Instrumental Analysis CHEM340

Atomic Spectroscopy Tutorial

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Describe the basic differences between atomic emission and atomic absorption.
Really the difference between absorption and emission spectroscopy, the source is the big
differences, there are other; go into your notes and make a table.
Explain why an internal standard can be used for ICP-OES but is not used for AAS.
This relates to the need for a Hollow Cathode Lamp in AAS which only deals with a single
element at a time, whereas ICP-OES is multi-element capable.
Concisely and clearly explain the importance of the hollow cathode lamp in AAS.
Concisely explain why chemical interferences are less common in ICP-OES than they are in
flame AAS.
To do with the much higher temperatures being able to breakdown stable compounds/oxides
and also the inert atmosphere.
Sodium atoms absorb at a wavelength of 589 nm.
What is the energy difference (in J) between the ground state and the excited state?
At a temperature of 2500 K, what is the ratio of excited state to ground state population
(N*/N0) if the relative degeneracy (g*/g0) is 2?

If you were asked this question in an exam you would be given a table with the relevant
constants all you would have to do is remember the relevant equation and plug in the data.

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7.

E = hc/ = 3.37 x10-19 J

N*/No = 1.15 x10-4
In which technique, atomic absorption or atomic emission is the flame temperature stability
more critical? Why?
Do the above calculation with a 10 C difference and then look at the % change in atoms in
the ground state compared to the % change in the excited state.
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. 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 follows:
Volume of
Fe taken (mL)
0.00
1.00
3.00
5.00
7.00
10.00

Absorbance
@ 248.3 nm
0.000
0.113
0.334
0.530
0.672
0.813

What is the true value of the Fe content in the municipals water (use absorbance in part 1).
Calculate the percent error between the results.
What assumption was made in part one that was not valid?

CHEM 340 Tutorial Atomic Spectroscopy

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Work out concentration of standard 0.1483g Fe in 250 mL is equivalent to 0.5932g/L =

593 ppm. A x 100 dilution was carried out on the solution 5.93 ppm Fe.
Only one standard solution prepared (bad analysis) so direct comparison of sample with
5.93ppm ppm
standard.

= 4.71ppmFe
0.813
0.646
take into account 5 dilution water solution contains 23.55 ppm or 23.55 g/mL
Convert the data on volumes of standard
solution into ppm (or whatever units you want)
draw graph.

Difference 23.55 - 19.65 = 3.9 as a %

3.9/19.65 x100 = 19.8%
The assumption was that the calibration was
linear. In AAS/FES graphs normally curve to
some extent. I always use at least 5
standards, some people use 3!
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9.

0.7
Absorbance

3.93 ppm is equivalent to (5 3.93) 19.65 ppm

in the water sample.

0.8

0.6
0.5
0.4
0.3
0.2

3.93ppm

0.1
0

3
4
ppm Fe

What are the main interferences that can occur in atomic spectroscopy, what can be done to
alleviate them? Look at your notes.
What is electrothermal atomisation or graphite furnace AAS, give the advantages and
disadvantages of this technique.
Look at your notes. It is about interferences, speed and detection limits. Make a table of
comparisions!

10. In electrothermal atomisation AAS analysis of lead in vinegar, ammonium nitrate and
ammonium phosphate can be added to the sample. What are the general names given to
these compounds and clearly explain how they function.
Ammonium nitrate is a matrix modifier and ammonium phosphate is a chemical modifier. Look
at your notes to see how they function.

Standards

11. What is the main advantage of a simultaneous ICP-OES? What is the most common
type of detector used in simultaneous ICP-OES instruments?
Fast multi-element analysis: Charge coupled detectors
12. 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
scandium (as an internal standard) was also added. The emission intensities for each of the
solutions was measured:
Sr Conc
Sr Emission
Sc Emission
(mg/L)
0.00
0.0
19.4
1.00
16.6
21.5
2.00
37.8
24.7
3.00
43.2
18.6
4.00
68.7
22.3
5.00
95.2
24.6
A
45.6
20.2
Samples
B
102.7
21.6
CHEM 340 Tutorial Atomic Spectroscopy

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Determine the strontium concentration (mg/L) in each of the samples.

