ENERGY LEvEL OF

ELECTRON E
2

E ∆E= E2-E1=
h

E
∆E = h 1

∆E =

hc/λ

7 (v=c/λ)
 BOLTzMANN
LAw
 T h e fraction of free atom that are thermally exited
is governed by a BoltzmannDistribution

 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
2 tempeature
 PRINCIPL
E
•

Excited state E1
• Emission
•

•
e
Ground state E0
•

3
 TABLE SHOwING
CHARECTERSTIC wAvELENGTH
AND COLOUR
ELEMENT WAVELENGHT OF
OR METAL COLOR EMISSION

SODIU 589
M YELLOW
POTTASSIU 76 VIOLE
M 6 T
CALCIU 66 ORANG
M 2 E

LITHIU 67 RE
M 0 D
LIME
BARIU 55 GREE
10
M 4 N
 INSTRUMENTATIO
N
 SAMPLE DELIEVERY
SYSTEM

 BURNER AND
FLAME OR SOURCE

 MONOCHROMATOR

 DETECTOR

5
 DIAGRAMMATIC
REPRESENTATION

6
 SAPMLE INTRODUCTION
TYPES AND
TECHNIQUES

7
 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 nebulization
Types of nebulizers:
 pneumatic nebulizers
 Electro-thermal vaporizers
 Ultrasound nebulizers
8
 PEBNEUMATIC
NEBULIZERS:

9
10
11
 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.

12
 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

13
 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 burner used:
 Mekker or Mecker burner
 Total consumption burner
 Premix burner
 Lundergarph’s burner
 Shielded burner
14

 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,
resulting in low excitation
energy.
21 best suited for alkali
 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.

 T h e advantage over other

 I t ’s disadvantage is the
22 is the entire consumption of
production
sample, of non uniform
 PREMIX
BURNER
 I n this burner the sample ,
fuel oxidant are thoroughly
mixed before aspiration
and reaching
to flame.

 The main advantage of it

is the uniformity of flame
produced.

 The main disadvantage is

23 the heavy loss of mix up
 LUNDENGARPH’S
 A smallBURNER
sample liquid droplets vaporized and move to
base of flame in the form of cloud

 Large droplets condensed at side and then drained off.

SHIELDED BURNER
• In this flame was shielded from
the ambient atmosphere by a
stream of inert gas.
• Shielding is done to get
better analytical
• sensitivity.
24
Following results are obtained
 NITROUS OXIDE-ACETYLENE
FLAME
• These flameswere superior to other
flames for effectively producing free
• atoms
E.g.-metals with very reflective oxides
 such as aluminum and titanium.
• The drawback of it is:
the high temperature reduces its
usefulness for the determination of
• alkali metals as they are easily ionized
Intense background emission, which
makes the measurement of metal
emission very difficult
19
 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

20
 LIST OF FUEL AND OXIDANT
FUEL
USED OXIDANT TEMPERATUR
Eº 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

21
 MIRROR
 The
S
radiation emitted by the
flame is generally towards all
the direction

 Hence a mirror is place behind

the flame to focus the radiation
towards the entrance slit of the
monochromator.

 A concave mirror is used as

22
it is front faced reflecting
type.
 MONOCHROMATO
RS
 The main of the monochromator is to convert
polychromatic light into the monochromatic one

 The 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

23
24
 DETECTOR
 PhotomultiplierS
tube

 Photo emissive
cell
 Photo voltaic
cell

25
 PHOTOMULTPLIER
 T h eTUBE
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

26
 PHOTOVOLTAIC
CELL
 I t has a thin metallic layer coated with silver or
gold act as electrode , also has metal base plate which
act as another electrode.

 Tw 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.

27
 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 wavelength Detection Element wavelength Detection
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

29
 OTHER
APPLICATIONS:
 T O 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.
30
 INTERFERNCES DURING
QUANTITAIVE ESTIMATION
 FOLLOWING TYPES OF
INTERFERENCES GENERALLY OCCUR
DURING QUANTITAIVE STIMATION
1.SPECTRAL INTERFERENCE

2.CHEMICAL
INTERFERENCES

3. IONIZATION
INTERFERENCES
31
 SPECTRAL
• The first type of interference arises when two elements exhibit
INTERFERENCES
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
38 spectral isolation system.
  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:

33
 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

34
 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.

35
 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.

36
 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
37
eliminated.
38