The reaction kinetics of ammonium bisulfate clusters with dimethylamine (DMA) gas were investigated using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Clusters ranged in size from 1 to 10 bisulfate ions. Although displacement of the first several ammonium ions by DMA occurred with near unit efficiency, displacement of the final ammonium ion was cluster size dependent. For small clusters, all ammonium ions are exposed to incoming DMA molecules, allowing for facile exchange (“surface” exchange). However, with increasing cluster size, an ammonium ion can be trapped in an inaccessible region of the cluster (“core” exchange), thereby rendering exchange difficult. DMA was also observed to add onto existing dimethylaminium bisulfate clusters above a critical size, whereas ammonia did not add onto ammonium bisulfate clusters. The results suggest that as the cluster size increases, di-dimethylaminium sulfate formation becomes more favorable. The results of this study give further evidence to suggest that ambient sub-3 nm diameter particles are likely to contain aminium salts rather than ammonium salts.