Abstract: A new approach based on the model-free method was proposed to deduce the most probable mechanism function.Firstly, the kinetic models were screened in accordance with the reaction process.Secondly,the Popescu method was adopted to do further screening by virtue of linear correlation coefficient of regression calculation.Finally, the apparent activation energy that was obtained by a combination of the differential method based on single-heating rate and the equi-conversion method based on the multiple-heating rate methods was used to confirm the most probable mechanism function.This approach could avoid the kinetic compensation effect, and in the course of calculation almost no hypothesis or approximation was made and the error caused by differential calculus could be reduced on account of the multiple-heating rate method.The mechanism functions could be easily distinguished when the apparent activation energy other than the linear correlation coefficient was served as the criterion.Thermogravimetry was used to analyze the decomposition of three kinds of limestone，and the result indicated that the shrinking cylinder mechanism with controlling surface reaction rate was the most probable kinetic function.

摘要： 提出一种基于无模式法推断反应机理函数的新方法。首先分析反应发生的过程，对机理函数作初步筛选;然后采用Popescu法通过函数拟合的线性相关度对机理函数作进一步的推断;最后采用单个扫描速率的微分法与等转化率法相结合的方法，以活化能为判据确定最概然机理函数。此方法可以从根本上消除动力学补偿效应的影响，而且计算过程中几乎没有作任何假设和近似处理，多重扫描速率法也可以减小微分计算所带来的误差。以活化能作为反应机理最终的判据，可以对机理函数进行明显的区分，避免了仅依赖函数拟合线性的微小差别进行判断的问题。因此，此方法得到的结果是可靠的。采用热重分析技术对3种石灰石分解反应进行研究，结果表明相界面反应控制的收缩圆柱体模型是石灰石分解的最概然机理函数，进一步证明了此方法的可行性。