Chem 155 Quiz 3 Review Topics:

Quiz 3 outline

1. Atomic absorption spectrometry

a. Principles of FAAS – where selectivity and sensitivity arise
b. Spectrometer design
c. Atomization processes
d. Sensitvitiy and atomization: protecting agents, releasing agents, radiation
buffers
e. Bandwidth considerations and calibration curve linearity
2. Atomic emission spectrometry
a. ICP – principles
i. Ar plasma
ii. Inductive coupling
iii. torch design
b. Ar-plasmas versus flames as atomizers
c. Bandwidth considerations and noise
d. Stability considerations, matrix effects and internal standards
e. Monochromators, simultaneous multielement detection, Echelle designs
and CCD array detection
3. UV-Vis absorbance spectrometry
a. Beer’s law
b. Molecular cross sections
c. Non-Beer’s law behavior
4. UV-Vis spectroscopy of Molecules
a. Pi, sigma, pistar and sigmastar molecular orbitals
b. Broad classifications
a.   *
b. n *
c. n  *,  *
c. Solvatochromism
a. Increase in solvent polarity  blue shift implies n  * character
b. Increase in solvent polarity  blue shift implies  * character
c. Conjugation usually:
i. Increases extinction of and
ii. red-shifts n  *,  * type transitions
d. Aromatic substitution with (-) charge density (e.g. –O-) can
destabilize pi system and red shift  *
e. Aromatic substitution with (+) charge density (e.g. -NH3+) can
stabilize pi system and blue shift  *
d. Aqueous transiton metal ions
a. Vis transitions are d-d based and weak
b. Ligands like SCN- and o-phenanthroline can make charge transfer
complexes with large  and therefore low DL (CMIN).
e. Photometric titration
a. uses CT and VT to determine concentration at inflection of A vs VT
b. does not use A, therefore does not
i. require strict Beer’s law behavior
ii. is insensitive to matrix effects that could change .
 Chem 155 Quiz 3 Review Topics:

1. Fill in the empty boxes consistent with the diagram. SEE NOTES
In boxes 1 to 6 inddicate in what form the
analyte is likely to exist: In boxes 7 and 8 below put the
Diluted gas 6 equation that relates concentration
and light power corresponding to
emission (7) and absorption (8):


or flame   

Emission
Excited gas atoms or 5 Optimal for atomic emission 7
ions spectroscopy (AES)

 h Absorption
Gas atoms 4 Optimal for atomic absorption8
HCL spectroscopy (AAS)


 Path of analyte through plasma

Gas molecules 3


Solid particles 2


Liquid droplets 1


Nebulize

Liquds Solids Gases

Chem 155 Quiz 3 Review Topics:

2. Compare Ar-plasma and air-C2H2 flames in the following categories:

Quality circle correct
Electron Ar-plasma has higher lower equal air-C2H2 flame.
density e- density than
Temperature Ar-plasma is higher lower equal air-C2H2 flame.
temperature than
Chemical Ar-plasma has higher lower equal air-C2H2 flame.
reactivity reactivity than
Formation of Ar-plasma is higher lower equal air-C2H2 flame.
oxides likelihood than
Atomization Ar-plasma is superior inferior air-C2H2 flame.
efficiency equal to

3. Compare inductively coupled plasma atomic emission spectrometry (ICP-AES)

to flame atomic absorption spectroscopy (FAAS) in the following categories:
Quality circle correct
choice
Cost to buy / ICP-AES is higher, lower, FAAS
operate equal cost than
Simultaneous ICP-AES is more, less, FAAS
Multielement equally
detection competent than
Dynamic Range ICP-AES has larger, smaller, FAAS
equal dynamic
range than
Detection Limit ICP-AES has higher, lower, FAAS
equal detection
limits than

