1 Nuclear Magnetic Resonance (NMR) Spectroscopy

1.1 Basic Principles

NMR spectroscopy allows us to detect atomic nuclei and determine what environments
they are in within a molecule. Clearly, hydrogen atoms in an alcohol group and those
on a carbon skeleton are chemically very different—only the hydroxyl hydrogen exhibits
hydrogen bonding and is easily replaced by, say, alkali metals in substitution reactions.
NMR is able to distinguish between these different types of hydrogens based on their
environments, in particular, the surrounding pattern of electron density and the presence
of other nuclei nearby.
NMR spectroscopy works only on certain nuclei—those that, like hydrogen-1 and
carbon-13, have an intrinsic magnetic field, also called ”spin”. These nuclei behave in
a way much like compass needles. A compass needle in an external magnetic field will
seek to align itself with that magnetic field, and an input of energy would be required
to force the needle to point in the opposite direction. Unlike compass needles, however,
there are only two energy levels available: aligned with the external magnetic field and
aligned against it; also unlike compasses, the energy difference between these states is so
small that, even in a strong magnetic field, thermal fluctuations ensure that the fraction of
nuclei in each state will be indistinguishable from 50%. This analogy makes it clear why
larger magnetic fields imply greater energy differences between these states; in fact, the
energy needed (and, by E = hν, the frequency of the radiation whose photons each carry
that amount of energy) is proportional to the strength of the magnetic field applied. In
order to bring the energy levels into a measurable range, then, the magnetic fields used in
NMR are phenomenally strong—some 105 times stronger than the Earth’s magnetic field.
There are two ways we might go about measuring this energy. We might consider
sweeping a radio transmitter (as the frequencies here are in the radio spectrum) across a
range of frequencies, then recording the amount of radiation absorbed at each frequency.
This is how early NMR machines worked, but it’s far slower than an alternative method:
irradiate the sample with a short pulse of radio-frequency energy at all frequencies in the
band in order to excite the nuclei into the higher-energy state, then ”listen” for the return
photons (with a radio receiver) released when the nuclei ”fall back” from the higher to the
lower energy level.

1.2 Chemical Shift

We have not yet explained why different nuclei absorb energy (or ”resonate”) at different
frequencies—the reason we are investigating NMR in the first place. This is due to the
subtle fact that not every nucleus experiences exactly the same magnetic field as the one we
apply. The external magnetic field induces small currents in the electron cloud surrounding
each nucleus, and these currents in turn generate magnetic fields that partially cancel out
the one we impose. The net result of this is called ”shielding”—higher electron densities

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around a nucleus ”shield” that nucleus from the effect of the external magnetic field,
reducing the frequency it resonates at. Neighboring atoms with high electronegativities
(think oxygen) reduce the electron density around a nucleus and reduce this shielding
effect, and are thus said to ”deshield” it. Conveniently, differing electron densities are
also a major factor in determining reactivity, so NMR can tell us a great deal about the
chemistry of a molecule at the same time as it informs us as to the molecule’s structure.
This variation in resonant frequency is called ”chemical shift” and symbolized δ, and
it’s measured in terms of the fraction by which the resonant frequency of a given nucleus
is lower than that of a reference nucleus, usually tetramethylsilane (TMS), and reported
in parts per million (ppm). NMR spectra thus are labeled with δ increasing from right to
left, although the resonant frequency and energy difference both increase from left to right.
Knowing nothing more than you know already, try identifying the following three 13 C-
NMR spectra as those of either n-butanol, isopropanol, or 2-methylbutane-1,3-diol:

Can you identify which peaks go with which carbon atoms?

1 H-NMR spectra are similar, but with one major additional benefit. Unlike in 13 C-

NMR, the heights (more properly, the areas) of the peaks in 1 H-NMR are proportional to
the number of hydrogen nuclei they represent. They are thus often shown along with their
integral, so that the area under each peak is readily apparent from the height of each step.
Wow...it’s been two hours and I’m still not at J-coupling...
TO BE CONTINUED, including J-coupling, WEIRD BENZENE STUFF (ring current
creates stronger field outside ring), etc.