New experimental results on the dc electrical conductance, between room temperature and 250°C, of potassium azide single crystals and pellets and potassium azide doped with barium azide are described. These data have been interpreted as involving cation current carrying species. Numerical values for the enthalpy of migration and enthalpy of defect pair formation are deduced. These are, respectively &Dgr;h1=0.79±0.05 andh=1.43±0.05. Isothermal dc conductance data are also presented and imply that the charge carriers are involved in the thermal decomposition processes of KN3.