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Chemical Interference in AAS Techniques

The document provides answers to tutorial questions on atomic absorption spectroscopy. It discusses several topics: 1) The use of cesium as an ionization suppressor to reduce interference from potassium emission lines. 2) Different types of interferences like chemical and spectral interferences and methods to address them such as using releasing agents or high resolution spectrometers. 3) Key differences between flame atomic absorption spectroscopy and flame atomic emission spectroscopy, including their light sources and measurement principles.

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100% found this document useful (1 vote)
201 views3 pages

Chemical Interference in AAS Techniques

The document provides answers to tutorial questions on atomic absorption spectroscopy. It discusses several topics: 1) The use of cesium as an ionization suppressor to reduce interference from potassium emission lines. 2) Different types of interferences like chemical and spectral interferences and methods to address them such as using releasing agents or high resolution spectrometers. 3) Key differences between flame atomic absorption spectroscopy and flame atomic emission spectroscopy, including their light sources and measurement principles.

Uploaded by

Echizen
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

SUGGESTED

ANSWER FOR TUTORIAL 3



1. To eliminate interference caused by emission of radiation by the flame. OR: To distinguish the
signal of the flame from the desired atomic line at the same wavelength

2. Cs is more easily ionized, a high concentration of electrons are produced in the flame. In an
application of Le Chateliers principle, the ionization of K is suppressed as follows:
K(g) K+ (g) + e- (g)

3. a) Hollow cathode Lamp (HCL)


(b) Transfomation of the liquid into a spray of small droplets/a fine spray or mist called aerosol
(c) To differentiate between the signal from HCL (the source) and the atomizer (flame)
(d) The use of one lamp per element during the analysis

4. a) Chemical interference
(b) i. Add releasing agents such as EDTA, La2+ solution, 8-hydroxyquinoline
ii. Use a higher flame temperature/ fuel-rich flame

5. In emission spectroscopy, the analyte signal is due to a small number of excited atoms.
Therefore, any change/ fluctuations in flame temperature will dramatically influence the
number of excited species. Therefore, the analytical signal will also be inconsistent

6. a) To reduce the matrix effects (due to the presence of a lot of impurities in the sample)

b)







The concentration of silicon in oil sample = |-11.6 | = 11.6 ppb

7.
Flame Atomic Absorption Spectroscopy Flame Atomic Emission Spectroscopy (AES)
(AAS)
The line source is HCL
Does not use any light source to excite the
electrons (it just uses the flame)
Detector measures the energies from a light
source which are absorbed by unexcited
atoms/ ions
The flame is used to atomize the sample The flame or plasma (ICP) atomizes and
(source of energy)
excites the electrons (source of energy)
The radiation absorbed by the ground state The radiation emitted by the excited atoms
are measured
are measured

8. a) The process in which a sample is converted into a gas-phase atoms or elementary ions
(b) The transformation of a liquid into a spray of small droplets or aerosols
(c) The process by which a sample solution is drawn by suction in atomic spectroscopy

9.
Interferences
Method to cure
Spectral interferences
Use high resolution spectrometers
Chemical interference
- Add releasing agens, i.e. EDTA, 8-
hydroxyquinoline, La3+ solution OR
- Use higher temperature flame
The flame is used to atomize the sample
Use ionization supressor , i.e. CsCl

10. (a)Functions as a source modulator to differentiate signal emitted by the source (HCL) and the
signal emitted by the flame (atomizer) AND eliminate the effects of radiation from the flame
AND to distinguish between component of radiation arising from source with flame background
(b) The most common source for atomic absorption measurements that consists of a tungsten
anode and a cylindrical cathode
(c) As an atomizer, in which a part of where aerosol, oxidant and fuel are burned. The burners
used are most often premixed, laminar flow

11. (a) Standard addition analysis is done for sample with complicated matrix (When sample matrix
is high)
(b) Cx
= bCstd / mVx

= (0.2662 x 10 ppm)

(1.645 mL-1 x 20 mL)

= 0.08175 ppm

12. a)

(b) Concentration of analyte in initial solution =


Vflask
Concentration of analyte in initial solution
Vinitial unknown

Concentration of Ca in wastewater =
-CSA (Vflask/ Valiquot)
CSA = | -7 ppb |


=
7 ppb





=
7 ppb x (50/10)





=
35 ppb

(c) Principles:



Process measured

Use of flame
Beers Law
Data presentation

FAES
Excitation of neutral atoms
is brought only by the
thermal energy
Measurement of the
intensity of light emitted
when a metal is introduced
into a flame
Atomization with excitation
Not applicable
Intensity vs. Concentration

FAAS
Excitation of neutral atom
is brought only by radiation
from HCL
Measurement of the
intensity of light absorbed
when a metal is
bombarded by HCL
Atomization
Applicable
Absorbance vs.
Concentration

13. To prevent chemical interference. This could form a compound of higher stability than that
formed by analyte
Example : Ca3(PO4)2 + LaCl3 3 CaCl2 + 2 LaPO4

14.


