4/03/20

NMR – nuclear magnetic resonance

This is the most powerful technique available for Chemists, determining the structure of
organic compounds, to check for impurities and to study the shape of molecules.
Magnetic resonance imaging can be used to look at internal structures of a body

All nuclei possess charge and mass

Those with an odd mass number also possess spin, this means they have angular
momentum

Possess spin:
1 13 19 31
H C F P
1 6 9 15

Doesn’t poses spin

12 2
C H A nucleus without spin cannot be detected by nuclear
6 1 magnetic resonance spectroscopy

When spinning, these nuclei generate a

magnetic field – they behave light tiny
magnets

In a strong magnetic field, the spinning

nuclei must align themselves either wit or
against the magnetic field

There will be a slight energy difference

between the two states

Irradiating a sample with

EMR (electromagnetic
radiation), causes the
nucleon to resonant at a
known frequency
This frequency corresponds to radio waves

The frequency can be detected in an NMR spectrometer

NMR spectrum tells us:

Different chemical environments (bonds and atoms surround a nucleus) affect the strength
of magnetic field that must be applied to a nucleus in order for it to enter the resonance
state

By measuring the strength of magnetic field that must be applied, NMR spectroscopy gives
us information about the local environment of a specific atoms in a molecular structure

The environments of C-13 and H-1 atoms are most commonly studying in NMR spectroscopy

If a compound is symmetrical it has fewer resonance states

Different shielded carbon atoms require different strengths of magnetic field to enter the
resonance state when a particular radio frequency is applied.

Chemical Shift and TMS

The horizontal scale on an NMR spectrum represents chemical shift. Chemical shift is
measured in parts per million (ppm) of the magnetic field strength needed for resonance in
a reference chemical called TMS.

TMS (tetrameythlsilane)is universally used as the reference

compound for NMR as methyl groups are particularly well shielded
and so it produces strong, single peak at the far right of an NMR
spectrum.

The signal from the carbon atoms in TMS is defined as having

chemical shift of 0.

Analysing organic molecules

NMR is used to detect proton in an organic compound e.g. H-1
The frequency at which a proton absorbs radiation depends on:
A) The strength pf the magnetic field
B) The chemical environment within the molecule
The chemical shifts give the effect of the chemical environment on the proton

Interpretation of Spectra:
1. Number of different signals in the spectrum – the number of environments
2. Position of the signals (chemical shift) – type of environment
 3. Intensity of the signals – number of atoms in each environment
4. Splitting pattern of the signals- adjacent environment

How is NMR carried out?

Sample is dissolved in an inert solvent (has no hydrogen, proton) – CCL4 or solvents with the
isotopes of H-1 H-2
The spectra are measured against a reference TMS
This produces a single peak calibrated at 0 ppm.

High vs Low Resolution NMR

- Low resolution gives 1 peak for each

environmentally different groups of
protons
- High resolution gives more complex
signals – doublets, triplets, quartets,
multiples. The signal produced
indicates the number of chemically
different protons on adjacent carbon
atoms. The splitting pattern depends
on the number of hydrogen atoms on
adjacent atoms.
- The area under the graph represents
the number of hydrogens in that
environment

Multiplicity (spin-spin splitting)

- The signal produced indicates the number of chemically different hydrogens
(protons) on adjacent carbon atoms
- Number of peaks = number of chemically different H’s on adjacent atom + 1