There is no denying the fact that Nuclei possessing angular moment
known as spin have an associated magnetic moment. A few examples of
magnetic isotopes are 13C, 1H, 19F,14N, 17O, 31P, and 33S. It may be
focused that not every isotope is magnetic. In particular, we should
also memo that 12C is not magnetic. If a nucleus is not magnetic, it
can't be studied by nuclear magnetic resonance spectroscopy. For the
purposes of this course, we will be most interested in 1H and 13C. I
will limit my planning to 1H in this short handling.
Generally speaking, you should think of these special nuclei as tiny, atomic, bar magnets. Suffice it to say that Nuclear Magnetic Spectroscopy is based on the fact that when a population of magnetic nuclei is placed in an external magnetic field, the nuclei become aligned in a unsurprising and finite number of orientations. For 1H there are two orientations. In one orientation the protons are aligned with the external magnetic field (North Pole of the nucleus aligned with the south pole of the magnet and south pole of the nucleus with the north pole of the magnet) and in the other where the nuclei are aligned against the field (north with north, south with south). The alignment with the field is also called the "alpha" orientation and the alignment against the field is called the "beta" orientation. From my description of the poles, which orientation do you think is the preferred or lower in energy? If you guessed the "alpha", you are correct. It might be worth noting at this point that before the nuclei are placed in the magnetic field they have random orientation random orientation outside of field alpha and beta orientation in field Since the alpha orientation is preferred, more of the population of nuclei are aligned with the field than against the field. You might wonder why any spins would align against the field. Realize that we are talking about atomic magnets. These are very, very weak magnets. The energy difference between the alpha and beta orientations is not large. There is enough energy for nuclei to exchange between the two orientations at room temperature, though a slight excess on average is in the lower energy, alpha state. The nuclear magnetic resonance (NMR) spectroscopy experiment involves using energy in the form of electromagnetic radiation to pump the excess alpha oriented nuclei into the beta state. When the energy is removed, the energized nuclei relax back to the alpha state. The fluctuation of the magnetic field associated with this relaxation process is called resonance and this resonance can be detected and converted into the peaks we see in an NMR spectrum. What sort of electromagnetic radiation is appropriate for the low energy transition involved in NMR? Well believe it or not, radio waves do the trick. Radio waves are at the very low energy end of the electromagnetic spectrum and are sufficient to induce the desired transition. It is for this reason that NMR is considered to be a safe method of analysis. The same technology is now used in hospitals in MRI (Magnetic Resonance Imagining - people are afraid of the word nuclear). If you have ever had an MRI done, realize that you were placed in a magnetic field and all your magnetic nuclei lined up in the manner described above. Excess nuclei were pumped to higher energy states as you were exposed to radio waves. The following are two very, very important points to accept and learn if you are going to understand the rest of the discussion. 1. Electric currents have associated magnetic fields. 2. Magnetic fields can generate electric currents. If you haven't had physics yet, try to accept these two points. Certainly most people have at least heard of electromagnets and if so, you probably have some idea about the first statement. The following is a very important NMR relationship. This expression relates the external field to the frequency of resonance.
In this equation, is frequency, is the magnetogyric ratio (not needed for this discussion - a constant for each nucleus). The big thing to glean from this equation is that the external field and the frequency are directly proportional. If the external field is larger , the frequency needed to induce the alpha to beta transition is larger. It follows then that in a larger field, higher frequency radio waves would be needed to induce the transition. In this context, it is relevant to note that different nuclear magnetic resonance spectrometers have different magnetic field strengths. For example, the NMR on the first floor of Park Hall has a relatively high field, superconducting magnet. Because the field is high (high enough to erase bank cards and interfere with pacemakers and watches), the frequency range needed to excite protons is relatively high. It is called a 300 MHz (MHz = megahertz, a hertz is a cycle per second - a frequency unit) spectrometer, referring to the excitation frequency. The NMR on the second floor of Park Hall has a much weaker electromagnet associated with it. It is a 60 MHz instrument. Since different NMRs have different operating frequencies, spectra cannot be compared from different machines if they are reported in frequency units. For this reason, the universal ppm (parts per million) units are used in NMR. Please note the following relationship between ppm and frequency. The fact that frequency and ppm are directly proportional is all you need to retain for the future discussion and the course in general. Chemical shift in ppm = peak position in Hz (relative to TMS) spectrometer frequency in MHz Now let us use these basic ideas to better understand and interpret NMR spectra.
