FLAME EMISSION

SPECTROSCOPY
 In Flame Emission

 Atoms in gaseous state in the flame absorb thermal

energy from the flame itself
 some of the atoms get excited & as they return back to the
ground state they emit radiation having energy equal to that
absorbed.
 The emission is proportional to the number of excited
atoms
 which is proportional to the total number of atoms in the flame
i.e. the sample concentration
 Flame Spectra
 The spectra of gaseous, atomic particles consist of well
defined narrow discrete lines arising from electronic
transition of outermost electrons
 Since there is no bonds, atoms undergo electronic
transition only, no vibrational or rotational transitions.
 The energy to which the atoms are subjected must be
less than the ionization potential
 The resonance wave - length (at which the most intense
absorption and emission occur) is : 671 nm for lithium,
589 nm for sodium and 767 nm for potassium.
Flame Spectra
 The number of atoms of an element excited by the
flame depends on
 Flame temperature
 The energy difference between the excited and ground
states.
 Accordingly : The number of excited atoms in the
flame is considerably small, even in the case of
alkaline metals which are easily excited.
 Sodium at 2500 k0, 0.017% of the atoms are excited.
Flame Spectra
 Other metals: the number of excited atoms is
extremely small
 e.g. in case of zinc only 10-9 are excited

 Any increase of the flame temperature is

accompanied by great increase in the number of
excited atoms
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Limitation of Flame Emission Photometry

 The number of excited atoms in flame is very small. It

is the alkali and alkaline earth metals that can be
practically determined.
 It needs perfect control of flame temperature.
 Interference by other elements is not easy to be
eliminated.
 In Heavy and transition metals , the number of
absorption and emission lines is enormous and the
spectra are complex.
INSTRUMENT FOR FLAME EMISSION

1-Flame atomizer.
2- Monochromator
3- Detector.
4- Readout meter.
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Flame Atomizer
1. Atomization of the sample.
2. Source : thermal energy to excite the atoms.
 The atomizer is composed of :
Nebulizer, and
 burner

 Nebulizer
 is a device by which sample solution is divided into very fine
droplets which are aspirated into fine spray or aerosol.
Flame Atomizer
 As the oxidant flows it withdraws the sample from the
capillary in very fine droplets
 Then mixed in the premixing chamber with the fuel
gas .
 The fuel-oxidant-sample aerosol mixture passes to the
burner producing the necessary heat for atomization
and excitation
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 In the burner

The combustion of fuel occurs producing the necessary heat for atomization
and excitation but not ionization .

The temperature of the flame produced depends on fuel-oxidant ratio and kind.
 In case of potassium, sodium, lithium and calcium, they are atomized and
excited below 20000 k above 25000 k ionization occurs.

The flame temperature must be :

Regular : an increase by 100 c is accompanied by increase of 4% in the excited atoms.

It must be sufficient to cause atomization only and not ionization.

2- Monochromator

Either grating or interference filters which allow the resonance wavelength

to pass to the detector
.
Determination of sodium/potassium by using
flame photometer

 Flame photometry is based on the fact that

compounds of alkali and alkaline earth metals can be
thermally excited in a low temperature flame and
when the atoms return to the ground state they emit
radiation which lies mainly in the visible region of the
spectrum.
 Each element emits radiation at a wavelength
specific to that element. Example. Na 589nm,
K 766nm, Ca 622nm, Li 670.8nm, etc.
Determination of sodium/potassium by using
flame photometer

 Over a certain range of concentration the intensity of

the emitted radiation is directly proportional to the
number of atoms returning to the ground state.
 This in turn is proportional to the absolute quantity of
the species volatized in the flame i.e. light emitted is
proportional to the sample concentration.
 The light emitted by the element at its characteristics
wavelength is isolated by an optical filter and the
intensity of that light is measured by photo detector
which provides a signal proportional to the sample
concentration.
Determination of sodium/potassium by using
flame photometer

 Such an electrical signal is processed with the help of

analog to digital converter and the microprocessor.
Procedure
 Prepare standard solutions of

NaCl/KCl(10,20,30,40, and 50 ppm respectively)

 Draw the calibration curve ( emission Vs
concentration)
 Determine the concentration of Na/K in the given
sample using calibration curve.