Exchange reactions between tetramethylthiuram disulfide, 2-mercaptobenzothiazole, and sulfur were studied by heating powdered mixes to vulcanization temperatures at a programmed rate in a DSC. The reaction was stopped at points along the thermal curve and the mixture was analyzed by HPLC. On dissolution, even unheated samples underao a sulfide exchange reaction leading to a mixed accelerator, while polysulfides of the thiuram and mixed accelerator form in low concentrations. On heating, higher concentrations of these polysulfides are formed, particularly in the presence of elemental sulfur. Dimethyl-dithiocarbamic acid, formed in the exchange, influences the product spectrum if it remains trapped in the DSC pan. Tetramethylthiourea is formed only at elevated temperatures when dimethylamine, a degradation product of the acid, is trapped in the DSC pan. A series of reactions is proposed to explain the product spectrum obtained under different conditions.