Mass Spectrometry Dry Lab CHM 1021

In mass spectrometry, a substance is bombarded with an electron beam having

sufficient energy to fragment the molecule. The positive fragments which are
produced (cations and radical cations) are accelerated in a vacuum through a magnetic
field and are sorted on the basis of mass-to-charge ratio. Since the bulk of the ions
produced in the mass spectrometer carry a unit positive charge, the value m/e is
equivalent to the molecular weight of the fragment. The analysis of mass spectroscopy
information involves the re-assembling of fragments, working backwards to generate
the original molecule. A schematic representation of a mass spectrometer is shown
below:

A very low concentration of sample molecules is allowed to leak into the ionization
chamber (which is under a very high vacuum) where they are bombarded by a high-
energy electron beam. The molecules fragment and the positive ions produced are
accelerated through a charged array into an analyzing tube. The path of the charged
molecules is bent by an applied magnetic field. Ions having low mass (low
momentum) will be deflected most by this field and will collide with the walls of the
analyzer. Likewise, high momentum ions will not be deflected enough and will also
collide with the analyzer wall. Ions having the proper mass-to-charge ratio, however,
will follow the path of the analyzer, exit through the slit and collide with the
Collector. This generates an electric current, which is then amplified and detected. By
varying the strength of the magnetic field, the mass-to-charge ratio which is analyzed
can be continuously varied.

The output of the mass spectrometer shows a plot of relative intensity vs the mass-to-
charge ratio (m/e). The most intense peak in the spectrum is termed the base peak and
all others are reported relative to it's intensity. The peaks themselves are typically very
sharp, and are often simply represented as vertical lines.

The process of fragmentation follows simple and predictable chemical pathways and
the ions which are formed will reflect the most stable cations and radical cations
Mass Spectrometry Dry Lab CHM 1021

which that molecule can form. The highest molecular weight peak observed in a
spectrum will typically represent the parent molecule, minus an electron, and is
termed the molecular ion (M+). Generally, small peaks are also observed above the
calculated molecular weight due to the natural isotopic abundance of 13C, 2H, etc.
Many molecules with especially labile protons do not display molecular ions; an
example of this is alcohols, where the highest molecular weight peak occurs at m/e
one less than the molecular ion (m-1). Fragments can be identified by their mass-to-
charge ratio, but it is often more informative to identify them by the mass which has
been lost. That is, loss of a methyl group will generate a peak at m-15; loss of an
ethyl, m-29, etc. Click here for a table of common fragments.

The mass spectrum of toluene (methyl benzene) is shown below. The spectrum
displays a strong molecular ion at m/e = 92, small m+1 and m+2 peaks, a base peak at
m/e = 91 and an assortment of minor peaks m/e = 65 and below.

The molecular ion, again, represents loss of an electron and the peaks above the
molecular ion are due to isotopic abundance. The base peak in toluene is due to loss of
a hydrogen atom to form the relatively stable benzyl cation. This is thought to
undergo rearrangement to form the very stable tropylium cation, and this strong peak
at m/e = 91 is a hallmark of compounds containing a benzyl unit. The minor peak at
m/e = 65 represents loss of neutral acetylene from the tropylium ion and the minor
peaks below this arise from more complex fragmentation.
Mass Spectrometry Dry Lab CHM 1021

Alkanes: Simple alkanes tend to undergo fragmentation by the initial loss of a methyl
group to form a (m-15) species. This carbocation can then undergo stepwise cleavage
down the alkyl chain, expelling neutral two-carbon units (ethene). Branched
hydrocarbons form more stable secondary and tertiary carbocations, and these peaks
will tend to dominate the mass spectrum.

Aromatic Hydrocarbons: The fragmentation of the aromatic nucleus is somewhat

complex, generating a series of peaks having m/e = 77, 65, 63, etc. While these peaks
are difficult to describe in simple terms, they do form a pattern (the "aromatic
cluster") that becomes recognizable with experience. If the molecule contains a benzyl
unit, the major cleavage will be to generate the benzyl carbocation, which rearranges
to form the tropylium ion. Expulsion of acetylene (ethyne) from this generates a
characteristic m/e = 65 peak.

Aldehydes and Ketones: The predominate cleavage in aldehydes and ketones is loss
of one of the side-chains to generate the substituted oxonium ion. This is an extremely
favorable cleavage and this ion often represents the base peak in the spectrum. The
methyl derivative (CH3C O+) is commonly referred to as the "acylium ion".

Another common fragmentation observed in carbonyl compounds (and in nitriles,

etc.) involves the expulsion of neutral ethene via a process known as the McLafferty
rearrangement, following the general mechanism shown below.
Mass Spectrometry Dry Lab CHM 1021

Esters, Acids and Amides: As with aldehydes and ketones, the major cleavage
observed for these compounds involves expulsion of the "X" group, as shown below,
to form the substituted oxonium ion. For carboxylic acids and unsubstituted amides,
characteristic peaks at m/e = 45 and 44 are also often observed.

Alcohols: In addition to losing a proton and hydroxy radical, alcohols tend to lose one
of the  -alkyl groups (or hydrogens) to form the oxonium ions shown below. For
primary alcohols, this generates a peak at m/e = 31; secondary alcohols generate peaks
with m/e = 45, 59, 73, etc., according to substitution.

Ethers: Following the trend of alcohols, ethers will fragment, often by loss of an alkyl
radical, to form a substituted oxonium ion, as shown below for diethyl ether.

Halides: Organic halides fragment with simple expulsion of the halogen, as shown
below. The molecular ions of chlorine and bromine-containing compounds will show
multiple peaks due to the fact that each of these exists as two isotopes in relatively
high abundance. Thus for chlorine, the 35Cl/37Cl ratio is roughly 3.08:1 and for
bromine, the 79Br/81Br ratio is 1.02:1. The molecular ion of a chlorine-containing
compound will have two peaks, separated by two mass units, in the ratio   3:1, and a
bromine-containing compound will have two peaks, again separated by two mass
units, having approximately equal intensities.
Mass Spectrometry Dry Lab CHM 1021

The lists given above are by no means exhaustive and represents only the simplest and
most common fragments seen in the mass spectrum.

1. Please use the above theory and provided information to draw an accurate molecular structure
of the unknown molecule.
Mass Spectrum

Analysis: C5H12O MW = 88.15
Mass Spectrometry Dry Lab CHM 1021

2. Please use the above theory and provided information to draw an accurate molecular structure
of the unknown molecule.
Mass Spectrum

Analysis: C7H12Br MW = 171.04

3. Please use the above theory and provided information to draw an accurate molecular structure
of the unknown molecule.

Mass Spectrum

Analysis: C9H10O MW = 134.18
Mass Spectrometry Dry Lab CHM 1021

4. Please use the above theory and provided information to draw an accurate molecular structure
of the unknown molecule.
Mass Spectrum

Analysis: C11H12O 3 MW = 192.21