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Department of Chemistry
Chem. 572 Advanced Instrumental Analyses
Instrumentation and interpretation of spectra
= 2 - log %T
= 2 - log %T
(a) When 0.140 mL of solution A was analyzed, an absorbance of 0.829 was recorded. A
blank carried through the same procedure gave an absorbance of 0.017. Find the
molar absorptivity of blue product.
(b) A solution of the phosphate-containing iron-storage protein ferritin was analyzed by
this procedure. The unknown contained 1.35 mg of ferritin, which was digested in a
total volume of 1.00 mL to release phosphate from the protein. Then 0.300 mL of this
solution was analyzed by the procedure above and found to give an absorbance of
0.836. A blank carried through this procedure gave an absorbance of 0.038. Find the
weight percent of phosphorus in the ferritin.
13. You are a supervisor in a laboratory which focuses on the determination of trace and
ultra-trace levels of toxic substances in water samples. Usually, for the determination of
Pb in water, a Graphite Furnace Atomic Absorption Spectrophotometer (GFAAS) is
used but, since it was down for repairs, one of the technicians that you supervise
decided to use the operable Flame AAS instrument. After establishing that absorbance
varied linearly with the amount of Pb, the following absorbance value data (for 5
replicate measurements) were obtained for a blank and for a sample submitted for
analysis: submitted for analysis:
a) Based on the average absorbance value obtained for the sample, the technician
reported that the water sample contained 500 ppb Pb (15 ppb Pb is the maximum Pb
level allowed in drinking water!). As the lab supervisor, you are ultimately
responsible for the analysis results that are reported. Should this result be reported?
EXPLAIN. (NOTE: your response should be based on the above data. HINT: you
may wish to calculate the S/N for the sample data . . . )
b) If a 5000 ppb Pb standard gave an average absorbance value of 0.024, what would the
detection limit (ppb Pb) be for the determination of Pb using this instrument?
14. a)
The
Pd
4,4'-bis(dimethylamino)thiobenzophenone
complex,
in
aqueous
solution,absorbs very strongly in the UV/Vis spectral region, with a molar absorptivity
of 2.12 x 105. Assuming that the minimum measurable absorbance is 0.010 and that a
cell with a 2.50-cm pathlength is available, what is the lowest possible concentration
(ppb) of Pd that can be determinedspectrophotometrically
b) Assuming that the readout uncertainty of the spectrophotometer is 0.10 %-T, what is
the %-relative uncertainty in making an absorbance measurement of 0.010?
c) Assuming that the Pd 4,4'-bis(dimethylamino)thiobenzophenone system follows
Beer's Law in this concentration range, calculate the detection limit for Pd with this
system (i.e., the concentration of Pd, in ppb, that wouldgive a S/N = 3).
d) Assuming that the Pd 4,4'-bis(dimethylamino) thiobenzophenone absorption
bandwidth is 50 nm and the monochromatoreffis 5 nm, what effect would a 10x
increase in the slitwidth of the monochromator have on theapplicability of Beers
Law with this system? Illustrate with a Beers Law plot.
15. a) The most common detector used in FT-IR is the so-called TGS (Triglycine Sulfate)
detector which is a thermal detector and has poor sensitivity. Explain why a
photoemissive detector (like the photomultiplier tube commonly used in UV/Vis
spectrometry) cannot be used in FT-IR.
b) Arrange the following stretches in order of increasing vibration frequency: C-H, C-C,
CC, C=O, C=C. Briefly justify/explain your answer.
c) How many fundamental vibrational modes are predicted for water (H2O)? Diagram
one vibrational mode that you would expect to be IR active.
16. Elemental analysis at ppb levels can be performed using ICP atomic emission
spectrometry (ICP-AES), graphite furnace atomic absorption spectrometry (GFAAS),
and anodic stripping voltammetry (ASV). Which one of these methods would be best
for the daily determination of carcinogenic Cr(VI) in water discharged from a
manufacturing facility? Briefly justify your choice.
17. Which of the following types of analysis involves interaction of the sample with the
least amount of energy? IR, NMR, UV-Vis, MS ,
18. Deduce the structure that corresponds to this spectral data. Mass spectrum: M: m/z 148
(100 %); M + 1: m/z 149 (11.25 %); M + 2: m/z 150 (0.54 %).
H-NMR: 7.5 - 8.0 ppm (multiplet, integral = 2.5), 3.0 ppm (triplet, integral = 1), 1.8 ppm
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(singlet), 137.0 ppm (singlet), 132.8 ppm (doublet), 128.5 ppm (doublet), 128.0 ppm
(doublet), 40.4 ppm (triplet), 17.7 ppm (triplet), 13.8 ppm (quartet).
19. Provide a molecular structure that is consistent with the spectral data. Mass spectrum:
M: m/z 132,( 100%); M + 1: m/z 133, 96.89%); M + 2: m/z 134, (1.42%).
1H-NMR: 4.0 ppm (triplet, integral = 1.0); 3.9 ppm (singlet, integral = 1.5); 3.0 ppm
(singlet, integral = 1.0); 1.3 ppm (sextet, integral = 1.0); 0.9 ppm (triplet, integral = 1.5).
13C-NMR (DEPT): 171 ppm (singlet), 70 ppm (triplet), 56 ppm (triplet), 52 ppm
(quartet), 30ppm (triplet), 18 ppm (quartet).
20. Propose a structure for the compound C5H10O based on the following spectroscopic data
21. Propose a structure for the compound C 6H12O2 based on the following spectroscopic
data
22. For each of the following compounds, calculate the number of multiplets for each band
and their relative areas: (a) C1(CH2)3CI; (b) CH3CHBrCH3; (c) CH3CH2OCH3.
23. The proton NMR spectra shown in Figure below are for colorless, isomeric liquids
containing only carbonand hydrogen. Identify the two compounds.
FIGURE NMR spectra for two organic Isomers in COCI]. (Courtesy of Varian Inc
...Palo Alto. CA.)
24. The two mass spectra belong to the isomers of C 6H12O below. The peak at m/z 71 is
C4H7O+, which comes from loss of an ethyl group (CH 3CH2., 29 Da). What is the
expected intensity of m/z 72 relative to that of m/z 71?
Mass spectra of isomeric ketones with the composition C 6H12O from NIST/EPA/NIH
MassSpectral Database.
25. Predict the splitting patterns (number of lines for each signal) you would predict for
each type of carbon and proton in the molecule below
26. Which bond has a higher (= larger) infrared vibrational frequency: C=N or C=S?
Explain briefly.
27. Which one of the following bonds has the highest/largest infrared vibrational
frequency?
a. C-N
b. C-O
c. C-F
d. C-C
e. C-B
28. How many signals would you see in the
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Compound?
29. Describe how you would quantitatively determine the following drugs using IR.