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UNIT 5 Summary

Atomic Spectrometric Methods:
• 17.1 Flame Emission Spectroscopy:
• -the source is flame , low-energy source, thus its simple with few emission lines.
Samples are introduced in the form of solution. Aspirator burners are used,
basically the solution is introduced into the flame as a fine spray.
• - the solvent evaporates, leaving dehydrated salt. The salt is dissociated into free
gaseous atoms in the ground state. A certain fraction of these atoms can absorb
energy from the flame and be raised to an exciting electric state. The excited
levels have a short life and thus drop back to ground state, emitting photons of
characteristic wavelengths , with energy = hv.
• -side reaction may decrease population of the free atoms, thus lower the emission.
• In early years, only cool flames were used, as temperature increases number of
atoms being excited also increases.
• 17.2 Ground and Excited States:
• the relative populations of ground state (N0) and excited state (Ne) populations at a
given flame temperature can be estimated from the Maxwell-Boltzmann

• short –wavelength elements require much more energy for excitation and exhibit
poor sensitivity.
• In flame emission we measure the excited population and in atomic absorption
methods we measure the ground state population.
• 17.3 Atomic Absorption Spectroscopy:
• -also uses flame as the atomizer as in AES
• Principles: the sample solution is aspirated into a flame , and is converted into
atomic vapour
• -the flame contains atoms of that element, the ground state atoms can absorb
radiation of a particular wavelength that is produced by a special source. The
wavelengths of radiation given off by the source are the same as those absorbed
by the atoms in the flame
• the absorbtion follows beer’s law – absorbance is directly proportional to the
pathlength in the flame and to the concentration of atomic vapour in the flame
• Instrumentation:
• A light source, a cell(the flame), a monochrometer, and a detector
• The flame is placed between the source and the monochrometer

• this is for a double-beam instrument that measures the ratio of P0\P. The source
beam is alternately sent through the flame and around the flame by the chopper.
The detector measures thses alternatively and the logarithm of the ratio is
• Double-beam instruments are required for background correction using deuterium
continuum lamps. Beam splitter increases the noise levels, need a good source to
compensate for a decreases signal-to-noise ratio.
• Sources:
• -a sharp line source is required because of the width of the absorption line is very
narrow, thus only a small fraction of the radiation from a continuum source
passed by the slit and reaching the detector would be absorbed.
• Source used the most is HOLLOW-TUBE LAMP (HCL)

• this is a sharp line source that emits specific wavelengthsin AAS only.
• It consists of a cylindrical hollow cathode made of the element to be determined,
and tungsten anode
• These are enclosed in a glass tube usually with a quartz window (UV region)
• The tube is under reduced pressure and filled with inert gas (argon or neon)
• A high voltage is impressed across the electrode, causing the gas atoms to be
ionized at the anode. These positive ions are accelerated towards the negative
cathode , when they bombard the cathode, they cause some of the metal to
‘sputter’ and become vaporized. The vaporized metal is excited to higher
electronic levels by continued collision with the high energy gas ions. When the
electrons return to the ground state, the characteristic lines that metallic element
are emitted. Also, are emitted the lines of the filler gas.
• Resonance line: the most strongly absorbed line is often, but not always, the one
corresponding to the most probable electronic transition, usually from the ground
state to the lowest excited state.
• .
• Burners:
• Laminar flow burner-
• The fuel and support gases are mixed together before they enter the burner head
where they combust
• The air creates a partial vacuum at the end of the capillary, drawing the sample
through the capillary , its broken into a fine spray at the tip. This is a usual
process of nebulization. The larger droplets of the resulting aerosol condense and
drain out of the chamber , the remaining fine droplets mix with the combustion
gases and enter the flame ( 90% of the droplets condense out, and 10% enter the
• Premix burners are usually limited to relatively low-burning velocity flames. But
droplets are finer and the path length is longer
• .
• Flames:
• There are many types of flames
• Most widely used AAS are air-acetylene flame and the nitrous oxide-acetylene
flame( is best for refractory elements) with premix burners.
• Cool flame is subject to chemical interferences more than other flames
• Hot flame is required for AES and thus nitrous oxide-acetylene is used, it has a
high burning velocity, can be used with premix burner

• Interferences:
• 1.Spectral Interferences:
• -in emission occurs whenever there is a another emission line or a molecular
emission band close to the emitted line of the test element and is not resolved by
the monochrometer
• light scatter or absorption by solid particles, unvapourized solvent droplets, or
molecular species in the flame will cause a positive interference in AAS (more so
for wavelengths below 300nm). Such background absorption may be corrected by
measuring the absorbance of a line that is close to the absorption line
• 2. Ionization interference
• a fraction of the alkali and alkaline earth elements in very hot flames me be
ionozed in the flame. The presence of other easily ionized elements in the sample
will add free e- to the flame and suppress ionization of the test element.
• It can be suppressed by adding a solution of a more easily ionized elements, for
example potassium or cesium.
• 3. Refractory Compound formation
• the sample solution may contain a chemical, usually an anion, that will form a
refractory (heat-stable) compound with the test element in the flame.
• Refractory compound formation is avoided by chemical competition or by use of
a high-temperature flame.
• Also releasing agent is being used such as EDTA that prevent ref. cmpd
• 4. Physical Interferences
• most of the interferences present
• such as variations of the gas flow rates, sample viscosity due to the temperature or
solvent variation, high solid content and flame temperature.
• Fix: calibration and use of internal standards

• Sensitivity is defined as the concentration required to give 1% absorption
(0.0044A). It is a measure of the slope of the analytical calibration curve and says
nothing about the signal-to-noise ratio (S/N).

• Detection Limit is generally defined as the concentration required to give a signal
equal to three times the standard deviation of the baseline (blank)

• Generally speaking, atomic absorption shows detectability for those elements that
emit below 300 nm because of the high thermal energy required to excite the
atoms for emission at these wavelengths.

• An internal standard undergoes similar interferences as the analyte. Measurement
of the ratio of the analyte to the internal standard signals cancels interferences.

• In standard addition calibration, the standard is added to the sample, and so it
experiences the same matrix effect as the analyte.

• Refer to her slides for the rest of stuff, im too lazy to type it.