NMRSpectroscopy(A) - NMR Spectroscopy Nuclear Magnetic...

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Unformatted text preview: NMR Spectroscopy Nuclear Magnetic Resonance Spectroscopy 1. Background Over the past fifty years nuclear magnetic resonance spectroscopy, commonly referred to as nmr, has become the preeminent technique for determining the structure of organic compounds. Of all the spectroscopic methods, it is the only one for which a complete analysis and interpretation of the entire spectrum is normally expected. Although larger amounts of sample are needed than for mass spectroscopy, nmr is non-destructive, and with modern instruments good data may be obtained from samples weighing less than a milligram. To be successful in using nmr as an analytical tool, it is necessary to understand the physical principles on which the methods are based . The nuclei of many elemental isotopes have a characteristic spin ( I ). Some nuclei have integral spins (e.g. I = 1, 2, 3 ....), some have fractional spins (e.g. I = 1/2, 3/2, 5/2 ....), and a few have no spin, I = 0 (e.g. 12 C, 16 O, 32 S, ....). Isotopes of particular interest and use to organic chemists are 1 H, 13 C, 19 F and 31 P, all of which have I = 1/2. Since the analysis of this spin state is fairly straightforeward, our discussion of nmr will be limited to these and other I = 1/2 nuclei. For a table of nuclear spin characteristics Click Here . The following features lead to the nmr phenomenon: 1. A spinning charge generates a magnetic field, as shown by the animation on the right. The resulting spin-magnet has a magnetic moment ( μ ) proportional to the spin. 2. In the presence of an external magnetic field ( B ), two spin states exist, +1/2 and -1/2 . The magnetic moment of the lower energy +1/2 state is alligned with the external field, but that of the higher energy -1/2 spin state is opposed to the external field. Note that the arrow representing the external field points North. 3. The difference in energy between the two spin states is dependent on the external magnetic field strength, and is always very small. The following diagram illustrates that the two spin states have the same energy when the external field is zero, but diverge as the field increases. At a field equal to B x a formula for the energy difference is given (remember I = 1/2 and μ is the magnetic moment of the nucleus in the field). Strong magnetic fields are necessary for nmr spectroscopy. The international unit for magnetic flux is the tesla ( T ). The earth's magnetic field is not constant, but is approximately 10-4 T at ground level. Modern nmr spectrometers use powerful magnets having fields of 1 to 20 T. Even with these high fields, the energy difference between the two spin states is less than 0.1 cal/mole. To put this in perspective, recall that infrared transitions involve 1 to 10 kcal/mole and electronic transitions are nearly 100 time greater....
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This note was uploaded on 04/07/2008 for the course CHEM 6a taught by Professor Pettus during the Winter '07 term at UCSB.

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NMRSpectroscopy(A) - NMR Spectroscopy Nuclear Magnetic...

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