Nitrated cellulose (NC) is highly susceptible to thermal runaway such as combustion or explosion during decomposition. Preventing and mitigating the related accidents require more comprehensive analysis of its thermal stability and chemical decomposition kinetics. To understand the effect of combustion on the decomposition mechanism of NC, it is necessary to compare the kinetics in stable decomposition and combustion. In this study, multiple kinetic analyses including model-free and master-plots approaches were used to determine the kinetic parameters and kinetic model of NC in these two cases. The average activation energy (E) was found to be lower in combustion than that in stable decomposition (89.5–97.5 vs. 123.3–145.8 kJ mol⁻¹). The stable decomposition kinetics fits the sigmoidal model, while the combustion kinetics fits the deceleration model. From the compensation effect, the pre-exponential factor was calculated to be 19.0–67.2 ln s⁻¹ for stable decomposition and 12.9–26.1 ln s⁻¹ for combustion. This study provides a new perspective on the methods to determine the compensation effect and expands the research scenarios of thermochemical kinetics.

硝化纤维素 (NC) 在分解过程中极易发生热失控，例如燃烧或爆炸。预防和减轻相关事故需要对其热稳定性和化学分解动力学进行更全面的分析。要了解燃烧对 NC 分解机理的影响，有必要比较稳定分解和燃烧的动力学。在这项研究中，包括无模型和主图方法在内的多种动力学分析被用于确定这两种情况下 NC 的动力学参数和动力学模型。发现燃烧中的平均活化能 ( E ) 低于稳定分解中的平均活化能(89.5–97.5 vs. 123.3–145.8 kJ mol ^-1）。稳定分解动力学符合 sigmoidal 模型，而燃烧动力学符合减速模型。从补偿效果，预指数因子计算为19.0-67.2 LN小号^-1稳定分解和12.9-26.1 LN小号^-1燃烧。该研究为确定补偿效应的方法提供了新的视角，并扩展了热化学动力学的研究场景。