The thermal decomposition of sodium azide has been investigated by monitoring changes in dielectric constant, dielectric loss, and pressure with time at a fixed frequency during decomposition at 262–305°C, and by monitoring changes in dielectric properties with frequency in the range 100 Hz to 300 kHz for samples cooled to 20°C after partial decomposition at 290°C. Curves of ε′ and ε″ against time both show maxima at the stage where the fractional decomposition α shows a marked increase. Three stages of decomposition (A, B and C) can be identified for α < ca. 0.02, and activation energies for the three stages and for two types of sodium azide vary between 28.0 and 73.4 kcal/mole. At 100 kHz, and during stage B, changes in ε′ and ε″ are both related to changes in α by simple power laws, the exponents for which show an approximate linear decrease with increasing temperature. At frequencies below ca. 1 kHz, d.c. conductance is mainly responsible for the dielectric loss, whereas at higher frequencies Debye or Maxwell-Wagner type relaxation processes predominate. The difference in static dielectric constant at 20°C between partially decomposed and undecomposed samples is directly proportional to α2 for values of α corresponding to stage B. Changes in dielectric properties during decomposition are discussed in terms of “dipoles” involving the defect structure of the solid.
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