Nuclear magnetic resonance spectroscopy

If the atomic nucleus possessing nonzero spin is placed in a magnetic field, absorption of radiofrequency
radiation causes the nuclear spin to realign in the higher-energy direction.
The rules for determining the spin quantum number of a nucleus are as follows:
1. If the atomic mass of nuclei and the number of neutrons are both even, then the nucleus has NO
spin (I = 0). (NMR inactive) e.g. 12C, 16O
2. Even atomic mass nuclei that have odd number of neutrons have an integer spin quantum number
(I = 1, 2, 3, etc) e.g. I= 1: 2H, 14N
3. Odd atomic mass nuclei have half-integer spin quantum number (I = 1/2, 3/2, 5/2, etc)
I= 1/2: 1H, 13 C, 19F, 31 P; I= 3/2: 15N
Number of possible energy levels (spin states) = 2I+1

magnetic field vector

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The energy difference between aligned and opposed to the external magnetic field (B0) is generally small
and depends upon B0. Applied radio wave causes the spin to flip when the nuclei are in resonance with B0.

 is gyromagnetic ratio (a fundamental nuclear constant which has a different value for every type of
nuclei e.g.  = 26,752 for 1H,  = 6.73 for 13C
B0 = external magnetic field strength
 is the radio wave frequency causing spin flip
h denotes the Planck constant
The stronger magnetic field is applied, the larger radio wave frequency causes spin flip.
Different types of nuclei absorb different radio wave frequency because  depends on the type of nuclei.

The absorption of radiation by a nucleus of spin 1/2 in a magnetic field

The nucleus is spinning on its axis. In the presence of a magnetic field, this axis of rotation will precess
around the magnetic field:

The frequency of precession is termed the Larmor frequency, which is identical to the radio wave frequency
causing spin flip.
Larmor frequency = B0 / (2)
If energy is absorbed by the nucleus of spin 1/2, the magnetic moment flips so that it opposes the applied
magnetic field. (This is a higher energy state).

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The importance of the environment of hydrogen atom

The effect of the electrons is to cut down the size of the external magnetic field felt by the hydrogen nucleus.
Stronger external magnetic field is needed to compensate for the effect of the electrons. (upfield shift of the
signal)

Due to the large electronegativity of Cl, the electron density around the H atoms of CH 3Cl becomes smaller
than around the H atoms of CH 4. Hence, the electrons around the H atoms of CH 3Cl weaken the effect of
the external magnetic field to a smaller extent. It is convenient to use a fixed radio wave frequency and vary
the current (and hence the strength of the magnetic field) in an electromagnet to observe the resonant
absorption signals. This is the origin of downfield and upfield terminology.
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Vertical scale= intensity of the signal

Horizontal scale= chemical shift (), which is usually expressed in parts per million (ppm) by frequency,
because it is calculated from:

sample and ref denote the resonance frequency of the sample and the reference compound, respectively.

Tetramethylsilane (TMS) is used as reference compound with chemical shift  = 0 for 1H NMR.
TMS is chosen as the standard because:
• It has 12 hydrogen atoms all of which are in exactly the same environment. Therefore, the 1H
NMR spectrum of TMS has only a strong single peak.
• TMS produces a peak on the spectrum at the extreme right-hand side. Almost everything else
produces peaks to the left of it.
• Chemically inert

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Chemical shift (ppm)

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Multiple substituents exert a cumulative effect

The extent of the downfield shift increases when the number of Cl atoms is raised.

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In the NMR spectrum of 2,2-dimethyl-1-propanol, there are three different peaks due to
absorptions by:

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 Spin-Spin Coupling: The Effect of Non‐Equivalent Neighbouring Hydrogens

Spliting is observed only between nuclei with different chemical shifts.

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This table illustrates the N+1 rule: Nuclei having N adjacent equivalent neighbours split into N+1 peaks.
The heights of the N+1 peaks follow Pascal’s triangle.

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 Coupling constant

3) The alcohol hydrogen –OH usually does not split neighboring hydrogen signals nor is it split.

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 Carbon-13 Nuclear Magnetic Resonance Spectroscopy
Low sensitivity
• Natural abundance of 13C is very low (1.1%)
• Gyromagnetic ratio of 13C nucleus is much smaller than that of 1H nucleus
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C: 1.404; 1H: 5.585.
Advantages
• Carbon NMR can used to determine the number of non-equivalent carbons and to identify the types
of carbon atoms (methyl, methylene, aromatic, carbonyl….) which may present in compound.
• 13
C signals are spread over a much wider range than 1H signals making it easier to identify & count
individual nuclei.
• 13C-13C coupling is negligible because of low natural abundance of 13C in the compound.
• It can be achieved with special techniques ( 1H decoupling) that each type of 13C provides a single
peak in the spectrum.

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Chemical shift (ppm)

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NMR instrument

Scheme

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