Flame Photometry PDF

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Objective:

To determine the concentration of alkali and alkaline earth metals


in various samples.

Introduction

Atomie spectroscopy is thought to be the oldest instrumenta


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 characteristie element present in the flame. The
potential of atomie spectroscopy in both the qualitative as well as
quantitative analysis were then well Theestablished.
developments in the instrumentation area led to the widespread
applieation of atomie spectrosecopy Atomie spectroscopy is an
unavoidable tool in the field of analytical chemistry. It is divided
into three types whieh are absorptio. 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).
(8) Inductively coupled plasma-atomic emission spectrometry
(ICP-AES).

Gustau Kirchhoff (left) and Robert Bunsen (right)


Theory
Photoelectrie flame branch of atomie spectroscopy
photometry. a

is used for inorganic chemical analysis for determining the


conentration of certain metal ions such as sodium. potassium.
ithium, elcium. Cesium. ete. n flame photometry the species
(metal ions) used in the spectrum are in the form of atoms. The
International Union of Pure and Applied Chemistry (IUPAC)
Committee on Spectroscopie Nomenclature has recommended it as
flame atomie emission spectrometry (PAES). The basis of flame
photometric uworking is that. the species of alkali metals (Group
1 and alkaline earth metals (Group ) metals are dissociated due
to the thermal energy provided by the flame source. Due to this
thermal exoitation. some of the atoms are excited to a higher
energy level where thoy are not stable. The absorbance of light
due to the electrons excitation ean 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 ean be visualized in
the visible reglon of the spectrum. The absorbance of light due to
the electrons excitation ean be measured by using the direet
absorption techniques while the emitting radiation intensity is
measured using the emission techniques. The waveleng th of
emitted light is specifie for specifie elements.

Flame Photometer
Parts of a flame photometer

1. Source of flame:
A burner that provides flame and can be maintained in a

constant form and ata constant temperature.

2. Nebuliser and mixing chamber:


the substance
Helps to transport the homogeneous solution of
into the flame at a steady rate.

3. Optical system (optieal filter):


mirror. lens
optical system comprises three parts:
convex
The
and filter. The convex mirror helps to transmit light emitted

focus the emissions to the lens. The


from the atoms and

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
emissions. Hence it acts as
from that of any other extraneous
interference type color filters.

4. Photo detector:
Detect the emitted light and measure the intensity of radiation

emitted byflame. That is. the emitted radiation is


the
converted to an electrical signal with the help of photo
detector. The produced electrical signals are directly
proportional to the intensity of light.

photometer is shown in
A schematic representation of flame
figure 1.

TLAME

3URNLR MosecnoMATON RINTE


PHOT0DEIEC TOR

ATONIZE

ALPHA SOMIRICAL
SAMPLL 3
UEL SEPPY

Fio 1: Aschematic representation of flame photometer


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:

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.
6. The intensity of emitted light is related to the
concentration of the element.

in flame

Molecdos

ors in blution

Energy e
in he lon
of igh

Relurr e
minsiai

Fig 2: Brief overview of the process

Events occurring in the flame:


Events occurring in the flame:

Flame photonmetry employs a variety of fuels mainly air. oxygen


or nitrous oxide (N20) as oxidant. The temperature of the flame

depends on fuel-oxidant ratio.

The various processes in the flame are discussed belouw:

1. Desolvation: The metal particles in the flame are dehydrated by


the flame and henee the solvent is evaporated.
2. Vapourisation: The metal particles in the sample are
dehydrated. This also led to the evaporation of the solvent.
3. Atomization: Reduction of metol ions in the solvent to metal
atoms by the flame heat.
4. Exeitation: The clectrostatie 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.
6. Emission process: Since the higher energy state is unstable the
atoms jump back to the stable low energy state with the emission
f energy in the form of radiation of characteristic wavelength.
which is measured by the photo detector.

The energy level diagram of the sodium atom is showm in figure 3

616nm 588nm

589nm

3s

Fig 3: Energy level diagram for atomic sodium

The intensity of the light emitted could be desoribed by the


Scheibe-Lomakin equation:
kXC"
The intensity of the light emitted could be described by the
Seheibe-Lomakin equation
kxC

Where:
Intensity of emitted light
the concentration of theelement
constant of proportionality
n- (at the linear part of the calibration curve)
Then.
I = k*xC

That is the intensity of emitted light is direetly 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.
The
flame emissions of the alkali and alkaline earth metals in terms of
wavelength and the eharacteristic color produced by each element
is shown in table 1
Name of the element mitted wavelength range (nm) Observed colour oftheflame

Potassium (u

Vielet

led

Lithium (L

Caleium (Go)

Ovange

Sodiun (Na 89

Heliow

Barum (Bal
Applications

Flame photometer has both quantitative and qualitative


applications. Flame photometer with monoohromators emits
radiations of characteristie waveleng ths which help to detect the
presence of a particular metal in the sample. This help to
determine the avalability of alkali and alkaline earth metals
whieh are eritical for sol cultivation. In ogriculture. the
fertilizer requirement of the soil is analyzed by flame test
analysis of the soil. In clinieal field. Nat and Kt ions in body
Fluids. muscles and heart can be determined by diButing the blood
serum and aspiration into the flame. Analysis of soft drinks.
fruit juices and alcoholic beverages can also be analyzed by using
flame photometry.

Advantages:

1. Simple quantitative analytical test based on the flame analysis.


2. Inexpensive.
3. The determination of elements such as alkali and al kaline earth
metals is performed easily with most reliable and convenient

methods.
convenient. and selective and sensitive to even parts
4. Quite quick.
per million (ppm) to parts per billion (ppb) range.
Disadvantages

Moreover the flame photometer has a wide range of applications


in the analytical chemistry. it possess many disadvantages which
are explained below:

1. The concentration of the metal ion in the solution cannot be


measured accurately..
2. A standard solution with known molarities is
required for
determining the concentration of the ions which will corresponds
to the emission spectra.
3. It is difficult to obtain the accurate results of ions with higher
concentration.
4. The information about the molecular structure of the compound
present in the sample solution cannot be determined.
5. The elements such carben.
as
hydrogen and halides cannot be
detected due to its non radiating nature.

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