Simple plot of Ratio of Sr:Sc emission to [Sr], the equation of the line is y = 0.7734x - 0.0041,
so A = 2.92 and B = 6.15 mg/L
Why do you not need the concentration of scandium to answer this question?
The concentration of Sc is not needed as we only use the Sc emission and as long as the [Sc]
is constant then it does not matter what is is.
13. Tributyl tin chloride (TBT) was a common pesticide added to paints used to prevent the
growth of barnacles on the hulls of ships. However, because of its persistent toxicity its use
has now been prohibited in many countries.
A common method of analysis of tributyl tin chloride in marine sediments is graphite furnace
AAS. A summary of the method is as follows.
A 0.5004 g sample of marine sediment was digested with 5.00 mL of acetic acid at 90C for
15 minutes. The sediment sample was centrifuged for 10 minutes at 2500 rpm. A 2.00 mL
aliquot was removed and 3 mL of an ammonium citrate buffer was added. The resulting
solution was diluted to final volume of 10.00 mL.
An aliquot of the sample was then analysed by graphite furnace AAS. The following conditions
were used.
20L
5 L
5 L
Step 1
Step 2
Step 3
Step 4

0.14

y = 0.0601x + 0.0006
2
R = 0.9999

0.12

105C for 20 s
- 1000C for 30 s
- 2300C for 5 s
- 2600C for 5 s

Peak area /s-1

Sample volume:
Ammonium nitrate:
Palladium nitrate:
Furnace conditions:

0.1
0.08
0.06
0.04
0.02
0
0

0.5

1.5

2.5

tin /ng

Results
Vol. of 100 ppb
Sn solution /L

Area of peak
/s-1

5 L

0.0310

10 L

0.0611

15 L

0.0909

20 L

0.1203

(a) What is the general name given to the ammonium nitrate solution?

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(b) What is the general name given to the palladium nitrate solution?

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(c) Explain in detail, the function of the palladium nitrate and ammonium nitrate
solutions.
(d) Briefly explain what is happening at the various furnace heating stages.

(4)
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You need to tell me about drying, ashing, atomising and cleaning

(e) If the signal for a 20 L aliquot of the sample was 0.0541 s-1, what was the
concentration of TBT (expressed as Sn) in the marine sediment?
The amount of Sn from the equation of the line is 0.89 ng.
0.89 ng in 20 L works out to be 44.2 ng/mL
This was from a 10 mL solution so we have 442 ng
But this was derived from 2 mL of a 5 mL solution so x (5/2) = 1105 ng
Convert this to a concentration 1105 / 0.5004 = 2208 ng/g 2.21 g/g
CHEM 340 Tutorial Atomic Spectroscopy

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(f) What other atomic absorption spectroscopic method of analysis could be used for the
trace analysis of tin?
You could hydride generation. Sn2+ + NaBH4 SnH2
14. In the analysis of a groundwater sample by AAS for Ba the presence of high amounts of
Ca gives rise to a molecular interference due to the presence of a broad molecular band
of CaOH.
(a) How will the use of deuterium background remove this problem?
(b) Why will swapping to a nitrous oxide flame resolve this problem?
Higher temperatures breaks down the oxide
(c) When they swapped to the N2O/C2H2 flame why did they swap burners?
To prevent an explosion
(d) On swapping to the N2O/C2H2 flame they added a large amount of K+. Why did they
do this? Explain the scientific principle.
Prevent ionisation
(e) If we swapped to an ICP-OES would there be a problem due to the presence of Ca?
No, the temperature is high enough to prevent formation of stable compounds,
however, you may end up with some spectral overlap if you were unlucky.
(f) Do we need to add K+ to the standards and sample like we did for part (d)?
No

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15. Sodium in tap water was analysed by flame emission spectroscopy using a simple flame
photometer utilising a butane/air flame. The following calibration graph was produced.
1200
30
25

1000

20
15

800

10
5
0

600

0.5

1.5

2.5

400

The insert is a zoomed in

area of the low concs.
The top line in each graph is
what a straight line would be.

200
0
0

20

40

60

80

100

Na /mg/L

(a) Why does the graph slope down at high concentrations? Self absorption
(b) What can be done, if anything, to get a straight line for the calibration? Dilute
(c) The inset shows a zoom of the low concentrations. Why does this show a negative
deviation from a straight line calibration? Ionisation
(d) What can be done to remedy, if anything, this part of the calibration graph?
Add ionisation suppressor
(e) Spectral interference can be a real problem in emission techniques, however in this
scenario we don't have to worry about spectra interference; why?
Temperature is so low that very few elements emit radiation therefore no spectral
overlap.
CHEM 340 Tutorial Atomic Spectroscopy

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