Mass Spectrometry Examples Solved Assignment

Looking at mass spectra

Below is typical output for an electron-ionization MS experiment (MS data in the section is derived from the Spectral Database for Organic Compounds, a free, web-based service provided by AIST in Japan.

The sample is acetone.  On the horizontal axis is the value for m/z (as we stated above, the charge z is almost always +1, so in practice this is the same as mass).  On the vertical axis is the relative abundance of each ion detected.  On this scale, the most abundant ion, called the base peak, is set to 100%, and all other peaks are recorded relative to this value. For acetone, the base peak is at m/z = 43 - we will discuss the formation of this fragment a bit later.  The molecular weight of acetone is 58, so we can identify the peak at m/z = 58 as that corresponding to the molecular ion peak, or parent peak.  Notice that there is a small peak at m/z = 59: this is referred to as the M+1 peak.  How can there be an ion that has a greater mass than the molecular ion?  Simple: a small fraction - about 1.1% - of all carbon atoms in nature are actually the 13C rather than the 12C isotope. The 13C isotope is, of course, heavier than 12C  by 1 mass unit.  In addition, about 0.015% of all hydrogen atoms are actually deuterium, the 2H isotope.   So the M+1 peak represents those few acetone molecules in the sample which contained either a 13C or 2H.   

Molecules with lots of oxygen atoms sometimes show a small M+2 peak (2 m/z units greater than the parent peak) in their mass spectra, due to the presence of a small amount of 18O (the most abundant isotope of oxygen is 16O). Because  there are two abundant isotopes of both chlorine (about 75% 35Cl and 25% 37Cl) and bromine (about 50% 79Br and 50% 81Br), chlorinated and brominated compounds have very large and recognizable  M+2 peaks. Fragments containing both isotopes of Br can be seen in the mass spectrum of ethyl bromide: 

Much of the utility in electron-ionization MS comes from the fact that the radical cations generated in the electron-bombardment process tend to fragment in predictable ways.  Detailed analysis of the typical fragmentation patterns of different functional groups is beyond the scope of this text, but it is worthwhile to see a few representative examples, even if we don’t attempt to understand the exact process by which the fragmentation occurs.  We saw, for example, that the base peak in the mass spectrum of acetone is m/z = 43.  This is the result of cleavage at the ‘alpha’ position - in other words, at the carbon-carbon bond adjacent to the carbonyl.  Alpha cleavage results in the formation of an acylium ion  (which accounts for the base peak at m/z = 43) and a methyl radical, which is neutral and therefore not detected.

After the parent peak and the base peak, the next largest peak, at a relative abundance of 23%, is at m/z = 15.  This, as you might expect, is the result of formation of a methyl cation, in addition to an acyl radical (which is neutral and not detected). 

A common fragmentation pattern for larger carbonyl compounds is called the McLafferty rearrangement:

The mass spectrum of 2-hexanone shows a 'McLafferty fragment' at m/z = 58, while the propene fragment is not observed because it is a neutral species (remember, only cationic fragments are observed in MS). The base peak in this spectrum is again an acylium ion.

When alcohols are subjected to electron ionization MS, the molecular ion is highly unstable and thus a parent peak is often not detected.  Often the base peak is from an ‘oxonium’ ion.

Other functional groups have predictable fragmentation patterns as well. By carefully analyzing the fragmentation information that a mass spectrum provides, a knowledgeable spectrometrist can often ‘put the puzzle together’ and make some very confident predictions about the structure of the starting sample.

 

You can see many more actual examples of mass spectra in the Spectral Database for Organic Compounds

 

 

 

 

Exercise 4.1: Using the fragmentation patterns for acetone  as a guide, predict the signals that you would find in the mass spectra of:

a) 2-butanone; b) 3-hexanone;  c) cyclopentanone.

 

Exercise 4.2: Predict some signals that you would expect to see in a mass spectrum of 2-chloropropane.

