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计算二聚体系平衡常数的三元方程组受实验数据的影响十分敏感,现有精确解法存在增根,且判定、消除增根困难。通过分析实验数据与三元方程组的关系发现:只要比例关系C_(t3)/C_(t1)=A_3/A_1、C_(t3)/C_(t2)=A_3/A_2、C_(t2)/C_(t1)=A_2/A_1和(A_3-A_2)/(A_2-A_1)=(C_(t3)-C_(t2))/(C_(t2)-C_(t1))中任何一个成立,则相应方程组无解,否则有解。经过一系列代数变换,导出了判定合法解的有效准则。并以拟合误差为判据提出了确定总常数的方法。用该方法算出二碳化和三磺化酞菁的平衡常数分别为47973.4和30271.8。
The ternary equations for calculating the equilibrium constants of dimeric system are very sensitive to the influence of the experimental data. The existence of the root of the existing exact solution exists, and the determination and elimination of rooting difficulties are eliminated. By analyzing the relationship between the experimental data and the ternary system of equations, it is found that as long as the proportional relationship C_ (t3) / C_ (t1) = A_3 / A_1, C_ (t3) / C_ (t2) = A_3 / A_2, C_ (t2) (t1) = A_2 / A_1 and (A_3-A_2) / (A_2-A_1) = (C_ (t3) -C_ (t2)) / (C_ (t2) -C_ (t1) Equations have no solution, otherwise there is solution. After a series of algebraic transformations, we derive the effective criteria for judging legal solutions. The method of determining the total constant is put forward based on the fitting error. The equilibrium constants for the dicarboxylation and trisulfonation phthalocyanines were calculated by this method to be 47973.4 and 30271.8, respectively.