Keleti T
Biochem J. 1983 Jan 1;209(1):277-80. doi: 10.1042/bj2090277.
Errors in the numerical values of activation or normal enthalpies, entropies and free enthalpies calculated from Arrhenius or van't Hoff plots, respectively, are due to the neglect of equidimensionality in equations, or to inappropriate approximations. The logarithmization of dimensioned quantities should be avoided, which demands the use of relative concentrations if a change in mole number occurs in the reaction. The application of the Arrhenius plot to enzymic reactions by using Vmax./ET instead of the rate constant of product formation has meaning only if the reaction follows the simplest Michaelis-Menten mechanism; however, the use of the van't Hoff plot using Km is questionable even in the latter case.
分别根据阿伦尼乌斯图或范特霍夫图计算的活化焓、标准焓、熵和自由焓的数值误差,是由于方程中忽略了量纲一致性,或由于近似不当。应避免对有量纲的量取对数,如果反应中摩尔数发生变化,则需要使用相对浓度。仅当反应遵循最简单的米氏机制时,通过使用Vmax./ET而非产物形成速率常数将阿伦尼乌斯图应用于酶促反应才有意义;然而,即使在后一种情况下,使用包含Km的范特霍夫图也存在问题。