isotope pattern
Carbon comes in two stable flavors: most atoms are carbon-12, but about one in a hundred is the slightly heavier carbon-13. Chlorine and bromine come in two heavy flavors each, in striking ratios. Because real samples are a mix of these isotopes, a molecule does not give a single clean mass line — it gives a small cluster, and the relative heights inside that cluster, the isotope pattern, can betray exactly which atoms are present.
Two patterns are especially useful and worth memorizing. Chlorine has two abundant isotopes, chlorine-35 and chlorine-37, in roughly a 3-to-1 ratio. So any molecule containing one chlorine shows two peaks two mass units apart (M and M+2) in about a 3-to-1 height ratio — a dead giveaway. Bromine is even cleaner: bromine-79 and bromine-81 are nearly equal in abundance, so one bromine gives an M and M+2 pair of almost equal height, like two twin towers. A small M+1 peak just above the molecular ion, from carbon-13, grows in proportion to how many carbons the molecule has, giving a rough carbon count.
These patterns turn the mass spectrometer into a quick element detector. Spotting a 3-to-1 doublet two units apart, a chemist immediately suspects chlorine; spotting a near-equal doublet, bromine. This is invaluable for drug metabolites, pesticides, flame retardants, and any halogen-containing molecule, where the isotope signature confirms the halogen long before the rest of the structure is solved.
Chloromethane (CH3Cl) shows two molecular-ion peaks: m/z 50 (with 35Cl) and m/z 52 (with 37Cl) in about a 3:1 height ratio. Bromomethane (CH3Br) instead shows m/z 94 and 96 in roughly 1:1, fingerprinting bromine.
Cl gives a 3:1 M/M+2 doublet; Br gives a roughly 1:1 doublet two mass units apart.
The M+2 doublet means a chlorine or bromine, not that the molecular weight is uncertain. Both peaks are real molecular ions differing only by which isotope happens to be in that particular molecule.