Analytical Chemistry

CHEM 221
Instrumental Analysis
EXAM #1
February 18, 2015
Name:
INSTRUCTIONS:
Read through the entire exam before you begin. Answer all of the
questions. For questions involving calculations, show all of your work -- HOW you arrived at a
particular answer is MORE important than the answer itself!
The entire exam is worth a total of 200 points. Attached are a periodic table and a formula
sheet jam-packed with useful stuff!
Good Luck!
CYCLIC VOLTAMMETRY
1. You are working in an environmental analysis lab and focusing on the determination of hexavalent
chromium (Cr(VI)) in drinking water samples. Five replicates are run of the first sample and the
following are data (averages and standard deviations) obtained for the Cr(VI) signal:
Blank:
Sample:
avg=0.03, std dev=0.01

avg=0.05, std dev=0.01
a. [20 pts] Based on the average signal obtained for the sample, you determine from your standard
calibration plot that the water sample contains 0.5 ppb of Cr(VI), five times the MCL (Maximum
Contamination Limit) proposed in California for Cr(VI) in drinking water!. Your supervisor, after
looking at the data, says that there is no detectable amount of Cr(VI) in the sample. Who is right and
why? (NOTE: your response should be based on the above data. HINT: you may wish to calculate the
S/N for the sample data.)
b. [15 pts] If a 10.0 ppb Cr(VI) standard gave an average signal of 0.43, what would the detection
limit (ppb Cr(VI)) be for the determination of Cr(VI) using this instrument?
2. [10 pts] What is usually the most likely decay route to the ground state after a molecule or atom
absorbs a photon of electromagnetic radiation (EMR)? Does this decay process result in the emission
of a photon of EMR?
3. a. [15 pts] After 4 years of hard work in the lab, you finally have a 3-day holiday weekend (72 hours)
to obtain a spectrum of the reaction mixture that can definitively determine whether the reaction
mechanism youve proposed in your dissertation research is correct. You watch the first spectrum
pop up on the display and find that the critical spectral feature is buried in the background noise of
the spectrum. If, after signal averaging 55 spectra, the S/N for this feature is 0.50, calculate the S/N
for this spectral feature after signal averaging the spectrum for the entire 3-day weekend (72 hours).
Assume that it takes 1.0 minutes to scan a single spectrum.
b. [15 pts] Alas, you find that the actual S/N of the feature after signal averaging for the weekend is LESS
than you predicted, above. Explain and identify the likely noise source that would account for this
discrepancy.
4. The following chromatogram was the result of your very first experiment performed as part of your
Ph.D. research:
a. [20 pts] Calculate and then report an estimate of the S/N for the first peak (i.e., the one eluting at
about 18 seconds). Is it above the detection limit? Show your work in the space below and, as
appropriate, on the figure above.
b. [15 pts] Identify and (briefly) describe one method you can use to improve the S/N, using the existing
dataset for this chromatogram.
5. A current-sampled dc polarogram of an unknown solution containing either Cd or Cr was acquired

and found to have a limiting current of 5.00 A. From the rising portion of the polarographic wave,
the following data were obtained:
E(applied), volts
-0.475
-0.490
-0.510
-0.525
Current, A
0.62
1.57
3.43
4.38
Further processing of these data produced the following plot, with the included linear least squares
fit to the data:
a. [15 pts] From the data and plot provided above, determine the value of Eo for the reduction
you must show how you determined Eo and any assumption implicit in that determination in order
to receive credit for your answer.
b. [15 pts] The reduction of Cr3+ to Cr2+ as well as the reduction of Cd2+ to Cd have the same Eo
(and it is equal to the Eo value determined in part a, above). Based on the data provided, is the
polarographic reduction wave due to Cr3+ or Cd2+?
5. QUICKIES (20 points each)

a. For transitions between two electronic energy states, the transition probabilities for absorption
and stimulated emission are numerically equal to each other. Why doesnt absorption cancel the
effects of stimulated emission in a LASER?
b. Explain how diffusion-controlled mass transport of oxidized species to the electrode surface is
ensured in hydrodynamic voltammetry, even though the solution is stirred.
c. Briefly describe the origin of the residual or background current in a voltammetric experiment.

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CHEM 221

avg=0.03, std dev=0.01

5. A current-sampled dc polarogram of an unknown solution containing either Cd or Cr was acquired

5. QUICKIES (20 points each)

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