Abstract: For Ma subsystem in a complex monomolecular reaction system containing irreversible reactions, the character of the only observed straight line reaction path in two dimensional coordinates is observed. A mathematical expression of ray vector as an implicit function of rate constants is derived. Taking advantage of the expression as a set of linear equality constraints, the relative rate constant matrix of hydroisomerization of C8-aromat-ics is estimated by means of flexible tolerance polyhedron. It is proved that the uncertainty of curve-fitting can be reduced because of these constraints. It provides an effective resort for parameter estimation of Ma monomolecular subsystem.

摘要： 线性反应系统和一些非线性反应系统的一个重要结构特点就是存在直线反应路线.本文指出了M~α(?)型线性反应系统中唯一可观测的直线反应路线的二维表达式的特点,并由此出发推导了该直线反应路线的初组成—射线向量的数学表达式和它与热力学平衡组成向量的关系;同时也指出了建立可逆线性反应系统和某些非线性反应系统的直线反应路线的初组成和速度常数之间的数学关系的可能性.本文利用射线向量的数学表达式作为反应系统中速度常数的线性等式约束,用可变误差多面体法求出了八碳芳烃临氢异构反应系统的相对速度常数,并在工业条件下的选择性动力学研究中得到验证.实践证明这种作法减少了曲线拟合时所估参数的不定性,从而为复杂反应系统速度常数的估值提供了一种有效的手段.