MASS SPECTROMETRY AND INFRA-RED SPECTROSCOPY AS INSTRUMENTAL METHODS OF ANALYSIS. By Patrick Mc Ilwaine.

Mass Spectrometry has a number of uses for example geologists use it to date rocks; anaesthetists use it to analyse compounds in a patient breath, pharmaceutical companies make use of mass spectrometry to determine the structure of novel compounds etc. The greatest property of mass spectrometry is that it is the most accurate method of determining relative atomic and molecular masses. How a mass spectrometer works: When a sample of a particular substance is placed in a mass spectrometer, it is firstly vaporised before being passed into an ionisation chamber. Here atoms of the substance are bombarded with a stream of high-energy electrons, which results in the formation of a molecular ion as well as a number of fragments. These ions are then fed into an electric field where they are accelerated and passed through a narrow slit, producing a narrow beam of positive ions. This beam is then subjected to a magnetic field causing the ions to be deflected a particular distance depending on the mass to charge ratio. The ions deflected are detected by a particular instrument, which then sends messages to a recorder resulting in the formation of a mass spectrum.

The greater the mass/charge ratio of the ion the less it is deflected; the molecular ion (M ) has the greatest mass/charge ratio and will appear furthest to the right of the spectrum. The different fragments produced provides useful information, each fragment gives a corresponding line in the mass spectrum

INTERPRETING MASS SPECTRA

To interpret mass spectra you must be aware of some key points:

Molecular ion (M ) If the molecular ion appears it will be the highest mass in the spectrum. This peak represents the molecular weight of the compound. Its appearance depends on the stability of the compound. Double bonds, cyclic structures and aromatic rings stabilises the molecular ion and therefore increases the probability of its appearance. Fragmentation- fragments are very useful in determining the structures of a compound. We can find the relative mass of the fragments and use this to work out its formula, it is then possible by piercing the fragments together to deduce the structure of the parent molecule.

Certain fragments are common in mass spectra. They include the following: Fragmen t CH3 OH CN C2H4, CO C2H 5 OCH3 Cl CH3CO CH3CH2O C4H 9 C6H 5 C6H5CH2 Mass 15 17 26 28 29 31 35 43 45 57 77 91

Apart from deciding the identity of the peaks, the other important thing to look for is the differences in masses between the peaks. For example a difference of 15 is almost certainly due to the loss of a methyl fragment. Therefore, its highly likely that the original molecule contains a methyl group.

Isotope peaks these may also be present in mass spectra and can aid in peak identification, as isotopic peaks are characteristic of particular compounds. Below is an example of a mass spectrum. (I have shown how you would interpret it)

From the spectra it can be seen that the molecular ion has a mass of 72 The next step is too identify some of the peaks: Peak at 15 is typical of a CH3 fragment, peak at 29 is typical of a C2H5 fragment and the peak at 43 is probably due to a CH3CO. From these fragments it is possible to deduce that the molecular ion present is either a ketone or an aldehyde due to the presence of the carbonyl group(C=O). On further examination it also becomes evident that it cant be a aldehyde as the carbon in the CH3CO fragment can only hold one more atom or group of atoms, and if this atom was hydrogen (indicating an aldehyde) then the spectra would not have produced a peak at 29 indicating a C2H5 fragment. The molecular ion is actually a ketone with molecular formula CH3COC2H5 (i.e. BUTANONE)

INFRA-RED SPECTROSCOPY
Infrared spectroscopy makes use of the fact that molecules can absorb infrared radiation of frequencies that match the energy of changes in molecular vibrations. Infrared spectroscopy is therefore often called vibrational spectroscopy. Different groups of atoms absorb different energies, and if a broad range of energies are shone at a sample of a compound, certain energies will be missing from the emergent beam of radiation. These energies are characteristic of the functional groups present in the sample. A spectrometer produces an infrared spectrum on a chart recorder. The x-axis of which shows wavenumber, which is the way in which the wavelength of radiation absorbed is expressed. [Wavenumber = 1/wavelength in cm]

Interpreting infrared spectra

The spectrum of each and every compound acts like a unique finger print and thus makes it possible to identify any compound, often through a computer database. A totally new compound will not match any spectrum in the database but a great deal can be found out from the peaks in its spectrum. The table and graph below shows some typical regions where particular bonds are found in an infrared

spectrum:

Points to note in interpreting IR spectroscopy

Certain troughs of the spectra may have a number of dips e.g.

This can be explained in terms of symmetrical and asymmetrical stretching of bonds. Consider NH2, which has two (N-H)

bonds. These bonds may vibrate in phase (symmetrically) or out of

phase (asymmetrical).

If a peak representing OH, is broad then hydrogen bonding is present. (Hydrogen bonding tends to broaden the peaks) A small peak with a very high wave number may occur these are referred too as overtones. For example(C=O) group may have a large peak at 1720. If another peak is present at 3440, its probably due to the overtone of a very strong carbonyl group. Aromatic compounds have characteristic bonds in the range of 700-900 (1/cm) By Patrick Mc Ilwaine: Loreto College, Coleraine.