Generally speaking, you should think of these special nuclei as tiny, atomic, bar magnets. Suffice it to say that Nuclear Magnetic Spectroscopy is based on the fact that when a population of magnetic nuclei is placed in an external magnetic field, the nuclei become aligned in a unsurprising and finite number of orientations. For 1H there are two orientations. In one orientation the protons are aligned with the external magnetic field (North Pole of the nucleus aligned with the south pole of the magnet and south pole of the nucleus with the north pole of the magnet) and in the other where the nuclei are aligned against the field (north with north, south with south). The alignment with the field is also called the "alpha" orientation and the alignment against the field is called the "beta" orientation. From my description of the poles, which orientation do you think is the preferred or lower in energy? If you guessed the "alpha", you are correct. It might be worth noting at this point that before the nuclei are placed in the magnetic field they have random orientation random orientation outside of field alpha and beta orientation in field Since the alpha orientation is preferred, more of the population of nuclei are aligned with the field than against the field. You might wonder why any spins would align against the field. Realize that we are talking about atomic magnets. These are very, very weak magnets. The energy difference between the alpha and beta orientations is not large. There is enough energy for nuclei to exchange between the two orientations at room temperature, though a slight excess on average is in the lower energy, alpha state. The nuclear magnetic resonance (NMR) spectroscopy experiment involves using energy in the form of electromagnetic radiation to pump the excess alpha oriented nuclei into the beta state. When the energy is removed, the energized nuclei relax back to the alpha state. The fluctuation of the magnetic field associated with this relaxation process is called resonance and this resonance can be detected and converted into the peaks we see in an NMR spectrum. What sort of electromagnetic radiation is appropriate for the low energy transition involved in NMR? Well believe it or not, radio waves do the trick. Radio waves are at the very low energy end of the electromagnetic spectrum and are sufficient to induce the desired transition. It is for this reason that NMR is considered to be a safe method of analysis. The same technology is now used in hospitals in MRI (Magnetic Resonance Imagining - people are afraid of the word nuclear). If you have ever had an MRI done, realize that you were placed in a magnetic field and all your magnetic nuclei lined up in the manner described above. Excess nuclei were pumped to higher energy states as you were exposed to radio waves. The following are two very, very important points to accept and learn if you are going to understand the rest of the discussion. 1. Electric currents have associated magnetic fields. 2. Magnetic fields can generate electric currents. If you haven't had physics yet, try to accept these two points. Certainly most people have at least heard of electromagnets and if so, you probably have some idea about the first statement. The following is a very important NMR relationship. This expression relates the external field to the frequency of resonance.
In this equation, is frequency, is the magnetogyric ratio (not needed for this discussion - a constant for each nucleus). The big thing to glean from this equation is that the external field and the frequency are directly proportional. If the external field is larger , the frequency needed to induce the alpha to beta transition is larger. It follows then that in a larger field, higher frequency radio waves would be needed to induce the transition. In this context, it is relevant to note that different nuclear magnetic resonance spectrometers have different magnetic field strengths. For example, the NMR on the first floor of Park Hall has a relatively high field, superconducting magnet. Because the field is high (high enough to erase bank cards and interfere with pacemakers and watches), the frequency range needed to excite protons is relatively high. It is called a 300 MHz (MHz = megahertz, a hertz is a cycle per second - a frequency unit) spectrometer, referring to the excitation frequency. The NMR on the second floor of Park Hall has a much weaker electromagnet associated with it. It is a 60 MHz instrument. Since different NMRs have different operating frequencies, spectra cannot be compared from different machines if they are reported in frequency units. For this reason, the universal ppm (parts per million) units are used in NMR. Please note the following relationship between ppm and frequency. The fact that frequency and ppm are directly proportional is all you need to retain for the future discussion and the course in general. Chemical shift in ppm = peak position in Hz (relative to TMS) spectrometer frequency in MHz Now let us use these basic ideas to better understand and interpret NMR spectra.
