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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: Planck’s constant = 6.62 x 10-34 J-s 1 einstein = 6.02 x 1023 photons Boltzmann’s constant = 1.3805 x 10-23 J/K Score: 12345___________________________ /310 speed of light = 3.00 x 108 m/s

100 mole of alprazolam. 100 mL of octanol and 250 mL of water. I asked you about Alprazolam.1. and you may know it as Xanax (ahem). Starting with 0. Starting with 0. I could do this with the judicious choice of a buffer. What buffer pH would you choose to insure the majority of the drug will go to the aqueous phase? Briefly defend your answer. its pKb is actually 11. a. and it also has some recreational use (so I’ve heard).water partition coefficient of alprazolam is 132. which is a potent.100 mole of alprazolam. (30 points) On our first in-class exam. Its primary use is for anxiety disorder and panic attacks. short-acting drug of the benzodiazepam class.6. what is the relative concentration (the concentration ratio) in the two phases at equilibrium? b. . and 100 mL of each phase. If I wanted to move the majority of the compound to the aqueous phase. You may ignore any possible acid-base character for the following questions (you’re welcome). The octanol . No longer ignoring the acid – base character of the drug. what is the relative concentration (the concentration ratio) in the two phases at equilibrium? c.

Why are capillary columns (≤ 100 µm) necessary for this experiment? That is.2. what physical phenomenon brings about the separation? c. which only became commercially available about 15 years ago. and label all components. Draw a block diagram for a CE instrument. a. (60 points) One of the separations techniques we discussed is capillary electrophoresis (CE). why wouldn’t free zone electrophoresis work in larger diameter tubes? . The enabling technology for CE was the invention of fused silica. What is the separation mechanism for CE? That is. b.

and that they calculated an efficiency of 50. .000 plates. f. What do we mean by reversed-phase LC? Identify a common reversed phase stationary phase material. By far. Being the brains of your friendship (because you had this course. Perhaps the most powerful experiment we can run in LC is a gradient elution separation. of course!). Explain the concept and advantages of gradient elution. e. the most popular mode of LC is reversed-phase. and identify a reasonable starting and ending mobile phase. A friend of yours brags they have just made the world’s most efficient chromatographic column. you know they haven’t given you enough information to make that claim.d. 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).

What controls retention of a solute on a polar stationary phase? Explain. In discussing GC stationary phases. There is no reward for length of answer. c. Please do not try to “surround” the answer. polar and nonpolar. I will not pick the correct answer from a list of guesses. Which two would work? Briefly justify your answer.3. The coupling of the GC with a mass spectrometer provides a very powerful means of chemical analysis. (60 points) For the following questions. That is. we can break their interactions with solutes into two broad categories. Why did packed-column GC fall into disfavor? b. and is still the fastest. you should be able to satisfactorily answer the question in one or two sentences. and easiest method of separations for those compounds amenable to the technique. cheapes. and two are not. Two of the ionization sources we discussed for mass spectrometry are suitable for GC. a. give a “short answer”. . Gas chromatography was the first instrumentalized method of chemical separations. We said in class the open-tubular columns (or capillary columns) is the preferred column technology for GC.

e. and label the components. . Draw a block diagram of a GC instrument.d. 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. 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. Still thinking of GC stationary phases.

4. atomic emission. (110 points) In the UV-visible region of the electromagnetic spectrum we perform absorbance. What is the approximate wavelength range where σ → σ* transitions occur? c. . fluorescence and phosphorescence. What is the approximate wavelength range for the fundamental IR region? You may list either wavelengths or wavenumbers. and Raman spectroscopies. a. What is the approximate wavelength range for the usable portion of the UV-visible spectrum? b. Why is this called the “vacuum UV”? d.

and identify which set of peaks is from Stokes scattering and which from anti-Stokes scattering. taken with a He-Ne laser. f. Also briefly explain your decision making process. . Label the components and identify what source and what detector you would use.e. This is a Raman spectrum of a 3 µL sample of pure carbon tetrachloride. Draw a block diagram of a Raman spectrometer. Label the Rayleigh scattering peak.

rather than broad bands.I tired to stop myself…. and atomic spectra are lines. These are known as “slot burners” because of their design. Why is a hot flame (or plasma) an advantage for atomic emission measurements? i. The radiation of the source lamp is directed down the long axis of the burner. Briefly explain why molecular spectra show broad bands. Atomic emission spectroscopy became a hot technique (Sorry…. Really) when plasma sources became commercially available. h. because this gives much better limits of detection than directing the radiation across the short axis. Explain the difference in LOD values resulting from radiation across the different axes. Below is a diagram of a typical burner head for atomic absorption spectroscopy.g. . Atomic spectral lines are truly lines.

the resolution of her monochromator would have to be much greater than if she used atomic absorption analysis.2 amu). .j.31 nm. Solder used for electrical circuitry is usually some composition of tin (118.00 nm and lead has a transition at 283.7 amu) and lead (207. 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. An analytical chemist wanted to measure the composition of solder by atomic spectroscopy. tin has a transition at 284. If she performed this analysis by inductively coupled plasma atomic emission.

differentiate between packed and open tubular columns. After the BP oil spill. (50 points) For the following separation or measurement problems pick the best technique from among those we discussed this semester.e. To study pharmacokinetics. McCauley. The FDA has long considered regulating nicotine as a “drug”. In that paper they invented a (great!) new unit. H. Wolnik. Justify your answer in one or two sentences. J. A. µeq / pinch ! (Who said scientists have no sense of humor?) How would you measure nicotine in tobacco? b. A. pick a separation mechanism (i.). Cefotaxime is a wide-spectrum. reversed-phase. B. The relative buffering capacities of saliva and moist snuff: Implications for nicotine absorption. If you choose GC. D. also pick a suitable detector. If you pick LC. Ciolino. as those would represent a clear indication of contamination by the leaking oil. . NOAA (National Oceanic and Atmospheric Administration) began routine testing of gulf caught seafood for 19 different polyaromatic hydrocarbons. For both GC and LC. size exclusion. 25 (2001) 15-25. Anal. A. etc. Fraser and K.5. a. third generation cephalosporin antibiotic. and is an addictive substance. also choose an ionization method.6 to 3% of the dry weight of tobacco. If you pick mass spectrometry. Nicotine constitutes from 0. and a recent study has investigated the nicotine content of smokeless tobaccos. you need to determine both the parent compound and any metabolites in blood plasma. Toxicol. L. How would you run these tests? c.. ion exchange.

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