INTERFERENCES
An increase and decrease in the size of the signal obtained from the analyte as a result of the presence of some other known or unknown
component in a sample is called interference.
It is the phenomenon in which two waves superimpose
to form a resultant wave of greater or lower amplitude. It decreases the
intensity of absorption of light.
Various factors may lead to interference with the
determination of the concentration of a given element.
Types of Interference
Ø Spectral
interferences
Ø Matrix
Interference
Ø Chemical
interferences
Ø Ionization
interferences
Spectral Interferences
This interference is caused by overlapping any radiation with the sample's radiation.
The interfering radiation may be due to another element,
radical, molecule unresolved spectra, or general background emission from flame
or solvent.
Example:
Vanadium (Va) line at 308.211nm interface in analysis based with the Aluminum (Al) line at 308.225nm. This can be avoided by choosing another (Al) line such as 309.270nm.
How to overcome it?
This can be overcome by selecting spectral lines properly
or by chemical separation.
Spectral interferences also result from the presence
of combustion products that exhibit broadband absorption or particulate
products that scatter radiation. Both reduce the power of the transmitted beam
and lead to positive analytical errors.
When the source of these products is the fuel and oxidant
mixture alone the analytical data can be corrected by making absorption
measurements while a blank is aspirated into the flame.
This
correction must be used with both double-beam and single-beam instruments because
the reference beam of a double-beam instrument does not pass through the flame.
Matrix Interference:
Spectral interference is also observed when the
source of absorption or scattering originates in the sample matrix.
The power of the transmitted beam P is reduced by
the matrix components but the incident beam power Po is not: a positive error
in absorbance and thus concentration results.
Example: Determination of Ba in alkaline-earth
mixtures. The wavelength of the barium line used for atomic absorption analysis
appears in the center of a broad absorption band for CaOH. Calcium is expected to interfere in barium determinations, but the effect is easily
eliminated by substituting nitrous oxide for air as the oxidant. The higher
temperature of the nitrous oxide flame decomposes the Ca(OH) and eliminates the absorption
band.
Chemical Interferences:
Chemical interference occurs when an analyte is not
totally decomposed in flame. There are fewer atoms present. Dissociation leads to low absorption.
Due
to anions: Phosphate ions interfere with the determination of Mg
and Ca. The absorption due to Mg and Ca is appreciably weaker in the presence
of PO43- ions. This is due to the formation of stable
phosphates of Mg and Ca which do not readily
split up into the respective atoms in the flame.
How to overcome it?
The addition of an excess of strontium (Sr) or
lanthanum (La), or thorium (Th) ions minimizes the interference of PO43- ion in
the determination of Mg and Ca by replacing the analyte in the compound formed
with the respective interfering species. In short, these ions combine
preferentially with PO43- ions.
Due
to Cations: In certain cases, cations also interfere
in atomic absorption measurements. For instance: Boron interferes with Mg and
Ca whereas aluminum interferes with alkaline earth elements.
Protective Agents
These agents are found to inhibit
the interferences by virtue of their ability to form relatively stable but
volatile species with the respective analyte.
Ionization interference:
It is observed that the ionization of atoms or
molecules is comparatively very small in combustion mixtures that involve air
as the oxidant.
The substitution of air occurs with either oxygen or
nitrous oxide. However, gives rise to temperatures that are high enough to
cause ionization.
M= Neutral atom or molecule
M= its corresponding ion
e= electron
Example: The intensity of atomic absorption lines for the alkali metals, such as K, Rb, and Cs is found to be affected by temperature and there is a noticeable decrease
How to overcome it?
The resulting effects of ionization equilibrium
shifts may be eliminated by the addition of an ionization Suppressor that
promptly gives a comparatively high concentration of electrons to the flame and
results in the suppression of analyte ionization.
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