Lecture 12

FLAME EMISSION & ATOMIC ABSORPTION SPECTROMETRY

12.1. Flame Photometer

Principles
Emission of electromagnetic radiation in the visible and ultraviolet
regions of the spectrum by atoms after electronic excitation in flames.

Instrumentation
Flame photometer or spectrophotometer incorporating nebulizer and
burner, filters, prism or grating monochromator, photocell or
photomultiplier detection system.

Applications
Quantitative determination of alkali and alkaline earth metals in
solution.

Disadvantages
Intensity of emission is very sensitive to changes in flame
temperature. Spectral interferences are common.

Instrumentation
The sample, in the form of a solution, is drawn into a nebulizer where
it is converted into a fine mist or aerosol. From there it passes into
the flame along with air or oxygen and a fuel gas. Following thermal
excitation, the radiation emitted as excited atoms relax is viewed by a
photocell or photomultiplier. The current generated in the detector
circuit is read directly or, more conveniently, converted to a meter or
digital readout in analyte concentration. It should be noted that the
relatively stable emission resulting from flame excitation, facilitates
the almost instantaneous measurement of line intensities.
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Low temperature flames produce spectra that are sufficiently

simple to allow the use of narrow bandpass filters to isolate the
required emission lines for quantitative measurement. Such an
instrument is called a flame photometer. If better resolution is needed
to isolate lines in ore complex spectra, or to minimize interference
from background emission, a flame emission spectrophotometer
incorporating prism or grating dispersion is necessary and the
technique is known as flame atomic emission spectrometry.

Fig. 1. Schematic diagram of a flame photometer

12.2. Atomic Absorption Spectrometry

Atomic absorption spectroscopy in analytical chemistry is a technique
for determining the concentration of a particular metal element in a
sample. Atomic Absorption Spectroscopy can be used to analyse the
concentration of over 62 different metals in a solution.

Atomic Absorption Spectroscopy was first developed during the

1950's by a team of Australian chemists, lead by Alan Walsh, working
at the CSIRO (Commonwealth Science and Industry Research
Organisation) Division of Chemical Physics, in Melbourne Australia.
Typically, the technique makes use of a flame to atomize the sample,
but other atomizers such as a graphite furnace are also used. Three
steps are involved in turning a liquid sample into an atomic gas:
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Desolvation – the liquid solvent is evaporated, and the dry

sample remains
Vaporisation – the solid sample vaporises to a gas
Volatilisation – the compounds making up the sample are broken
into free atoms.

The light that is focused into the flame is produced by a hollow

cathode lamp. Inside the lamp is a cylindrical metal cathode
containing the metal for excitation and an anode. When a high voltage
is applied across the anode and cathode, the metal atoms in the
cathode are excited into producing light with a certain emission
spectra. The type of hollow cathode tube depends on the metal being
analysed. For analysing the concentration of copper in an ore, a
copper cathode tube would be used, and likewise for any other metal
being analysed.

A minute quantity of the liquid sample solution, about 0.01–0.02

the size of a raindrop (20–50 μL), is sprayed into a nitrous oxide–
acetylene or air–acetylene flame, which vaporizes the solution,
releasing metal atoms from their chemical compounds and converting
them into their elemental forms. A beam of light passes through the
flame, and some of the atoms in the sample vapor absorb energy from
this light.

A detector on the other side measures the intensity of the light

after it has passed through the flame and sample vapor and this
intensity is compared to the original intensity of the light. This
difference is an indication of the number of light-absorbing atoms in
the sample.

Fuel / oxidant mixtures

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For a medium temperature flame, acetylene and air is used. A hotter

flame can be produced using acetylene and pure oxygen, and an even
hotter flame can be attained using nitrous oxide and acetylene, for
determination of aluminum, boron.

We can find the concentrations of metals in a sample running a

series of calibration standards through the instrument. The
instrument will record the absorption generated by a given
concentration. By plotting the absorption versus the concentrations of
the standards, a calibration curve can be plotted. We can then look at
the absorption for a sample solution and use the calibration curves to
determine the concentration in that sample.

Parts
The main parts of the AAS system are a hollow cathode lamp,
nebulizer, air/acetylene flame, and optical system. Alternate sample
introduction systems such as graphite furnaces are also available but
will not be discussed here. The job of each is detailed below:

Job of the hollow cathode lamp (HCL)

Provide the analytical light line for the element of interest
Provide a constant yet intense beam of that analytical line
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Job of the nebulizer

Suck up liquid sample at a controlled rate
Create a fine aerosol for introduction into the flame
Mix the aerosol and fuel and oxidant thoroughly for introduction into
the flame

Job of the flame

Destroy any analyte ions and breakdown complexes
Create atoms (the elemental form) of the element of interest Fe 0, Cu0,
Zn0, etc.

Job of the monochromator

Isolate analytical lines' photons passing through the flame
Remove scattered light of other wavelengths from the flame
In doing this, only a narrow spectral line impinges on the PMT.

Job of the photomultiplier tube (PMT)

As the detector the PMT determines the intensity of photons of the
analytical line exiting the monochromator.

The Hollow Cathode Lamp

The hollow cathode lamp (HCL) uses a cathode made of the element
of interest with a low internal pressure of an inert gas. A low
electrical current (~ 10 mA) is imposed in such a way that the metal is
excited and emits a few spectral lines characteristic of that element
(for instance, Cu 324.7 nm and a couple of other lines; Se 196 nm and
other lines, etc.). The light is emitted directionally through the lamp's
window, a window made of a glass transparent in the UV and visible
wavelengths.

The Monochromator and PMT

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Tuned to a specific wavelength and with a specified slit width chosen,

the monochromator isolates the hollow cathode lamp's analytical line.
Since the basis for the AAS process is atomic ABSORPTION, the
monochromator seeks to only allow the light not absorbed by the
analyte atoms in the flame to reach the PMT. That is, before an
analyte is aspirated, a measured signal is generated by the PMT as
light from the HCL passes through the flame. When analyte atoms are
present in the flame--while the sample is aspirated--some of that light
is absorbed by those atoms (remember it is not the ionic but
elemental form that absorbs). This causes a decrease in PMT signal
that is proportional to the amount of analyte. This last is true inside
the linear range for that element using that slit and that analytical
line. The signal is therefore a decrease in measure light: atomic
absorption spectroscopy.
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