The bromomethane would have peaks at m/z = 94 and m/z = 96 corresponding to 79Br and 81Br respectively while the peak for the molecular ion of Chlorohexane can only occur at m/z = 66.
The molecular ion in a mass spectra refers to the tallest pick in the spectrum. This would always belong to the specie with the highest mass. Let us recall that the mass spectrum could be used to identify the mass of the compound.
We look at the spectrum to understand the tallest mass and this gives us the mass of the compound that is under examination.
Now we can see that the bromomethane would have peaks at m/z = 94 and m/z = 96 corresponding to 79Br and 81Br respectively while the peak for the molecular ion of Chlorohexane can only occur at m/z = 66.
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