Mass Spectrometry (OCR A Level Chemistry)

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Interpreting Mass Spectra

  • 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:

Interpreting Mass Spectra equation 1
  • 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/z 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

Worked example

Determine whether the following mass spectrum belongs to propanal or butanalAnalytical Techniques Spec 1_Mass Spectrometry, downloadable AS & A Level Chemistry revision notes

Answer:

    • The mass spectrum corresponds to propanal as the molecular ion peak is at m/z = 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

Fragmentation Peaks in Mass Spectra

  • 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 gives rise to differences between peaks of, for example, 18 (H2O), 28 (CO), and 44 (CO2)
    • An alcohol can typically dehydrate in a MS, so one peak to look for is M-18

Alkanes

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

m/z values of Fragments Table

Analytical Techniques - m_e values of fragments table, downloadable AS & A Level Chemistry revision notes

Analytical Techniques Alkane Spectrum, downloadable AS & A Level Chemistry revision notes

Mass spectrum showing fragmentation of alkanes

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

Analytical Techniques Alcohols Spectrum_2, downloadable AS & A Level Chemistry revision notes

Mass spectrum showing the fragmentation patterns in propan-1-ol (alcohol)

Worked example

Alcohol fragmentation

Which alcohol is not likely to have a fragment ion at m/z at 43 in its mass spectrum?

  1. (CH3)2CHCH2OH
  2. CH3CH(OH)CH2CH2CH3
  3. CH3CH2CH2CH2OH
  4. CH3CH2CH(OH)CH3

Answer

The correct answer is option D

    • Because a line at m/z = 43 corresponds to an ion with a mass of 43 for example:
      • [CH3CH2CH2]+
      • [(CH3)2CH]+
    • 2-butanol is not likely to have a fragment at m/z = 43 as it does not have either of these fragments in its structure.

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Richard

Author: Richard

Expertise: Chemistry

Richard has taught Chemistry for over 15 years as well as working as a science tutor, examiner, content creator and author. He wasn’t the greatest at exams and only discovered how to revise in his final year at university. That knowledge made him want to help students learn how to revise, challenge them to think about what they actually know and hopefully succeed; so here he is, happily, at SME.