• When a compound is analysed in a mass spectrometer, vaporised molecules are bombarded with a beam of high-speed electrons
• These knock off an electron from some of the molecules, creating?molecular ions:

• The relative abundances of the detected ions form a?mass spectrum: a kind of molecular fingerprint that can be identified by computer using a spectral database
• The peak with the highest?m/e?value is the molecular ion (M⁺) peak which gives information about the?molecular?mass?of the compound
• This value of m/z is equal to the?relative molecular mass?of the compound

The M+1 peak

• The [M+1]?peak is a smaller peak which is due to the natural abundance of the isotope?carbon-13
• The height of the?[M+1]?peak for a particular ion depends on how many carbon atoms are present in that molecule; The more carbon atoms, the larger the?[M+1]?peak is
  • For example, the height of the?[M+1]?peak for an hexane (containing six carbon atoms) ion will be greater than the height of the?[M+1]?peak of an ethane (containing two carbon atoms) ion

Answer:

• • The mass spectrum corresponds to?propanal?as the molecular ion peak is at?m/e?= 58
  • Propanal arises from the CH₃CH₂CHO⁺?ion which has a molecular mass of 58
  • Butanal arises from the CH₃CH₂CH₂CHO^+?ion which has a molecular mass of 72

• The molecular ion peak can be used to identify the?molecular mass?of a compound
• However, different compounds may have the same molecular mass
• To further determine the structure of the unknown compound,?fragmentation analysis?is used
• Fragments may appear due to the formation of?characteristic?fragments?or the?loss?of?small?molecules
  • For example, a peak at 29 is due to the characteristic fragment C₂H₅⁺--
  • Loss of small molecules give rise to peaks at 18 (H₂O), 28 (CO), and 44 (CO₂)

Alkanes

• Simple alkanes are fragmented in mass spectroscopy by breaking the C-C bonds
• M/e?values of some of the common alkane fragments are given in the table below

m/e?values of Fragments Table

Mass spectrum showing fragmentation of alkanes

Halogenoalkanes

• Halogenoalkanes have often multiple peaks around the molecular ion peak
• This is caused by the fact that there are different isotopes of the halogens

Alcohols

• Alcohols often tend to lose a?water molecule?giving rise to a peak at?18 below the molecular ion
• Another common peak is found at?m/e?value 31 which corresponds to the CH₂OH⁺-- fragment
• For example, the mass spectrum of propan-1-ol shows that the compound has fragmented in four different ways:
  • Loss of H to form a C₃H₇O⁺?fragment with?m/e?= 59
  • Loss of a water molecule to form a C₃H₆⁺?fragment with?m/e?= 42
  • Loss of a C₂H₅?to form a CH₂OH⁺?fragment with?m/e?= 31
  • And the loss of CH₂OH to form a C₂H₅⁺?fragment with?m/e?= 29