The use of permanent magnet [to the thirteenth power]C NMR in large-section first-semester organic chemistry lab courses is limited by the availability of experiments that not only hinge on first-semester lecture topics, but which also produce at least 0.5 mL of neat liquid sample. This article reports a discovery-based experiment that meets both of these criteria. Students convert three alcohols to alkyl halides under acidic conditions and record the [to the thirteenth power]C NMR spectrum in each case. By comparing the number of resonances observed with the number of resonances predicted for each possible product, they conclude that (i) with 1-propanol there is no carbocation rearrangement, (ii) with 2-pentanol there is a considerable degree of secondary-to-secondary carbocation rearrangement, and (iii) with 2,4-dimethyl-3-pentanol all of the alkyl halide formed is the result of a secondary-to-tertiary carbocation rearrangement. (Contains 1 table.)