4. Because of the mulit-element capability and atomization / temperature sensitivity

of emission intensity, the following analytical method has proved highly
successful in ICP-AES:
a. Standard additions c. D2 background correction
b. Internal standards d. nonlinear calibration analysis
5. Formation of oxides or molecular species in flame/plasma can be suppressed
by:
a. EDTA or other complexing agents
b. Addition of KCl to the matrix
c. Addition of oxyanions such as sulfate or phosphate.
d. Standard additions methods.
6. Ionization of analyte atoms in flame/plasma can be suppressed by:
a. EDTA or other complexing agents
b. Addition of KCl to the matrix
c. Addition of oxyanions such as sulfate or phosphate.
d. Internal standards methods.
Chem 155 Quiz 3 Review Topics:

7. Fill in the following table assuming Beer’s law is obeyed:

Absorbance P Po %T C/M
0.00 1 1.00 100 0.0000
0.30 0.5 1.00 50 0.0003
1.00 0.1 1.00 10 0.001
2.00 0.01 1.00 1 0.002
3.00 0.001 1.00 0.1 0.003

log
%T  A %T A
A  10 %T 100 10
 100  100

 0.3 1 2 3
100 10  50 100 10  10 100 10 1 100 10  0.1

P %T
%T 100 P  P0
P0 100

8. Based on this, comment on the relative reliability (i.e. accuracy or precision) of

absorbance measurements at A=1 and A=3.

Absorbance is much more reliable at A < 2 because the light transmittance

quickly becomes too small to measure as absorbance increases.

9. Associate each of the

following spectra with
the following solvent:
a. Gas phase
b. Water
c. Cyclohexane
d. Perfluorooctane
e. Dioxane
Chem 155 Quiz 3 Review Topics:

10. What is the function of the reagent blank in the metals experiment?
To evaluate analyte levels in the blank and assess interferants from sample
preparation steps.

11. What is the function of the spike recovery analysis in the metals experiment?
To validate the analysis especially the sample preparation steps and show that
they do not underreport analyte concentrations.

12. Circle the correct answer. In comparison to double-beam scanning

spectrophotometers, diode array spectrophotometers are:
Quality Spectrometer Type
Diode Array Double Beam
more accurate absorbance x
more accurate wavelength x
much faster x
more complex x
more expensive x

13. Solvatochromism: correlate the following:

Spectral Shift on transfer from hexane to alcohol
Predominant effect seen in spectrum is:
Transition Shift nonbonding (n) * orbital
type direction orbital
red blue stabilize destabilize stabilize destabilize
n* x x
* x x
14. Aromatic substitution:
Spectral Shift on 254 nm * transition of benzene upon substitution with:
Substituent Shift Effect on  orbital Effect on * orbital
direction
red blue stabilize destabilize stabilize destabilize
OH x x
-
O xx xx
NH2 xx xx
+
NH3 xx xx
Chem 155 Quiz 3 Review Topics:

15. Assuming that the absorption noise in your spectrometer, σA = 0.001, what is
your detection limit for Fe+2 aquo (MAX=1.0 M-1cm-1) and FeSCN+2
(MAX=5000 M-1cm-1) in the 300-800 nm range?
a. CMIN=3sb/m
b. sb = A
c. m = slope of calibration curve
d. slope of calibration curve is  (M-1cm-1)
3 sb 3 0.001 3
CM  3  10 cmM
m 1 1
1 M cm

3 0.001 7
 6  10 cmM
1 1
5000M cm

16. Photometric titration of Fe+3 with SCN- solution to make FeSCN would give
what titration curve?

17. Why such a photometric titration be more accurate than relying on Beer’s law to
make the concentration estimate? Select all that apply:
a. Matrix effects are unimportant in photometric titration.
b. Photometric titration uses an internal standard.
c. Beer’s law is always obeyed in photometric titrations.
d. Beer’s law need not be obeyed in photometric titrations.
e. Photometric titration relies on titrant volume and titrant
concentration which can be measured accurately.
f. Photometric titration relies on absolute absorbance which can be
measured exactly.
g. Photometric titration does not require sample preparation.