Concentration of Pb in sample by extrapolation of graph,
= | -1.76 ppm|
= 1.76 ppm

15. a) Spectral interference: It refers to the overlap of analyte signals due to other elements or
molecules in the sample or with signals due to the flame/ atomizer
b) - Use a high resolution spectrometer
- Interference can be subtracted using D2 or Zeeman background correction
- Choose another wavelength for analysis

16. i) Use high- resolution spectrometers
ii) Use another wavelength for analysis
iii) Do a background correction method (i.e. based on Zeeman effect, two line correction, etc)

17. When the matrix effects are high

Common questions

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Using a flame for atomization in atomic spectroscopy provides a straightforward and effective means to disaggregate sample molecules into free atoms. Benefits include simple setup and relatively low cost. However, limitations arise from variability in flame temperature, which can affect excitation and lead to inconsistent analytical signals, especially in emission methods where temperature fluctuations have significant impact. Additionally, the method is limited to elements that can be efficiently atomized at the flame's temperature .

Matrix effects can lead to significant inaccuracies in atomic spectroscopy by altering the signal due to interfering substances in the sample. These effects are mitigated through methods such as standard addition analysis, which normalizes matrix variations, or optimization of the sample preparation such as dilution and volatilization techniques. Additionally, modifying the flame condition or using suitable releasing agents can prevent formation of non-volatile compounds, thus enhancing the precision and reliability of the analysis .

Chemical interference in flame spectroscopy can be minimized by adding releasing agents like EDTA, La2+ solution, or 8-hydroxyquinoline, which bind to the interfering species, or by using a higher-temperature (fuel-rich) flame to break down stable compounds, thereby enhancing the accuracy of analytical results .

Standard addition analysis helps in dealing with complex sample matrices by compensating for matrix effects that can affect the accuracy of the results. This is achieved by adding known quantities of the analyte to the sample and measuring the change in signal, which can then be used to calculate the concentration of the analyte in the original matrix. It corrects for matrix-related deviations by effectively normalizing the sample with an internal standard .

A source modulator is used in atomic absorption measurements to distinguish the signal from the hollow cathode lamp (HCL) and the flame. It functions as a differentiator, eliminating the effects of radiation emitted by the flame and identifying the component of radiation that arises from the source against the flame's background .

Cesium (Cs) is used as an ionization suppressor because it is easily ionized, producing a high concentration of electrons in the flame. According to Le Chatelier’s principle, this suppresses the ionization of other elements, such as potassium (K), by shifting the equilibrium of their ionization reactions to favor the un-ionized form, effectively reducing ionization interference .

The addition of lanthanum chloride (LaCl3) in analytical measurements prevents chemical interference by reacting with the interfering substances to form more stable compounds. For example, it prevents the formation of less volatile and more stable matrices—like calcium phosphate—by converting them into more volatile forms, thereby freeing the analyte for accurate measurement .

In flame atomic absorption spectroscopy (FAAS), a hollow cathode lamp (HCL) is used to provide specific wavelengths of light that are absorbed by the ground state atoms in the sample, allowing for quantitative analysis. In flame atomic emission spectroscopy (FAES), the sample itself generates light when excited by the flame, negating the need for an external light source. This distinction influences the setup and sensitivity of each technique, with FAAS relying on external excitation and FAES relying on thermal excitation by the flame .

Spectral interferences occur when signals from different elements or flame emissions overlap, leading to inaccuracies. These are addressed using high-resolution spectrometers to separate overlapping signals and by applying background correction methods such as D2 or Zeeman correction. Selecting an alternative wavelength for analysis can also mitigate these interferences, ensuring accurate detection and quantification .

Flame atomic absorption spectroscopy (AAS) uses a hollow cathode lamp (HCL) as its line source, where the detector measures energies absorbed by the unexcited atoms or ions. In contrast, flame atomic emission spectroscopy (AES) does not use a source to excite the electrons; instead, it relies solely on the flame. AES measures the radiation emitted by the excited atoms. Thus, AAS requires an external light source, while AES depends on the flame for both atomization and excitation .

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