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Understanding Mass Spectrometry Basics

A mass spectrometer performs three functions: 1) creation of ions from a sample, 2) separation of ions based on mass-to-charge ratio, and 3) detection of separated ions. The mass spectrum presents data as ion abundance versus m/e ratio, with the most abundant ion as the base peak. Molecular ions are observed at the molecular weight if only one electron is lost. Fragment ions are also observed and indicate bond breaking within the molecule. The presence of a molecular ion peak requires it to be the highest mass ion and an odd number of electrons to form other fragments.

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72 views14 pages

Understanding Mass Spectrometry Basics

A mass spectrometer performs three functions: 1) creation of ions from a sample, 2) separation of ions based on mass-to-charge ratio, and 3) detection of separated ions. The mass spectrum presents data as ion abundance versus m/e ratio, with the most abundant ion as the base peak. Molecular ions are observed at the molecular weight if only one electron is lost. Fragment ions are also observed and indicate bond breaking within the molecule. The presence of a molecular ion peak requires it to be the highest mass ion and an odd number of electrons to form other fragments.

Uploaded by

Aditya Garg
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© © All Rights Reserved
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Mass Spectrometry

The Mass Spectrometer


General Schematic
A mass spectrometer needs to perform three functions:
• Creation of ions – the sample molecules are subjected to a high energy
beam of electrons, converting some of them to ions

• Separation of ions – as they are accelerated in an electric field, the ions


are separated according to mass-to-charge ratio (m/z)

• Detection of ions – as each separated population of ions is generated,


the spectrometer needs to qualify and quantify them
The Mass Spectrum
Presentation of data

base peak, m/e 43


❑The mass spectrum is presented in terms
of ion abundance vs. m/e ratio (mass)
❑The most abundant ion formed in
ionization gives rise to the tallest peak on

M+, m/e 114


the mass spectrum – this is the base peak
❑All other peak intensities are relative to
the base peak as a percentage
❑If a molecule loses only one electron in
the ionization process, a molecular ion is
observed that gives its molecular weight –
this is designated as M+ on the spectrum
❑ In most cases, when a molecule loses a
valence electron, bonds are broken, or
the ion formed quickly fragment to
lower energy ions fragment ions

❑ The masses of charged ions are


recorded as fragment ions by the
spectrometer – neutral fragments are
not recorded !
Molecular Ion Peak

Three facts must apply for a molecular ion peak:


1) The peak must correspond to the highest
mass ion on the spectrum excluding the
isotopic peaks

2) The ion must have an odd number of


electrons – usually a radical cation

3) The ion must be able to form the other


fragments on the spectrum by loss of logical
neutral fragments
Important points about MI peak
• In case of hydrocarbons, MI peak intensity decreases with branching
• If MI peak is intense then compound must be highly conjugated
alkene, polycyclic aromatic compound, compound containing I, Br, S,
N
• If MI peak is absent, then compound must be highly branched alkane,
alcohol, ether, PhOH, R-F
• If MI peak is moderately intense then compound must be a straight
chain alkane, R-Cl, compound containing C=O, aldehyde, ketone,
acid, derivatives of acid, R-NO2
Nitrogen Rule
• If MI peak is observed at odd no. Compound must contain odd no.
of N atoms

• If MI peak is observed at even no. Compound contains even no. of


N or no N atom
Example MS: cycloalkanes – cyclohexane

M - 28 = 56
M+ 84
Example MS: alkenes – cis- 2-pentene

55

M+ 70

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