AbstractCalcium carbonate fillers react with hydrogen chloride liberated during pyrolysis of PVC to an extent depending on their particle sizes and concentrations. The effects of these and other fillers on the critical oxygen index is more complex and depends on a number of factors additional to the extent of hydrogen chloride retention, of which char formation in particular is not readily assessed numerically. Differential thermal analyses suggest that the reaction of hydrogen chloride with calcium carbonate or calcium oxide fillers proceeds rapidly upon liberation. Hydrogen chloride added to the gas stream raises the critical oxygen index to a considerably greater extent than do carbon dioxide or nitrogen. It is concluded that the exotherm due to reaction between calcium carbonate fillers and pyrolysis hydrogen chloride contributes only slightly to flammability, and that the involvement of hydrogen chloride in reducing flammability is chemical rather than physical.