Mass spectrometry is based on slightly different principles to the other spectroscopic methods.

Mass spectrometry is based on slightly different principles to the other spectroscopic methods. The physics behind mass spectrometry is that a charged particle passing through a magnetic field is deflected along a circular path on a radius that is proportional to the mass to charge ratio, m/e.  In an electron impact mass spectrometer, a high energy beam of electrons is used to displace an electron from the organic molecule to form a radical cation known as the molecular ion. If the molecular ion is too unstable then it can fragment to give other smaller ions. The collection of ions is then focused into a beam and accelerated into the magnetic field and deflected along circular paths according to the masses of the ions. By adjusting the magnetic field, the ions can be focused on the detector and recorded.

• Probably the most useful information you should be able to obtain from a MS spectrum is the molecular weight of the sample.
• This will often be the heaviest ion observed from the sample provided this ion is stable enough to be observed.

Terminology
 

Molecular ion	The ion obtained by the loss of an electron from the molecule
Base peak	The most intense peak in the MS, assigned 100% intensity
M+	Symbol often given to the molecular ion
Radical cation	+ve charged species with an odd number of electrons
Fragment ions	Lighter cations formed by the decomposition of the molecular ion.  These often correspond to stable carbcations.

Spectra
The MS of a typical hydrocarbon, n-decane is shown below. The molecular ion is seen as a small peak at m/z = 142.  Notice the series ions detected that correspond to fragments that differ by 14 mass units, formed by the cleaving of bonds at successive -CH₂- units
The MS of benzyl alcohol is shown below. The molecular ion is seen at m/z = 108.  Fragmentation via loss of 17 (-OH) gives a common fragment seen for alkyl benzenes at m/z = 91.  Loss of 31 (-CH₂OH) from the molecular ion gives 77 corresponding to the phenyl cation. Note the small peaks at 109 and 110 which correspond to the presence of small amounts of 13C in the sample (which has about 1% natural abundance).

Isotope patterns

• Mass spectrometers are capable of separating and detecting individual ions even those that only differ by a single atomic mass unit.
• As a  result molecules containing different isotopes can be distinguished.
• This is most apparent when atoms such as bromine or chlorine are present (⁷⁹Br : ⁸¹Br, intensity 1:1 and ³⁵Cl : ³⁷Cl, intensity 3:1) where peaks at "M" and "M+2" are obtained.
• The intensity ratios in the isotope patterns are due to the natural abundance of the isotopes.
• "M+1" peaks are seen due the the presence of ¹³C in the sample.

The following two mass spectra show examples of haloalkanes with characteristic isotope patterns. The first MS is of 2-chloropropane. Note the isotope pattern at 78 and 80 that represent the M amd M+2 in a 3:1 ratio.
Loss of ³⁵Cl from 78 or ³⁷Cl from 80 gives the base peak a m/z = 43, corresponding to the secondary propyl cation. Note that the peaks at m/z = 63 and 65 still contain Cl and therefore also show the 3:1 isotope pattern.
 




 

The second MS is of 1-bromopropane. Note the isotope pattern at 122 and 124 that represent the M amd M+2 in a 1:1 ratio. Loss of ⁷⁹Br from 122 or ⁸¹Br from 124 gives the base peak a m/z = 43, corresponding to the propyl cation. Note that other peaks, such as those at m/z = 107 and 109 still contain Br and therefore also show the 1:1 isotope pattern.