AbstractThis paper addresses the unusual combustion hazards of silane and its chlorides, comprising the homologous chlorosilane series SiHnCl4‐n. The literature on silane is briefly reviewed and new experimental data presented showing the effects of sudden releases into free air. New data are presented for ignition sensitivities and deflagration rates of chlorosilane mixtures with air. Specific hazardous reactions of this group of materials are described and contrasted with those of the analogous alkanes. Mechanisms for flame acceleration and transition to detonation are discusse