ATOMIC ABSORPTION SPECTROMETRY

1.1 Explain the working principle of the FAAS.

1.2 List the processes that occur when a solution is introduced into a flame in FAAS.

1.3 Define the following terms used in AAS:

1.3.1 Sputtering

1.3.2 Source modulation

1.3.3 Nebulization

1.4 List four advantage of a premix/laminar flow burner.

1.5 List four characteristics of an ideal atomization-excitation source

1.6 List three advantages of the ET AAS.

1.7 Discus the major differences between the two main (common) light sources used in the AAS.

1.8 Explain the mechanisms behind the emission of radiation by a hollow cathode lamb.

1.9 Explain how the AA spectrometer delineates between the radiation from the source like the
HCL and emission from the flame or the atomizer.

1.10 Discuss with basic AAS theory, the reasons for following observations

1.10.1 The addition of K to a Li solution greatly increases its absorbance.

1.10.2 The addition of Lanthanum chloride to a plant-digest solution containing phosphates

1.11 Describe the heating stages involved in the operation of ET atomizers for AAS.

1.12 Determine graphically the concentration of Mn in tea (in ppm) if 1.30 g of the sample was
ashed, the residue dissolved in a few drops of HCl, and the final volume of the solution
adjusted to 100 mL with distilled water.

1.13 For the following types of interferences, briefly explain what causes them and one of ways
minimizing it.
 1.13.1 Spectral overlap in emission

1.13.2 Ionization interference in AAS.

1.14 Briefly discuss three ways of alleviating chemical interferences in AAS

1.15 An atomic absorption spectrophotometric method for the quantitative analysis of Pb2+ in blood
yields an Ssamp of 0.193 when a 1.00 mL sample of blood is diluted to 5.00 mL. A second 1.00
mL sample of blood is spiked with 1.00 mL of a 1560-ppb Pb2+ external standard and diluted
to 5.00 mL, yielding an Sspike of 0.419. What is the concentration of Pb2+ in the original sample
of blood?

1.16 A spectrophotometric method for the quantitative analysis of Pb2+ in blood yields an Sstd of
0.474 for a single standard whose concentration of lead is 1.75 ppb. What is the concentration
of Pb2+ in a sample of blood for which Ssamp is 0.361?

1.17 A municipal water company was having problems with its water analysis. The problem lay in
the AAS determination of Fe at 248.3 nm. The absorbance of the water, after 5 fold dilution
was 0.646 at 248.3 nm. A standard solution prepared by dissolving 0.1483g of iron wire in
acid, diluting to 250 mL. After a further x100 dilution the solution had an absorbance of 0.813.

1.17.1 Calculate the ppm in the water sample. What is wrong with this analysis?

On a proper investigation of the above problem a series of iron standards were prepared by
taking various volumes of a 0.0593 mg Fe per mL and diluting up to 100 mL. The absorbance
of the solutions were as given in the table.

Volume of Fe taken (mL) Absorbance at 248.3 nm

0.00 0.000

1.00 0.113

3.00 0.334

5.00 0.530

7.00 0.672

10.00 0.813

1.17.2 Using data in the table above, determine the true value of the Fe content
in the municipal’s water.

1.18 The sodium in a series of cement samples was determined by FAES. The flame photometer
was calibrated with the following standards:
 Standard Concentration Emission Reading
(µg Na2O/mL)
0.0 3.1
20.0 21.5
40.0 40.9
60.0 57.1
80.0 77.3

1.18.1 Plot the calibration curve using the corrected values for emission.

1.18.2 A 1.000 g sample of cement was dissolved in HCl and diluted to 100,0 mL
after neutralisation. The emission reading was 41.2. Calculate the percent
Na2O in the sample.

ATOMIC EMISSION SPECTROSCOPY

2.1 Give reasons why atomic emission methods with an inductively coupled plasma (ICP) source
are better suited for multi-element analysis than are flame atomic absorption methods.

2.2 List three advantages of plasma over flame atomization in atomic spectroscopy

2.3 Explain the working principle of the AES.

2.4 Draw a labelled schematic diagram of the ICP torch.

2.5 Describe the process of how the plasma works.

2.6 Explain why the plasma does the scotch or melt the instrument.

2.7 The plasma consists of three argon streams. Explain the function of the three streams.

2.8 Explain why determining several elements would be too much time consuming and laborious
using the FAAS compared to the ICO-AES.

