CHEM340: Instrumental Analysis

Tutorial: Atomic spectroscopy

Question one

Explain clearly why:

a) the burner head of the flame atomizer is shaped into a slot.

b) atomic spectral lines chosen for quantification span a finite range of wavelengths instead of just being
a single wavelength as specified on instrumental set up methods for elements.
c) hollow cathode lamps are the most appropriate sources of radiation for analysis by atomic absorption
spectroscopy.
d) for the analysis of Group 1 elements by flame atomic absorption spectrophotometry (Flame AAS), a
constant amount of salt of an element lower down the group is always added to both samples and
analyte standards.
e) absolute detection limits of electrothermal atomic absorption spectroscopy are much lower than those
of the flame atomic absorption spectroscopy.
f) better and more precise results are measured when the electrographite tube is transversely heated
than when it is longitudinally heated.
g) spectral interferences present a major challenge to ICP-OES analysis than they are in Flame Atomic
absorption analysis.
h) you cannot do speciation studies using optical atomic spectroscopy.
i) Flame AAS and ICP-OES spectrometers are fitted with a nebulizer and a spray chamber.
j) ICP-OES is a multi-element quantitative technique where as Flame AAS and the electrothermal AAS are
usually single-element techniques.
k) an internal standard can be used for ICP-OES but is not used for AAS.

Question two

a) Describe what happens to a solution stream from the time it is aspirated into the capillary tube up to
the time it reaches the flame. Include its fate as it passes through the nebulizer, the spray chamber up
to a time when it attains thermal equilibration with the flame.
b) Why is it necessary to supply a stream of a noble inert gas (but not nitrogen) to an electrothermally-
heated graphite tube?
c) How do you control chemical interference during Electrothermal vaporization AAS analysis?

Question three

For each of the following applications, state with a reason which technique (i.e. flame AAS, electrothermal
AAS or ICP-OES) would you use to quantitatively determine analytes in the following samples. If you think
none of the technique is suitable, explain briefly.

a) Determination of Cd, Cu, Cr, Pb & Tl at mg/L in an acid mine drainage water.
b) Determination of Pb in children blood- the blood sample is taken from a finger prick; a small drop of
blood is extracted.
c) Determination of Pb calcium in fertilizer sample- the fertilizer is dissolved in distilled water for
analysis.
d) Determination of P, S, Si, Na & Mg in water sample at g/L levels.
e) Determination of two heavy metals in a single strand of hair fiber (mass < g) swabbed off from a
crime scene.

Question Four

Silicon in sugar syrup was being determined using the method of standard additions. Aliquots of the syrup
(50.00 mL) were taken, mixed with various volumes of a standard (500.0 mg/L) silicon solution and made up
to volume with pure water to 100 mL in a volumetric flasks. The resultant solution was analyzed by ICP-OES,
with the following results:

Volume of the syrup, mL Volume of the standard, Final volume, mL Emission intensity
L
50.00 0.00 100.0 787
50.00 25.0 100.0 1141
50.00 50.0 100.0 1499
50.00 75.0 100.0 1889
50.00 100.0 100.0 2280

a) Calculate the mass (g) of Si added to the 100.00 mL syrup solution.

b) Plot emission intensity versus mass of added silicon standard.
c) Find the mass of silicon in the dilute 100 mL aliquot.
d) Find the concentration (g/L) Si in the original syrup.
e) What is the advantage of this method over external calibration?
f) If this sample were to be analyzed by absorption (Flame AAS or Electrothermal vaporization AAS?
Which one would you choose? Give your reasons.

Question five

Strontium was being determined by flame emission spectrophotometry. A set of strontium standards was
prepared and to each of the standards and the samples a fixed amount of yttrium (Y) was also added. The
emission intensities for each of the solutions were measured.

[Sr], mg/L Sr Emission Y Emission

0.00 0.0 19.4
1.00 16.6 21.5
2.00 37.8 24.7
standards

3.00 43.2 18.6

4.00 68.7 22.3
5.00 95.2 24.6
Rain water 45.6 20.2
samples Effluent water diluted by 102.7 21.6
transferring 25.00 mL into 100
mL volumetric flask
Calibration equation: y = 0.7734x - 0.0041.

a) What variables were plotted on the y- and x-axes in order to come up with the calibration curve?
b) Use the emission data for 1.00 mg/L and the 5.00 mg/L standards to confirm roughly your answers
given in a)
c) Determine the concentration of strontium in the rain water and effluent samples.
d) Why was yttrium added to both standards and samples?