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对于非等温过程中的动力学方程,正确的Arrhenius方程的温度积分应该是从T2到T1,但是许多动力学方程中的温度积分是从T到0K,例如Ozawa等方程。我们的研究指出对于某些反应,这些方程中的活化能存在较大的误差,因此我们提出了一个新的动力学方程。凭借等转化率法,应用新的方程可以精确求解线性或非线性加热过程中化学反应的活化能。用新方程对2个经典反应(聚酰胺的热裂解和一水草酸钙的热分解)的研究表明:Ozawa方程的活化能有时是精确的,有时偏差太大。
For kinetic equations in non-isothermal processes, the temperature integral of the correct Arrhenius equation should be from T2 to T1, but the temperature integration in many kinetic equations is from T to 0K, such as Ozawa’s equation. Our research indicates that there is a large error in the activation energies of these equations for some reactions, so we propose a new kinetic equation. With the equal conversion method, the new equation can be used to solve the activation energy of chemical reaction during linear or non-linear heating. The study of two classical reactions (pyrolysis of polyamide and pyrolysis of calcium oxalate monohydrate) by the new equation shows that the activation energy of the Ozawa equation is sometimes accurate and sometimes large.