 

Exercise 4.3: The mass spectrum of an aldehyde shows a parent peak at m/z = 58 and a base peak at m/z = 29.  Propose a structure, and identify the two species whose m/z values were listed. (

Solutions

Gas Chromatography - Mass Spectrometry

Quite often, mass spectrometry is used in conjunction with a separation technique called gas chromatography (GC).  The combined GC-MS procedure is very useful when dealing with a sample that is a mixture of two or more different compounds, because the various compounds are separated from one another before being subjected individually to MS analysis.  We will not go into the details of gas chromatography here, although if you are taking an organic laboratory course you might well get a chance to try your hand at GC, and you will almost certainly be exposed to the conceptually analogous techniques of thin layer and column chromatography.  Suffice it to say that in GC, a very small amount of a liquid sample is vaporized, injected into a long, coiled metal column, and pushed though the column by helium gas.  Along the way, different compounds in the sample stick to the walls of the column to different extents, and thus travel at different speeds and emerge separately from the end of the column.  In GC-MS, each purified compound is sent directly from the end of GC column into the MS instrument, so in the end we get a separate mass spectrum for each of the compounds in the original mixed sample.  Because a compound's MS spectrum is a very reliable and reproducible  'fingerprint', we can instruct the instrument to search an MS database and identify each compound in the sample.

 

Gas chromatography-mass spectrometry (GC-MS) schematic

(Image from Wikipedia by K. Murray)

 

The extremely high sensitivity of modern GC-MS instrumentation makes it possible to detect and identify very small trace amounts of organic compounds.  GC-MS is being used increasingly by environmental chemists to detect the presence of harmful organic contaminants in food and water samples.   Airport security screeners  also use high-speed GC-MS instruments to look for residue from bomb-making chemicals on checked luggage. 

 

This section will ignore the information you can get from the molecular ion (or ions). That is covered in three other pages which you can get at via the mass spectrometry menu. You will find a link at the bottom of the page.

Working out which ion produces which line

This is generally the simplest thing you can be asked to do.

The mass spectrum of pentane

Let's have another look at the mass spectrum for pentane:

What causes the line at m/z = 57?

How many carbon atoms are there in this ion? There can't be 5 because 5 x 12 = 60. What about 4? 4 x 12 = 48. That leaves 9 to make up a total of 57. How about C4H9+ then?

C4H9+ would be [CH3CH2CH2CH2]+, and this would be produced by the following fragmentation:

The methyl radical produced will simply get lost in the machine.

The line at m/z = 43 can be worked out similarly. If you play around with the numbers, you will find that this corresponds to a break producing a 3-carbon ion:

The line at m/z = 29 is typical of an ethyl ion, [CH3CH2]+:

The other lines in the mass spectrum are more difficult to explain. For example, lines with m/z values 1 or 2 less than one of the easy lines are often due to loss of one or more hydrogen atoms during the fragmentation process. You are very unlikely to have to explain any but the most obvious cases in an A'level exam.

The mass spectrum of pentan-3-one

This time the base peak (the tallest peak - and so the commonest fragment ion) is at m/z = 57. But this isn't produced by the same ion as the same m/z value peak in pentane.

If you remember, the m/z = 57 peak in pentane was produced by [CH3CH2CH2CH2]+. If you look at the structure of pentan-3-one, it's impossible to get that particular fragment from it.

Work along the molecule mentally chopping bits off until you come up with something that adds up to 57. With a small amount of patience, you'll eventually find [CH3CH2CO]+ - which is produced by this fragmentation:

You would get exactly the same products whichever side of the CO group you split the molecular ion.

The m/z = 29 peak is produced by the ethyl ion - which once again could be formed by splitting the molecular ion either side of the CO group.

Peak heights and the stability of ions

The more stable an ion is, the more likely it is to form. The more of a particular sort of ion that's formed, the higher its peak height will be. We'll look at two common examples of this.

Examples involving carbocations (carbonium ions)

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