1

Laboratory material for advanced analytical chemistry course

Part II: Analytical Atomic Spectrometry
Course leader: Assoc. Prof. Nguyen Van Dong
Lab instructor: MSc. Le Thi Huynh Mai, MSc To Hong Chuyen, BSc Le Thanh Long, BSc Do Thi Tu Trinh

FLAME ATOMIC ABSORPTION SPECTROMETRY

The following experiments are designed to provide a basis for the correct use of flame
atomic spectrometry as an analytical technique.
EXPERIMENT 1
Optimization of instrument parameters
A correct adjustment of an AAS instrument is necessary to obtain maximal sensitivity (S)
and optimal signal to noise ratios (S/N). The following optimization is made:
1. Lamp current and alignment of the lamp position
2. Wavelength and spectral bandwidth (SBW)
3. Burner position (horizontal, vertical and rotational alignment)
4. Flame stoichiometry (acetylene/oxidant mixture)
5. Glass impactor beads position in front of the spray nozzle
Element: Chromium (Cr)
Lamp current: 10 mA
Wavelength: 357.9 nm
SBW: 0.7 nm
Flame: acetylene/air
Solution: 2 ppm
Experiment:
1. Start the instrument and select the recommended lamp current and spectral
bandwidth (SBW)
2. Select ABS mode.
3. Place the burner in its lowest position with the vertical control.
4. Isolate the resonance wavelength. Note that it can be difficult to locate the correct
wavelength if the lamp emits a line-rich spectrum in the region of interest. Therefore,
the appearance of the spectrum should be checked in the lamp catalogue.
5. Optimize the position of the lamp with the adjustment screws on the lamp holder.
1
 2

6. Select the measurement replicates (this should be 3 to 11), integration time. (should
be 3 to 5 seconds)
7. Check that the liquid trap is full.
SWITCH ON THE FLAME BETWEEN EXPERIMENTS
8. Visually optimize the burner’s position
9. Light the flame
10. Aspirate distilled water and wait until the decrease in absorption signal ceases then
zero the instrument.
11. Aspirate 2 ppm Cr, select a somewhat reducing flame and then:
a. Adjust the horizontal, rotational and vertical position of the burner until the
maximum absorption is obtained.
b. With a constant oxidant flow, adjust the acetylene flow for maximal signal.
c. Adjust the position of the glass impactor bead for maximal signal.
12. Aspirate distilled water and check the instrument zero level.
13. Determine the characteristic concentration for Cr under optimal conditions and
compare with corresponding data from the manual. Some cookbooks provide the
sensitivity in form of the calibration curve, the student should recalculate the required
characteristic concentration.

Definition
Characteristic concentration is the concentration giving 1% absorption of the lamp
intensity (e.g. 99% T), which corresponds to A = 0.0044 (denoted S1%).
Formula for calculating S1%:
[𝐶𝑟]
𝑆1% = 0.0044 ×
𝐴𝑏𝑠
Measured value S1% = _____________ppm
Typical value according to the manual = ____________ppm
Comments:

2
 3

EXPERIMENT 2
Determination of the optimal working range
Element: Cr
Parameters: As in Experiment 1 (optimal conditions)
Solutions: blank, 0.1; 0.2; 0.5; 1; 2; 5; 10; 20; 30; 50; and 80 ppm in HNO3 1%
Experiment
1. Optimize for Cr-determination as for Experiment 1
2. Prepare a calibration curve using all solutions – integration time 2s, n=8 (using the
instruments’ statistical functions).
3. From the calibration curve, calculate the standard deviation expressed in
concentration units. Thereafter plot the relative standard deviation (conc./conc.)
against the concentration of Cr.
4. Determine the optimal working range (e.g. the range for which the relative standard
deviation (RSD%) is less than 2% AND the sensitivity (S) is still better than
80%×S1%).
5. Calculate the detection limit, CL, for Cr from the relationship.
𝑆𝐵
𝐶𝐿 = 3 ×
𝑆
Where SB is the standard deviation for the blank (Abs)
S is the sensitivity, i.e. the slope of the calibration curve (Abs/conc.) at low
concentrations for Cr.

3
 4

EXPERIMENT 3
Effect of the spectral bandwidth on the calibration curve for nickel
Atomic absorption measurements are based on the assumption that a resonance line can
be isolated and that only light from one wavelength reaches the detector (Beer’s Law: A =
a.b.c). Other light reaches detector, a stray light effect will be obtained that reduces the
sensitivity and results in curvature of the calibration function. This can occur during the
determination of Ni if an overly wide slit is used, because other, nearby, non -absorbing
lines pass through the flame and spectrometer and reach the detector.
Element: Nickel (Ni)
Lamp current: 5 mA
Wavelength: 232.0 nm
Flame: acetylene/air
Solution: 0; 2; 4; 6; 8; and 10 ppm in HNO3 1%
Experiment
1. Optimize the instrument for Ni-determination.
2. Check the optimization by comparing your measured S1% value with the manual
value. The measured value should agree to within a factor of two of the manual
value. Report the results.
3. Prepare the calibration curves with the slit widths of 0.2; 0.5 and 1.0 nm SBW.
Optimize the wavelength after each change of slit width.
4. Plot the calibration curves.
5. Why do the calibration curves bend more with increasing SBW?
Comments

