B- Use of Heavier Isotope Peaks:

Whether or not a high-resolution mass spectrometer is available, molecular ion peaks

often provide information about the molecular formula. Most elements do not consist of
a single isotope, but contain heavier isotopes in varying amounts. These heavier
isotopes give rise to small peaks at higher mass numbers than the major M+ molecular
ion peak.

A peak that is one mass unit heavier than the M+ peak is called the M+1 peak; two units
heavier, the M+2 peak, and so on. See the table below:

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Ideally, we could use the isotopic compositions to determine the entire molecular
formula of a compound, by carefully measuring the abundances of the M+, M + 1, and
M +2 peaks.
In practice, however, there are background peaks at every mass number. These
background peaks are often similar in intensity to the M + 1 peak, preventing an
accurate measurement of the M + 1 peak. High-resolution mass spectrometry is much
more reliable.
Some elements (particularly S, CI, Br, I, and N) are recognizable from molecular ion
peaks.

 A typical compound with no sulfur, chlorine, or bromine has a small M + 1 peak and
an even smaller M + 2 peak.

 If a compound contains sulfur, the M + 2 peak is larger than the M + 1 peak: about 4%
of the M+ peak.
 If chlorine is present, the M + 2 peak is about a third as large as the M+ peak.

 If bromine is present, the M+ and M + 2 ions have about equal abundances; the
molecular ion appears as a doublet separated by two mass units, with one mass
corresponding to 79Br and one to 81Br.

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 Iodine is recognized by the presence of the iodonium ion, I+, at m/z 127 . This clue
is combined with a characteristic 127-unit gap in the spectrum corresponding to
loss of the iodine radical.

 Nitrogen (or an odd number of nitrogen atoms) is suggested by an odd molecular

weight.

 Stable compounds containing only carbon, hydrogen, and oxygen have even
molecular weights.

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Fragmentation Patterns in Mass Spectrometry:
In addition to the molecular formula, the mass spectrum provides structural information.
An electron with a typical energy of 70 eV (6740 kllmol or 1610 kcal/mol) has far more
energy than needed to ionize a molecule.
The impact forms the radical cation, and it often breaks a bond to give a cation and a
radical. The resulting cation is observed by the mass spectrometer, but the uncharged
radical is not accelerated or detected. We can infer the mass of the uncharged radical
from the amount of mass lost from the molecular ion to give the observed cation
fragment.

This bond breaking does not occur randomly; it tends to form the most stable fragments.
By knowing what stable fragments result from different kinds of compounds, we can
recognize structural features and use the mass spectrum to confirm a proposed structure.
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A- Mass Spectra of Alkanes:
The mass spectrum of n-hexane shows several characteristics typical of straight-chain
alkanes. The base peak (m/z 57) corresponds to loss of an ethyl group, giving an ethyl
radical and a butyl cation. The neutral ethyl radical is not detected, because it is not
charged and is not accelerated or deflected.

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A similar fragmentation gives an ethyl cation and a butyl radical. In this case, the
ethyl fragment (m/z 29) is detected.

Symmetric cleavage of hexane gives a propyl cation and a propyl radical.

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Cleavage to give a pentyl cation (m/z 71) and a methyl radical is weak because the methyl
radical is less stable than a substituted radical. Cleavage to give a methyl cation (m/z 15)
and a pentyl radical is not visible because the methyl cation is less stable than a
substituted cation. The stability of the cation is apparently more important than the
stability of the radical, since a weak peak appears corresponding to loss of a methyl
radical, but we see no cleavage to give a methyl cation.

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Cation and radical stabilities help to explain the mass spectra of branched alkanes as well.
See the mass spectrum of 2-methylpentane.
Fragmentation of a branched alkane commonly occurs at a branch carbon atom to give
the most highly substituted cation and radical.

Fragmentation of 2-methylpentane at the branched carbon atom can give a secondary

carbocation in either of two way s :

Both fragmentations give secondary cations, but

the second gives a primary radical instead of a
methyl radical. Therefore, the second
fragmentation accounts for the base (largest)
peak, while the first accounts for another large
peak at m/z 71. Other fragmentations (to give
primary cations) account for the weaker peaks.
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