
 Several kinds of burners are used to convert
the fine droplets of sample solution into
neutral atom ,which further due to the high
heat or temperature of flame are excited
hence emit radiation of characteristic
wavelength and color.
 Types of b u
n
re
r used:
 Mekker or Mecker burner
 Tot a l consumption burner
 Premix burner
 Lundergarph’sr
e
nru
b
 Shielded burner
20

 MECKER OR MEKKER
 T h i sBURNER
was the primitive
type of burner used in flame
photometry and was used
earlier.

 I t generally works with aid

of natural gas and oxygen
as fuel and oxidant.

 The temperature so
produced in the flame
was relatively low,
2 best suited for
1 resulting in low excitation
 TOTAL CONSUMPTION
 D uBURNER
e to the high
pressure of fuel and
oxidant the sample
solution is aspirated
through capillary and
burnt at the tip of
burner

 Hydrogen and oxygen

are generally employed as
fuel and oxidant.
 It’s disadvantage is the
2
2  Tproduction of non
h e advantage uniform
over
 PREMIX
 In BURNER
this burner the
sample , fuel oxidant
are thoroughly mixed
before aspiration and
reaching
to flame.

 T h e main
advantage of it is the
uniformity of flame
produced.
2
3
 LUNDENGARPH’S
 A BURNER
small sample liquid droplets vaporized
and move to base of flame in the form of
cloud

L a r g e droplets condensed at side and then

drained off.
• In this flame was
shielded SHIELDED
from the BURNER
ambient atmosphere by
• a stream of inert gas.
Shielding is done to
• get better analytical
2 sensitivity.
4
 NITROUS OXIDE-ACETYLENE
FLAME
• These flames were
superior to other flames for
• effectively producing free atoms
E.g.-metals with very reflective
 oxides such as aluminum and
• titanium.
The drawback ofit is:
the high temperature reduces
• its usefulness for the
determination of alkali metals
as they are easily ionized
Intense background emission,
25 which makes the measurement
of metal emission very
 STRUCTURE OF
• FLAME
As seen in the figure, the flame
may be divided into the
following regions or zones.
i) Preheating zones
ii) Primary reaction zone or
inner zone
iii) Internal zone
iv) Secondary reaction
zone

26
 LIST OF FUEL AND OXIDANT
FUEL
USED OXIDANT TEMPERATU
REº C

TOWN GAS AIR 1700

PROPANE AIR 1900

BUTANE AIR 1925

ACETYLENE AIR 2200

TOWN GAS OXYGEN 2700

PROPANE OXYGEN 2800

BUTANE OXYGEN 2900

ACETYLENE NITROUS OXIDE 2955

27
 MIRROR
 The
S
radiation emitted by
the flame is generally
towards all the direction

 H e n c e a mirror is place
behind the flame to focus
the radiation towards the
entrance slit of the
monochromator.

 A concave mirror is
28
used as it is front
 MONOCHROMATO
RS
 T h e main of the monochromator is to
convert polychromatic light into the
monochromatic one

 T h e two types of monochromator

generally used are as under:
1. Prism : Quartz material is used for making prism, as quartz
is transparent over entire region
2. Grating : it employs a grating which is essentially a series
of parallel straight lines cut into a plane surface

29
30
 DETECTORS

 Photomulti plier utbe

 P h o t o emissive cell

 P h o t o voltaic cel

3
1
 PHOTOMULTPLIER
 T h TUBE
e intensity of the light is fairly low, so
a photomultiplier tube (PMT) is used to boost
the signal intensity
 A detector (a special type of transducer)
is used to generate voltage from the
impingement of electrons generated by
the photomultiplier tube

32
 PHOTOVOLTAIC
 It has a CELL
thin metallic layer coated with silver or
gold act as electrode , also has metal base plate which
act as another electrode.

 T w o layers are separated by semiconductor layer of

selenium, when light radiation falls on selenium
layer.

 This creates potential diff. between the two

electrode and cause flow of current.

