CE 772
18 Dec 1997
FINAL EXAM
Open Book, Open Notes
Answer five of the following eight questions:
(each is
worth 20%)
1. Sample Preparation
A 1-liter aqueous sample is being extracted in a
sequential batch mode with diethyl ether.
Pollutant "Y" has an ether/water dimensionless partition
coefficient of 95.
a. After
one extraction with 25 mL of ether, how much of the original amount of pollutant
"Y" remains in the water phase?
b. If it is
desired that 99% of pollutant "Y" be extracted into the ether phase,
how many sequential extractions using 25 mL of the organic phase must be made?
2. Chromatographic Theory
An extract of drinking water shows two closely-eluting
GC (ECD) peaks which are believed to be methyl trichloroacetate and methyl
dichloroacetate. The column used is a 2
m x 4 mm glass column packed with 3% SP-1000 on 100/200 mesh Supelcoport. The stationary phase weight is 2.54 g, and it
has a density of 0.699 g/mL. The inlet
column pressure was 22 psig, the outlet flow rate was 60 mL/min, and the column
temperature was isothermal at 65oC.
Retention Time (min) |
Peak Width (min) |
Identity |
0.40 |
|
Unretained solvent |
8.85 |
0.63 |
methyl trichloroacetate? |
9.55 |
0.71 |
methyl dichloroacetate? |
a.
Calculate k' for each of the suspected esters
b.
Calculate and average number of theoretical plates
c. Describe
how you would determine the true identity of the two suspected esters. Your only have access to a GC with an FID
and an ECD.
3. GC/MS
Interpret the mass spectrum summarized on the table
below and the attached figure. Indicate
your rationale for the determination of empirical formulae for each of the
major fragment ions, as well as for the molecular ion. Propose a structure for the parent molecule.
m/e |
% Abundance |
m/e |
% Abundance |
28 |
0.9 |
70 |
5.1 |
29 |
0.6 |
71 |
2.1 |
30 |
15.1 |
72 |
100 |
31 |
0.2 |
73 |
3.7 |
42 |
16.2 |
86 |
1.5 |
43 |
14.1 |
100 |
2.1 |
44 |
39.2 |
112 |
1.1 |
45 |
1.0 |
113 |
0.6 |
55 |
2.1 |
114 |
25.8 |
56 |
3.1 |
115 |
2.1 |
57 |
4.4 |
127 |
0.8 |
58 |
5.3 |
128 |
0.5 |
|
|
129 |
18.1 |
|
|
130 |
1.7 |
4. General
You have a surface water sample that you suspect to be
contaminated with pentabromobenzoic acid (C6Br5COOH). This aromatic compound is considered to be
very toxic, so you are interested in trace quantities. One of your concerns is interference from
naturally-occurring organic matter which is present at concentrations that are
3 or more orders of magnitude greater than the analyte. Propose how you would analyze such a sample
for pentabromobenzoic acid. Explain the
reasons for your choice of methods and procedures. Consider the following points:
a.
extraction and/or concentration
b.
sample cleanup
c.
derivatization
d.
separation and quantification
e.
identification
5. Error Analysis
A series of replicate measurements were made for
pollutant "X" in identical aliquots of a sludge sample. The measurements are as follows:
33.5 µg |
35.9 µg |
29.1 µg |
22.6 µg |
35.0 µg |
38.2 µg |
a.
What is the
mean and relative standard deviation for these measurements?
b.
Assuming
these measurements were all made on aliquots of precisely 5 g each, what is the
mean concentration in ppm, and the associated relative standard deviation?
c.
Repeat
"b", but this time assume that the standard error on the weight
measurements for each aliquot was 0.5 g
6. UV-Vis Spectrophotometry
Answer each of the following as either true (T) or
false (F).
a. Double-beam spectrophotometers exhibit a greater light throughput
than single-beam instruments
b. Diode array spectrophotometers are commonly reverse optics
(geometry) instruments
c. Normal optics (geometry) spectrophotometers are more susceptible
to problems with sample photodegredation
d. Stray light will result in abnormally high absorbance readings
with double-beam instruments
e. Absorbance is affected by sample pH
f. Transmission of polychromatic radiation through a monochromator
leads to positive deviations from Beer's Law
g. Double dispersing spectrophotometers are less subject to stray
light.
7. TOC
Propose a method for the analysis of Total Organic
Carbon (TOC) in solid samples (soils/sediments). Consider matrix problems, interferents, analyte recovery and any
other pertinent issues. Be as specific
as you can. How could one best verify
the accuracy of this method?
8. General
Bromate (BrO3)is a disinfection byproduct
found in some drinking waters containing small amounts of naturally-occurring
bromide. Since it is a known animal
carcinogen, it will probably be regulated (at the high ppb range) in the next
few years by U.S. EPA. However, at the
present, one obstacle to the regulation of this chemical is the lack of an
accepted method for its analysis at these low levels. In particular, classical sample concentration techniques give
losses, because bromate is a strong general oxidant (i.e., it is subject to
chemical reduction). Discuss the issue
of bromate analysis and propose an outline for a sensitive (detection limit
~100 ppb) analytical method. Be as
specific as you can. Discuss important
analyte properties that determine how it can be analyzed at low concentrations.
9. GC/MS
Interpret the attached mass spectrum. Indicate your rationale for the
determination of empirical formulae for each of the major fragment ions, as
well as for the molecular ion. Propose
a structure for the parent molecule.