A GUIDE TO INTERPRETING MASS SPECTRA

Mass spectrometry is an analytical technique that allows us to measure the masses of atoms and molecules. The most important peak in a mass spectrum
is the molecular ion peak, which can be used to determine the mass of the molecule, but fragment ions can also provide information on chemical structure.

2 3 H H H
H
H
H
H Cl
H
H H
ELEC
1 TRO
M
H C H C C N C O C 2 peaks seen due to the 35Cl & C C C
AG H
37
Cl isotopes, in a 3:1 ratio due
N H H H H H to their natural abundance. H
H

ET
15 29 30 31 35/37 41
3:1

4
H H H H O H H O H H H H H
H H
H C C C H C C N C C N C
Cl C H C C C C
HOW MASS SPECTROMETRY WORKS H
H H H H H H H H H H H H

5 43 43 44 44 49/51 57
3:1

H H O H H H H O H H H H H H H H
The sample is introduced to the mass spectrometer. H
1 Only very small samples are required. A heater is often
present to vapourise the sample. H C C C N C C C H C O C H C C O C H C C C C C

H
H H H H H H H H H H H H H H

An electron gun ionises molecules in the sample by

2 knocking out electrons, producing positive ions. Some
molecules break into smaller ions & fragments.
57 58 59 59 71
H H
H H H O Br H H H H H H H
The positive ions generated are passed through an C C

3 electric field which accelerates them into a magnetic

field generated by an electromagnet.
H C C C C H C C
2 peaks seen due to the 79Br & H C C C C C C Br C
C C Br isotopes, in a 1:1 ratio due
81

H H H to their natural abundance. H H H H H H H

H H

As the positive ions pass through the magnetic field,

71 77 79/81 85 93/95
4 they are deflected. Lighter ions are deflected more
than heavier ions, as are those with higher charges.
1:1 1:1

The positive ions hit a charged plate & accept electrons,
5 creating a signal. The more ions that hit, the greater the
signal. The output is a complex stick diagram.
Above are shown a selection of common fragment ions seen in mass spectra, along with their masses. Note that
the structures shown are general representations, and it can also be possible for isomeric structures (those with the
same constituent atoms, but a different structure) to cause the peaks in spectra. There are also many more fragments
possible than those shown, but knowledge of these should suffice to interpret spectra of most simple molecules.

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