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The M+1 Peak

Look closely at a mass spectrum and you will usually see a very small peak one unit to the right of the molecular ion peak. This is the M+1 peak.It is caused by molecules that contain one atom of carbon-13, 13C, instead of carbon-12. About 1.1% of all carbon atoms are carbon-13, so a small fraction of molecules are one mass unit heavier than the rest. For example, most ethane molecules have Mr = 30, but a few contain one 13C atom and have a mass of 31.The more carbon atoms a molecule has, the greater the chance that one of them is 13C, so the M+1 peak becomes larger compared with the M+ peak.The M+1 peak matters when you read a spectrum: the molecular ion is the tall line just before the tiny M+1 line, not the tiny line itself. For a compound with Mr = 58, the M+1 peak is at m/z = 59.Extension, estimating the number of carbon atoms: dividing the percentage ratio of the M+1 and M+ peak heights by 1.1 gives the approximate number of carbon atoms.
number of C atoms ≈ (height of M+1 ÷ height of M+) × 100 ÷ 1.1
Worked example: M+ has relative abundance 40% and M+1 has 1.8%.
1.8 ÷ 40 × 100 = 4.5%, and 4.5 ÷ 1.1 = 4.1, so the molecule contains 4 carbon atoms.

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Specification: OCR Chemistry A (H032), AS-level, 4.2.4 Analytical techniques. Topic: Analytical Techniques.

Key terms in this lesson

molecular ion
The positive ion, M+, formed in a mass spectrometer when a molecule loses one electron; its mass gives the relative molecular mass.
mass-to-charge ratio
The ratio of the mass of an ion to its charge, given the symbol m/z, used to identify ions in a mass spectrum.

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