【摘要】 本文以气相色谱数据处理了草酸配位化合物热分解动力学。提出了热分解动力学方程计算结果表明,该方程与实验符合程度比一些常见的动力学方程为好。通过量子化学计算,讨论了Fe（C₂O₄）₃³-的热分解活化步骤。更多还原

【Abstract】 The general method used to derive kinetic parameters from TG or DTA curves is unsatisfactory when the compound decomposed in two or more simultaneous reactions. Such are the thermal decomposition reactions of the oxalato coordination compounds of metals and they were coped with successfully by means of gas chromatography. Moreover, the models of the published kinetic equations are too simple to decipher the results of the pertinent experiments. On the basis of the principle of statistical mechanics, a better kinetic equation has been proposed: da/dt=κ（1-α）(C_-1α^-1+1+C₁α+C₂α²). To compare this equation with the related equations published previously, ten of them were chosen （Table 1 in the Chinese Text） and they were merged mathematically into 6 equations [Eq.（17）～（22）]. The relative deviation was defined as D=1/nΣ_n,（??）/H₁^e×100%,where H₄^c was the peak height calculated by formula（6）and H₄^e the experimental value at T_i（K）. A.computer program which was written in FORTRAN-IV language has been worked out to evaluate the activation energy and the Arrhenius pre-exponential factor. The results of calculation showed in equation （17） gave E_a in better agreement with the experimental data （Table 2）. The results of calculation by EHMO method showed that the activation step in the decomposition of Fe（C₂O₄）₃^3- might be described as the promotion of an electron from an oxalate to the antibonding orbital of Fe3³⁺, the required energy of this process being 46 kcal/mol （Fig. 4 in the Chinese Text）. However, the activation energy of configuration change of Fe（C₂O₄）₂^2-(C₂→D_2h, Fig.5) is 58 kcal/mol. Since the experimental activation energy of the thermal decomposition of Fe（C₂O₄）₃^3- was found to be 69 kcal/mol, the change of configuration might be the activation step.更多还原