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 APPLICATION
SANALYSIS:
 QUALITATIVE

Generally alkali and alkaline earth metal can

be estimated by flame photometry
As characteristic wavelength is emitted by
the element hence detector recognizes
that wavelength and atom is detected.
Manual method of detection is via flame
characteristic color e.g.
Na produces yellow color.
• QUANTITATIVE ANALYSIS :
many alkali and alkaline metals amount can
be detected by the flame photometry by:
 CHARACHETRISTIC
WAVELENGTHOF
EMISSION AND DETECTION
LIMIT
Element waveleng Detecti Element waveleng Detecti
th on th on
limit limit
Al 396 0.5 Pb 406 14

Ba 455 3 Li 461 0.067

Ca 423 0.07 Mg 285 1

Cu 325 0.6 Ni 355 1.6

Fe 372 2.5 Hg 254 2.5

35
 OTHER
 TO APPLICATIONS:
ESTIMATE Na , K, Ca, Li IN SERUM,
BODY FLUID, CSF AND URINE.
N a IN EXTRACELLULAR FLUID AND K
INTERACELLULAR FLUID.
 LITHIUM ESTIMATION IN PSYCHIATRIC
THERAPY.
 I N SOIL ANALYSIS.
 I N INDUSTRIAL WASTE ,
GLASS,CEMENT AND PETROLUEM
PRODUCTS.
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 INTERFERNCES DURING
QUANTITAIVE ESTIMATION
 FOLLOWING TYPES OF
INTERFERENCES GENERALLY OCCUR
DURING QUANTITAIVE STIMATION
1.SPECTRAL INTERFERENCE

2.CHEMICAL
INTERFERENCES

3.IONIZATION
INTERFERENCES
37
 SPECTRAL
•
INTERFERENCES
The first type of interference arises when two elements exhibit
spectra, which partially overlap, and both emit radiation at some
particular wavelength.
eg. - the Fe line at 324.73 nm overlaps
with the Cu line at 324.75 nm.
SOLUTION:It can overcome either by taking measurements at
an alternative wavelength which has no overlap, if available, or
by removing the interfering element by extraction.
• The second type of spectral interference deals with spectral lines of
two or more elements which are close but their spectra do not
overlap
• SOLUTION:It can be reduced by increasing the resolution of the
3 spectral isolation system.
8
  A third type of spectral interference occurs due to the
presence of continuous background which arises due to
high concentration of salts in the sample, especially of
alkali and alkaline earth metals
SOLUTION:This type of interference can be corrected
by using suitable scanning technique.

CHEMICAL INTERFERENCE
The chemical interferences arise out of the
reaction between different interferens and
the analyte . These are of different types:

39
 CATION- CATION
•INTERFERENCE
Due to mutual interferences of cations
• These interferences are neither spectral nor ionic
in nature
• Eg. aluminum interferes with calcium and
magnesium.

Interference due to oxide formation:

It arises due to the formation of stable metal oxide
if oxygen is present in the flame

40
 CATION- ANION
•INTERFERENCES
The presence of certain anions, such as oxalate,
phosphate, sulphate , in a solution may affect
the intensity of radiation emitted by an element,
resulting in serious analytical error.
• For example, calcium in the presence of phosphate
ion forms a stable substance, as Ca3(PO4) which
2

does not decompose easily, resulting in the

production of lesser atoms.

41
 IONIZATION
•INTERFERENCES
high temperature flame may cause ionzation of some of the
metal atoms, e.g. sodium

Na Na+ + e_

The Na+ ion possesses an emission spectrum of its own

with frequencies, which are different from those of atomic
spectrum of the Na atom.

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 LIMITATION
• S is not high enough to excite
The temperature
transition metals, therefore the method is selective
towards detection of alkali and alkaline earth
metals.
• The relatively low energy available from the flame
leads to relatively low intensity of the radiation
from the metal atoms.
• The low temperature renders to interference and
the stability of the flame and aspiration conditions.
• Interference by other elements is not easy to be
43
eliminated.
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