Mass Spectroscopy

The purpose of this topic is analysis. Alongside infra-red spectroscopy, mass spectroscopy can give a lot of
useful information about an unknown organic molecule.

the emphasis is on organic molecules in topic 7. But remember you already briefly looked at mass
spectroscopy in topic 1.

Spectrum Analysis

The main purpose of mass spectroscopy is to identify the molecular weight of your compound.

The spectrum of ethanol is shown below. Ethanol has a molecular mass of 46 and if you look at the far
right side of the spectrum you can see a peak at 46. This represents the molecular mass of ethanol and is
named the "molecular ion peak".

breakdown
peaks molecular
relative
abundance ion peak

mass/charge

The rest of the peaks to the left are called the "breakdown peaks", which represent smaller fragments of
the molecule.

They are like a fingerprint for different molecules and should help to identify unknown compounds.

Breakdown Peaks
When your sample goes into the mass spectrometer it is bombarded with electrons causing the molecule
to ionise (lose an electron). Due to the high energy, it also causes the molecule to break up into
fragments.

Ethanol has the formula CH3-CH2-OH. We know the molecular mass = 46.

After the sample is placed in the spectrometer it is ionised to give:

This is the ion that gives the peak at m/z = 46.

the mass spectrometer only measure the mass of ions. So always put a little + sign when writing out
the molecule responsible for a particular peak.

To identify the breakdown peaks you have to "remove groups from the original molecule at either end.

You could break off the OH group to give CH3-CH2+, which has a mass of 29 and is seen in the spectrum.

You could break off the CH3 group to leave you with CH2-OH+, which has a mass of 31.

You can remove groups from either end of the molecule. Just keep doing this until you get a structure
that matches the peak in question.

it is only the ion that you are interested in when looking at these spectra. But there is another part of
the molecule that isnt an ion and isnt detected when you break the molecule into fragments. The
other part of the fragment is a free radical.

Using the breakdown peaks

The point of the breakdown peaks is to allow you to tell the difference between two similar structures.

For example, propanal and propanone both have a molecular mass of 58, so will both have the same
molecular ion peak.

But the structures are slightly different, therefore they will have different breakdown peaks. You can
predict them. Here are a few examples of ions that will be in the spectra:
These are just a few examples of possible breakdown peaks. The important ones are the propanal peaks
at 57 and 29 as these are not possible for propanone.

Both molecules will still have one or two identical breakdown peaks, for example CH3+ 15, C=O+ 28 etc.

Its actually easier looking at the spectra as you can instantly see that they are not identical and can pick
out the peaks that are in one but not in the other.

Mass spectroscopy isnt going to reveal the structure of an unknown compound on its own. But along
with other techniques such as infra-red, you can start to piece together the structure.