N,N'-pentamethylenethiuram disulfide (CPTD), CPTD/sulfur, and N,N'-pentamethylenethiuram hexasulfide (CPTP6) were heated in a DSC at a programmed heating rate and isothermally at 140 degrees C. Residual reactants and reaction products were analyzed by HPLC at various temperatures or reaction times. CPTD rapidly formed N,N'-pentamethylenethiuram monosulfide (CPTM) and N,N'-pentamethylenethiuram polysulfides (CPTP) of different sulfur rank, CPTP of higher sulfur rank forming sequentially, as reported earlier for tetramethylthiuram disulfide (TMTD). As with TMTD, the high concentration of the accelerator monosulfide that develops is attributed to an exchange between CPTD and sulfenyl radicals, produced on homolysis of CPTD. However, a different mechanism for CPTP formation to that suggested for TMTD is proposed. It is suggested that disulfenyl radicals, resulting from CPTM formation, exchange with CPTD and/or CPTP already formed, to give CPTP of higher sulfur rank. CPTD/sulfur and CPTP6 very rapidly form a similar product spectrum with CPTP of sulfur rank 1-14 being detectable. Unlike with TMTD/sulfur, polysulfides of high sulfur rank did not form sequentially when sulfur was present, CPTP of all sulfur rank being detected after 30 s. It is proposed that sulfur adds directly to thiuram sulfenyl radicals. Recombination with sulfenyl radicals, which would be the most plentiful in the system, would result in highly sulfurated unstable CPTP. CPTP of higher sulfur rank are less stable than are disulfides as persulfenyl radicals are stabilized by cyclization, and the rapid random dissociation of the highly sulfurated CPTP, followed by the rapid random recombination of the radicals, would result in the observed product spectrum. CPTP is thermally less stable than is TMTD and at 140 degrees C decomposed rapidly to N,N'-pentamethylenethiourea (CPTU), sulfur, and CS2. At 120 degrees C, little degradation was observed. The zinc complex, zinc bis(pentamethylenedithiocarbamate), did not form at vulcanization temperatures, although limited formation was observed above 170 degrees C. ZnO inhibits degradation of CPTD to CPTU.