Monoisotopic mass

For some atoms like carbon, oxygen, hydrogen, nitrogen, and sulfur, the Mmi of these elements is exactly the same as the mass of its natural isotope, which is the lightest one.

(2*12)+(4*1)= 28 Da What this means, is when using mass spectrometer with insufficient source of power "low resolution" like a quadrupole mass analyser or a quadrupolar ion trap, these two molecules won't be able to be distinguished after ionization, this will be shown by the cross lapping of the m/z peaks.

If a high-resolution instrument like an orbitrap or an ion cyclotron resonance is used, these two molecules can be distinguished.

This concept is most helpful in mass spectrometry because individual molecules (or atoms, as in ICP-MS) are measured, and not their statistical average as a whole.

Since mass spectrometry is often used for quantifying trace-level compounds, maximizing the sensitivity of the analysis is usually desired.

By choosing to look for the most abundant isotopic version of a molecule, the analysis is likely to be most sensitive, which enables even smaller amounts of the target compounds to be quantified.

The isotopic substitution changes the vibrational frequencies of various bonds in the molecule, which can have observable effects on the chemical reactivity via the kinetic isotope effect, and even by extension the biological activity in some cases.

Orbitrap Mass Analyzers