How does 2-butanone fragment during electron-ionization mass spectrometry?

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In electron-ionization mass spectrometry, 2-butanone undergoes fragmentation primarily at the bonds where the alkane chains are attached to the carbonyl group.12

The fragmentation process occurs as follows:

  • Molecular Ion: The molecule is initially ionized to form a molecular ion at m/z = 72.12
  • Loss of Methyl Group: The loss of a CH₃ group (mass 15) from the molecular ion generates a fragment at m/z = 57.12
  • Loss of Ethyl Group: The loss of the heavier CH₃CH₂ group (mass 29) generates a fragment at m/z = 43. This specific fragment corresponds to the base peak of the spectrum, which is the most intense peak recorded.12