CHEM 4130 Final Exam April 28, 2011 Name ________________________________________________ Instructions: There are five questions on eleven

pages, not counting this cover page; please make sure you have them all. Please be complete and specific in your answers. You must show all of your work, and I must be able to logically follow your problem solving. You will not get credit for the correct answer if I cannot see how you arrived at that answer. If you have any questions concerning the exam, please ask! Some useful information: Plancks constant = 6.62 x 10-34 J-s 1 einstein = 6.02 x 1023 photons Boltzmanns constant = 1.3805 x 10-23 J/K Score: 12345___________________________ /310 speed of light = 3.00 x 108 m/s

1. (30 points) On our first in-class exam, I asked you about Alprazolam, which is a potent, short-acting drug of the benzodiazepam class, and you may know it as Xanax (ahem). Its primary use is for anxiety disorder and panic attacks, and it also has some recreational use (so Ive heard). The octanol - water partition coefficient of alprazolam is 132. You may ignore any possible acid-base character for the following questions (youre welcome).

a. Starting with 0.100 mole of alprazolam, and 100 mL of each phase, what is the relative concentration (the concentration ratio) in the two phases at equilibrium?

b. Starting with 0.100 mole of alprazolam, 100 mL of octanol and 250 mL of water, what is the relative concentration (the concentration ratio) in the two phases at equilibrium?

c. If I wanted to move the majority of the compound to the aqueous phase, I could do this with the judicious choice of a buffer. No longer ignoring the acid base character of the drug, its pKb is actually 11.6. What buffer pH would you choose to insure the majority of the drug will go to the aqueous phase? Briefly defend your answer.

2. (60 points) One of the separations techniques we discussed is capillary electrophoresis (CE), which only became commercially available about 15 years ago. a. Draw a block diagram for a CE instrument, and label all components.

b. What is the separation mechanism for CE? That is, what physical phenomenon brings about the separation?

c. The enabling technology for CE was the invention of fused silica. Why are capillary columns ( 100 m) necessary for this experiment? That is, why wouldnt free zone electrophoresis work in larger diameter tubes?

d. By far, the most popular mode of LC is reversed-phase. What do we mean by reversed-phase LC? Identify a common reversed phase stationary phase material.

e. Perhaps the most powerful experiment we can run in LC is a gradient elution separation. Explain the concept and advantages of gradient elution, and identify a reasonable starting and ending mobile phase.

f. A friend of yours brags they have just made the worlds most efficient chromatographic column, and that they calculated an efficiency of 50,000 plates. Being the brains of your friendship (because you had this course, of course!), you know they havent given you enough information to make that claim. How would you better evaluate the efficiency to see if in fact they are on their way to Fame and Fortune (and you can tag along to keep them honest).

3. (60 points) For the following questions, give a short answer. That is, you should be able to satisfactorily answer the question in one or two sentences. There is no reward for length of answer. Please do not try to surround the answer; I will not pick the correct answer from a list of guesses. Gas chromatography was the first instrumentalized method of chemical separations, and is still the fastest, cheapes, and easiest method of separations for those compounds amenable to the technique. a. We said in class the open-tubular columns (or capillary columns) is the preferred column technology for GC. Why did packed-column GC fall into disfavor?

b. The coupling of the GC with a mass spectrometer provides a very powerful means of chemical analysis. Two of the ionization sources we discussed for mass spectrometry are suitable for GC, and two are not. Which two would work? Briefly justify your answer.

c. In discussing GC stationary phases, we can break their interactions with solutes into two broad categories; polar and nonpolar. What controls retention of a solute on a polar stationary phase? Explain.

d. Still thinking of GC stationary phases, can the retention of any solute ever be less on a polar phase than on a nonpolar phase of the same thickness and at the same column temperature? Explain.

e. Still thinking of GC stationary phases, can the retention of any solute ever be greater on a polar phase than on a nonpolar phase of the same thickness and at the same column temperature? Explain.

f. Draw a block diagram of a GC instrument, and label the components.

4. (110 points) In the UV-visible region of the electromagnetic spectrum we perform absorbance, fluorescence and phosphorescence, atomic emission, and Raman spectroscopies. a. What is the approximate wavelength range for the usable portion of the UV-visible spectrum?

b. What is the approximate wavelength range where * transitions occur?

c. Why is this called the vacuum UV?

d. What is the approximate wavelength range for the fundamental IR region? You may list either wavelengths or wavenumbers.

e. This is a Raman spectrum of a 3 L sample of pure carbon tetrachloride, taken with a He-Ne laser. Label the Rayleigh scattering peak, and identify which set of peaks is from Stokes scattering and which from anti-Stokes scattering. Also briefly explain your decision making process.

f. Draw a block diagram of a Raman spectrometer. Label the components and identify what source and what detector you would use.

g. Atomic spectral lines are truly lines, rather than broad bands. Briefly explain why molecular spectra show broad bands, and atomic spectra are lines.

h. Atomic emission spectroscopy became a hot technique (Sorry.I tired to stop myself. Really) when plasma sources became commercially available. Why is a hot flame (or plasma) an advantage for atomic emission measurements?

i. Below is a diagram of a typical burner head for atomic absorption spectroscopy. The radiation of the source lamp is directed down the long axis of the burner, because this gives much better limits of detection than directing the radiation across the short axis. These are known as slot burners because of their design. Explain the difference in LOD values resulting from radiation across the different axes.

j. Solder used for electrical circuitry is usually some composition of tin (118.7 amu) and lead (207.2 amu). An analytical chemist wanted to measure the composition of solder by atomic spectroscopy; tin has a transition at 284.00 nm and lead has a transition at 283.31 nm. If she performed this analysis by inductively coupled plasma atomic emission, the resolution of her monochromator would have to be much greater than if she used atomic absorption analysis. Why would these two elements cause resolution problems with ICP-AE and not AA?

k. Would there be problems in the simultaneous determination of these elements by ICP mass spectrometry? Briefly explain.

5. (50 points) For the following separation or measurement problems pick the best technique from among those we discussed this semester. For both GC and LC, also pick a suitable detector. If you choose GC, differentiate between packed and open tubular columns. If you pick LC, pick a separation mechanism (i.e., reversed-phase, ion exchange, size exclusion, etc.). If you pick mass spectrometry, also choose an ionization method. Justify your answer in one or two sentences. a. Nicotine constitutes from 0.6 to 3% of the dry weight of tobacco, and is an addictive substance. The FDA has long considered regulating nicotine as a drug, and a recent study has investigated the nicotine content of smokeless tobaccos. L. A. Ciolino, H. A. McCauley, D. B. Fraser and K. A. Wolnik, The relative buffering capacities of saliva and moist snuff: Implications for nicotine absorption, J. Anal. Toxicol. 25 (2001) 15-25. In that paper they invented a (great!) new unit, eq / pinch ! (Who said scientists have no sense of humor?) How would you measure nicotine in tobacco?

b. After the BP oil spill, NOAA (National Oceanic and Atmospheric Administration) began routine testing of gulf caught seafood for 19 different polyaromatic hydrocarbons, as those would represent a clear indication of contamination by the leaking oil. How would you run these tests?

c. Cefotaxime is a wide-spectrum, third generation cephalosporin antibiotic. To study pharmacokinetics, you need to determine both the parent compound and any metabolites in blood plasma.

d. How could you quantitatively determine the effectiveness of various sunscreen lotions for the purpose of assigning SPF ratings?

e. You need to perform a quantitative determination of lead in a drinking water sample in an older home you are thinking of buying. It was not until 1986 that lead pipes and lead solder were banned from drinking water supply systems.