4
 5

EXPERIMENT 4
Chemical interferences, e.g. Al – interference on Mg
Chemical interferences occur in many situations in AA. Interferences can both increase and
decrease the absorption signal relative to the signal for a standard, even though the later
effect is the more common. Many interferences are well-documented and there are various
methods to avoid the errors which otherwise could occur.
1. Sample and standard are matched so that any interferences effect both to the same
degree.
2. Use of releasing agent.
3. Use of a high temperature flame
4. A releasing agent is a chemical that, when added to the sample, binds up the
interfering species such that the element to be determined is freed. A typical
example is the interfering effect of phosphates on Ca – determination. By adding La,
phosphate ion is complexed so that Ca can be atomized. The example in this
experiment shows the effect of a releasing agent.
Element: Magnesium (Mg)
Lamp current: 5 mA
Wavelength: 285.2 nm
SBW: 0.7 nm
Flame: acetylene/air
Solution: all solutions are prepared in HNO3 1%
a. 0.5 ppm Mg
b. 0.5 ppm Mg + 200 ppm Al
c. 0.5 ppm Mg + 200 ppm Al + 10000 ppm La
d. Blank 1 (200 ppm Al)
e. Blank 2 (200 ppm Al + 10000 ppm La)
In fact, a peristaltic pump is used to mix online the sample and the releasing reagent in a
certain ratio. This helps to save the expensive releasing reagent and to make the
preparation more precise, faster and less tedious. It is therefore only 3 solutions named
a., b., and d., are required.

5
 6

The peristaltic pump uses 2 peristaltic tubings for sample (large bore) and releasing
reagent (small bore). The inside diameters of the tubings should be selected so as the
flow rate ratio should be of 3:1 and the total flow rate should be within 4-6 mL/min at the
normal working range of the peristaltic pump.
Experiment
1. Optimize the instrument for Mg-determination.
2. Check as usual, the optimization by comparing your measured S1% value with the
manual value. Report the results.
3. Measure the absorbance for solutions from a. to e.
Explain the observed effects.
Solution Absorbance (air/C2H2)
Blank 1 (200 ppm Al)
Blank 2 (200 ppm Al + 10000 ppm La)
0.5 ppm Mg
0.5 ppm Mg + 200 ppm Al
0.5 ppm Mg + 200 ppm Al + 10000 ppm La
0.5 ppm Mg + 200 ppm Al (corrected for blank)
0.5 ppm Mg + 200 ppm Al + 10000 ppm La (corrected for blank)

Comments

6
 7

EXPERIMENT 5
Flame emission.
In flame emission the flames thermal energy is used to excite atoms in the ground state to a
higher energy level. When the excited atoms return to the ground state, light is emitted at a
characteristic wavelength. The intensity at this wavelength is measured, and since it is
proportional to the number of excited atoms, a calibration curve can be produced. Flame
emission is most effective for alkali metals. This is because their characteristic resonance
frequencies lie in the visible region of the spectrum where the energy of the excited state is
low. The degree of excitation in determined by Boltzmann’s distribution law.
𝑁∗ 𝐸
= 𝑘1 × 𝑒 −𝑘𝑇
𝑁𝑜
Where
- 𝑁 ∗ is the number of excited atoms. - E is excitation potential.
- 𝑁𝑜 is the number of atoms at ground state. - 𝑘 is Boltzmann’s constant.
- 𝑘1 is constant. - T is temperature (K).
Element: Sodium (Na)
Wavelength: 589.0 nm
SBW: 0.2 nm
Flame: acetylene/air
Integration time: 2s,
Number of replicates: 8
Solutions: blank; 0.1; 0.2; 0.5; 1; 2.0; 5.0 and 10.0 ppm Na in HNO31%.
Experiment
1. Optimize the instrument for Na-determination by flame emission. For details consult
the instrument manual.
2. The student should take tap or drinking water as sample. The sample must have no
suspended solid that could block the nebulizer of the FAAS.
3. Prepare a calibration curve and determine the concentration of Na in the sample.
Comments

7
 8

EXPERIMENT 6
Flame absorption (vs flame emission)
In principle, flame atomic absorption and atomic emission spectrometry are both used for
quantitation. This can be done using the same instrumental parameters such as
wavelengths, slit width, nebulization and atomization conditions, etc…. In practice, sodium,
potassium, lithium and even calcium can be quantitatively determined by atomic absorption
and atomic emission using the acetylene/air flame. However, the detection limit (a
combination of the sensitivity and the baseline noise) of the measurements of the two
modes of analysis i.e. atomic absorption and atomic emission should be taken into
consideration.
Element: Sodium (Na)
Wavelength: 589.0 nm
SBW: 0.2 nm
Flame: acetylene/air
Integration time: 2s,
Number of replicates: 8
Solutions: blank, 0.1; 0.2; 0.5; 1.0; 2.0; 5.0 and 10.0 ppm Na in HNO31%;
Experiment
a. Atomic absorption measurement
1. Optimize for Na-determination as described in Experiment 1
2. Prepare a calibration curve using all solutions – integration time 2s, n=8 (using
the instruments’ statistical functions).
b. Atomic emission measurement: those measurements have been performed in
experiment 5 and students can use the data for further evaluation as required.
Calculation
1. From the calibration curves obtained from each measurement modes, calculate
the standard deviation expressed in concentration units.
2. Calculate the detection limit, CL, for Na from the relationship.
𝑆𝐵
𝐶𝐿 = 3 ×
𝑆
Where SB is the standard deviation for the blank (Abs)
S is the sensitivity, i.e. the slope of the calibration curve (Abs or I/conc.) at low
concentrations for Na.

8
 9

Comments