2.9 List and briefly explain the four types of sources used in AES.

2.10 Calculate the frequency, the energy and the wavenumbers for a 3.517-micron vibrational
absorption band. Use c = 2.998 x 108 m/s

2.11 Explain in detail the ignition process of an inductively coupled plasma source. You may use a
sequence of clearly labelled illustrations to demonstrate this.

2.12 Describe the function of each of the three flows of argon in the ICP torch.

2.13 For what reason is quartz used for the manufacture of the concentric tubes?

2.14 How is the inductively coupled discharge sustained in the torch?

2.15 List the characteristics of an ideal emission source.

2.15 Discuss the reasons for arc sources being blanketed with a stream of an inert gas?

2.16 Why do ion lines predominate in spark spectra and atom lines in arc and ICP spectra?

2.17 Describe the reasons for carbon being the ideal electrode material for arc and spark
spectroscopy measurements.

2.18 The gold concentration of a rock sample was determined by fusing the sample with a suitable
flux and dissolving it in a solution. This solution (containing gold as well as high concentrations
of diverse ions) was analysed by ICP-atomic emission spectroscopy (ICP-AES). Aliquots of
50 mL of the sample solution were added to each of two 100 mL volumetric flasks. A 5.0 mL
volume of a solution of 10.0 mg/L Au was added to the second flask and both were made up
to a total volume of 100 mL and mixed. The ICP-AES measurements were as follows:

Volume (mL) added Au standard Emission Intensity,

2.18.1 Calculate the concentration of gold in the sample solution in mg/L

2.18.3 Suggest, with reasons, an organic solvent that would enhance the readings with a
solution containing other metal ions (non-gold). What chelating agent would you add
to the solution to expedite the organic solvent’s function?

X-RAY SPECTROSCOPY
3.1 Describe how electrons in atoms give rise to X-rays; and give the wavelength range of
these X-rays

3.2 Draw and label a diagram to illustrate the radiation spectrum emitted from an X-ray tube.

3.2.1 In detail, explain how the continuum spectrum is formed.

3.2.2 Show the ‘short wavelength limit’ on the diagram in 3.2.1 and give its dependency

3.3 Calculate the minimum voltage required to excite the Kβ series of lines for tungsten if the
wavelength is 0.111 Å for the Kβ series.

3.4 Describe the process of X-ray absorption by an element such as lead.

3.5 Define the term ‘absorption edge’.

3.6 Below is an unlabelled diagram of a wavelength dispersive X-ray spectrometer.

3.6.2 Calculate the angle (2θ) required to position a goniometer in order to observe the
Kα1 lines of the first order diffraction for Mn at 3.824 Å when the diffracting crystal
is ammonium di-hydrogen phosphate, with lattice inter-planar spacing d of 4.485
Å.

3.6.3 Give two requirements of a crystal for x-ray diffraction to take place
effectively.

3.7 Briefly explain the phenomenon x-ray fluorescence and x-ray diffraction and state their
analytical applications

3.8 Calculate the frequency and the energy in kJ/mol of an X-Ray photon with a wavelength of
2.38A.

3.9 List and discuss three parameters that affect the emission of X-Ray continuum from a
source.

3.10 Differentiate between the EDXRF and WDXRF.

3.11 How can you minimize matrix effects in X-Ray spectroscopy

3.12 Define the following terms in X-Ray spectroscopy

3.12.1 L-Series emission lines

3.12.2 Kg line for Cu

3.12.3 Mass absorption coefficient

3.12.4 Absorption edge

3.12.5 Continuum from an X-Ray tube

3.12.6 Rayleigh Scattering

3.12.7 Collimator

3.12.8 Filter
3.13 Explain why it is important to ensure that the thickness of the analysed sample is more than
the infinite thickness of the sample.

3.14 The analysis of an iron ore sample was performed as follows: 1g of the ore sample was
mixed with 9.0 g of the fluxing agent, fluxed at 800oC, cooled and analysed. The standard
was prepared by mixing 2.000 g of standard ore containing 25% of iron ore, with 8.000 g of
the flucxing material. The counts obtained for the Ka line of Fe was 1240 for the standard
and 1650 for the sample. Calculate the %Fe in the ore sample.