动力学参数数目与法方程条件数的关系

多相催化反应动力学研究的基本问题是动力学方程中的参数估计，它一直是动力学研究中的活跃领域·在参数估计中最常用的方法是最小二乘法．早在1947年［刘开始用线性最小二乘法处理动力学模型的数据．1958年在线性最小二乘法中应用置信区间问题［21．1959年MarguardM出非线性最小二乘法问．前人提出如何求非线性最小二乘法的初值［4］，及加权最小二乘法的重要性问，并对最小二乘法在动力学中的应用做了综述卜］．在多相催化动力学研究中，关干线性最小二乘法遇到根本性困难的问题前人未涉及．我们曾在动力学研究中发现线性最小二乘法的法…

The Dependence of the Number of Kinetic Parameters on the Condition Number of Normal Equation

The kinetics of isomerisation of 1-butene over Lu2O3/SiO2 catalyst has beeninvestigated by the flow-recirculation glass reactor. The heats of adsorption for 1-butene,2-butene and water were deteched by the pulse method. The kinetics of isomerizationof 1-butene obeys the L-H mechaniasm Kinetic equation. We observed that L-H kineticequation with two parameters is the good-conditioned equation. The L-H kinetic equation with more than three paramters is a ill-conditioned equation. The condition numberof normal equation increases with the increase of paramter numbers for kinetic equation.In addition, we observed that the condition number is not less than the square of ratio oflong to short in column vector for the coefficient matrix of contradiction equation.