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Mass Spectrometry

Mass Spectrometry is basically an experimental technique where a molecule is bombarded with high
energy electrons, breaking the molecule up into various fragments. The abundance of all of the
fragments are then recorded in a graph, represented by a mass spectrum. An example of a Mass
spectrum is shown below

The molecular weight of the molecule is represented by the symbol M+. All of the different bars shown
in the spectrum represent all of the different fragments that are created after fragmenting the
molecule. The higher the bar, the more abundant the fragment will be. The M/Z ratio represents the
mass to charge ratio of the ion. Most, if not all, of the fragments shown in the spectrum have a charge
of +1 since they are carbocations. Therefore, for our purposes, the m/z ratio simply represents the
mass of the fragment.
So what do you have to be able to do with a mass spectrum? You have to be able to

Determine the molecular weight of the original molecule. (This is usually given, but when it is
not, you have to be able to find the molecular weight directly from the mass spectrum)
Draw and predict the structures of the most abundant fragments with the corresponding
molecular weight shown by the mass spectrum. This is the most common type of question they
will ask you regarding MS
Be able to predict the presence of certain elements (particularly the presence of Br, Cl, I, N or S)

Some VERY important facts to keep in mind:

Whenever a molecule is fragmented by an electron, the molecule is split into 2 fragments: 1 of


the fragment is a carbocation, and one is a radical. The carbocation fragment is the ONLY
fragment that will be detected on the mass spectrum! Therefore, when asked to draw out the
structure of the fragment represented by the MS, draw the carbocation!
The fragment that is formed from breaking up the molecule is determined by the stability of the
fragment. Because the fragments are high energy carbocation/radicals, the more stable they

are, the more likely they will form. Therefore, the fragments that you need to be concerned
with are the most stable fragments produced from fragmenting the original molecule. If you
are ever stuck on how to fragment a molecule, always go for the more stable one. If you can
remember this fact, then predicting the fragments will be much easier
Remember that you want to form the most stable fragment, or in the case of MS, the most stable
carbocation. Therefore, keep in mind the stability rules of carbocation!

The more carbon-carbon groups, the more stable the carbocation (3o>2o>1o)
RESONANCE! Most of the fragments that are produced will have resonance if it can form!
Keep this in mind!
Mass Spectrum of Alkanes

Since alkanes only contain simple carbon chains, the most abundant fragment will be the most
substituted carbocation. Take for example 2-butane. To produce the most stable carbocations, the
molecule can be fragmented into 2 different ways, shown below

The first fragmentation is produced by breaking the 2-3 carbon bond. The carbocation will form on the
2nd carbon, producing the most stable carbocation (2o in this case). To figure out the mass of the
fragment, count each individual element involved. In the first case, the carbocation has a mass of: (12 x
3) + (1 x 7) = 36 (mass of carbons) + 7 ( mass of hydrogens) = 43. Dont forget that the carbocation
makes the carbon unsaturated, so the carbon with the positive charge only has 1 hydrogen.
For the second fragmentation will break the 1-2 carbon bond, forming the carbocation shown above.
The mass of the 2nd carbocation fragment is: (12 x 4) + (1 x 9) = 48 + 9 = 57. The mass spectrum is
shown below, with the structure of the most abundant fragment drawn corresponding to the peak seen.

Fragmentation of alkenes
Whenever an alkene becomes fragmented, the most common fragmentation is the cleavage of an
allylic bond to create a resonance stabilized allylic carbocation.

Fragmentation of alcohols
Alcohols commonly go through two types of fragmentations:

Dehydration: The alcohol can often lose water, forming an alkene (similar to an elimination
reaction). This is usually easy to detect because water has a mass of 18, so if you see a peak that
is 18 less than the original M+ value of an alcohol, it will be caused by dehydration of the
original alcohol. Also keep in mind that the alkene can still continue to fragment.

Alpha () cleavage of an alcohol: The alcohol also commonly cleaves off the carbon with the
oxygen bonded to it that is connecting to the alpha carbon (carbon adjacent to the alcohol
carbon). This allows for the fragmented carbocation to have resonance with the oxygen

Fragmentation of Amines
This is not covered in Biewers notes, but just in case, Im putting this in. Amine fragmentation is similar
to the fragmentation of alcohols. It will produce fragments that resonate with the nitrogen!

Fragmentation of ethers
Again, this is not covered in Biewers notes, but just in case, Im putting this in. Ethers also fragment
similarly to amines. However, since there is an R group attached to the oxygen instead of a hydrogen, it
has a more unique fragmenting pattern. They are:

Alpha cleavage: Similar to alcohol alpha cleavage, the alpha carbon is cleaved off to form a
carbocation with resonance with the oxygen
Loss of alkyl group: An adjacent alkyl group attached to the oxygen can get cleaved. The
carbocation can go on either the oxygen or the alkyl group attached. Note that the other alkyl
group attached on the other side can also get cleaved as well

Fragmentation of carbonyl groups (ketones and aldehydes)


Fragmentation of ketones and aldehydes can commonly occur in two ways:

Alpha cleavage: Similar to an alpha cleavage of an alcohol, the alpha carbon-beta carbon bond
will cleave, forming an acylium ion that has resonance with the oxygen.
McLafferty rearrangement: This is a common fragmentation unique to carbonyl compounds.
This process involves a transfer of a hydrogen atom from the gamma () carbon to the carbonyl
carbon. This generates an enol (alcohol with an adjacent alkene), with the loss of an alkene.
The enol fragment created can also keep fragmenting (although you dont need to know the
fragments it produces)

Distinguishing between different elements


There are different patterns that can are recognizable on a mass spectrum that indicates the
prescence of specific elements. These are usually due to the presence of heavier isotopes that contain a
higher molecular mass. The heavier isotopes give rise to peaks that are higher in mass number
compared to the original m/z peak (M+). A peak that is one m/z value heavier is noted as M+1, and a
peak that is 2 m/z values heavier is noted as M+2. The different elements that can be distinguished are

Bromine (Br): Bromine always a M+ peak and a M+2 peak that are roughly the same size
(50.5% vs. 49.5% respectively)

Chloride (Cl): Chlorine has a M+2 peak that is roughly a third the size of the M+ peak (75.5% to
24.5%)

Iodine (I): There is a LARGE (127 m/z value) gap between the M+ peak and the fragments, due
to the loss of Iodine, which is very heavy

Nitrogen (N): Nitrogen is the only element that contains an odd M/Z M+ value! During
fragmentation, it will usually produce even and odd m/z fragments. Whenever you see an odd
M+ value, suspect the presence of nitrogen.

Sulfur (S): Sulfur is usually identified on the MS by the presence of a larger than normal M+2
fragment. Usually, a compound with no diagnostic element will contain a very small M+1 peak
and an even smaller M+2 peak. A M+2 peak that is larger than usual (but not as large as Cl or
Br M+2 peak), is indicative of sulfur.

MS is usually only tested on the first exam. It is not as important as IR or NMR for diagnostic
information. I did not get any MS questions on the 2nd and 3rd exam, nor the final. If you can remember
the basic fragmentation patterns as well as identifying the unique elements present, you will be fine!