Wednesday, 3 June 2015

2.12a: interpret fragment ion peaks in the mass spectra of simple organic compounds, eg the difference between propanal and propanone

Mass spectrometry can be used to:
  • determine the RAM of an element by measuring the ratio of isotopes present
  • determine the molecular mass (Mr) of a compound as this will be the largest mass detected - the molecular ion peak
  • find the structure of an unknown compound by identifying fragments of the original molecule
  • advantages:
    • only requires tiny amounts of a sample
    • very fast process
How does a mass spectrometer work?:
  • the sample is vaporized by heating in a vacuum, then ionised by bombarding it with high energy electrons from an electron gun which knock an electron off each atom in the sample to generate a positive ion
    • sometimes more than one electron is knocked off, affecting the mass/charge ratio
  • the ions are highly unstable, so are very reactive
    • the inside of the mass spectrometer is a vacuum, so there is nothing for them to react with, but they may fragment
      • fragmentation patterns are useful as they give characteristic masses that can allow us to build up a “jigsaw” of the parent molecule
    • molecules usually fragment along the weakest bond (eg. tertiary more stable than secondary, secondary more stable than primary -  due to the electron donating effect of the alkyl groups to stabilise the positive charge)
Some common fragment ions:

mass to charge ratio (m/z)
possible fragment ion
17
OH+
15
CH3+
29
CH2CH3+ or CHO+
31
CH2OH+ or OCH3+
43
CH3CO+

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