Thermal decomposition of solid azobisisobutyronitrile
Thermal decomposition of solid azobisisobutyronitrile
复制标题
固体偶氮二异丁腈的热分解
作者：
V. V. Dubikhin;E. I. Knerel’man;L. Nazina;V. G. Prokudin;A. Shastin;I. G. Shunina;G. M. Nazin
固体偶氮二异丁腈的热分解速率在这样的条件下测量，使得副过程，例如气相分解、液体产物的形成、晶体裂化和多晶型转变，对过程速率没有影响。反应发生在晶体的内表面，其速率取决于结晶的方法。在低过饱和度条件下结晶的样品最稳定。反应的动力学参数为E = 134.9 ± 3.5 kJ/mol和log A = 14.12 ± 1.5 [s−1]。固体偶氮二异丁腈在苯溶液中的分解速率常数比偶氮二异丁腈低50倍。在固相中的低反应速率的解释在分子晶体中的单分子反应提出的附加体积模型。
The rate of the thermal decomposition of solid azobisisobutyronitrile was measured under conditions such that the side processes, such as gas-phase decomposition, the formation of liquid products, crystal cracking, and polymorphic transitions, had no effect on the process rate. The reaction occurs on the inner crystal surface, and its rate depends on the method of crystallization. The sample crystallized under conditions of low supersaturation is the most stable. The kinetic parameters of the reaction are E = 134.9 ± 3.5 kJ/mol and log A = 14.12 ± 1.5 [s−1]. The decomposition rate constant of solid azobisisobutyronitrile is 50 times lower than that of azobisisobutyronitrile in benzene solution. The low reaction rate in the solid phase is explained in terms of the additional-volume model proposed for unimolecular reactions in molecular crystals.