Random experimental errors are known to provoke the appearance of false isokinetic enthalpy–entropy relationships under some circumstances. In this contribution, it is shown that the observation of a false error-caused isokinetic plot, with a slope close to the mean working temperature (T_m), does not necessarily preclude the occurrence of a real isokinetic temperature (T_ik) that might be quite different from T_m, for that particular homologous reaction series. However, since accidental errors cause a shift in the value of parameter T_ik toward that of T_m, different numerical simulation methods have been tried to discount this effect and so obtain the most probable (extrapolated) value of T_ik. The method leading to the best results was that of shifting the maximum probability curve for each reaction series until it matched the experimental point (defined by both the T_ik value and the activation enthalpy mean fitting error). Finally, the applicability of this method has been checked out for 17 reaction families selected from chemical bibliographic sources. According to the results found in this study, when the experimental isokinetic temperature is higher than the mean working temperature (T_ik,exp > T_m) the most probable value should be looked for in the high temperature range (T_ik,sim > T_ik,exp), and when T_ik,exp < T_m in the low temperature range (T_ik,sim < T_ik,exp). Moreover, the best parameter to predict the relative error that must be allowed to T_ik,sim is the correlation coefficient of the experimental compensation plot.

Graphic abstract

中文翻译：

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动力学补偿效果：消除了等速温度值中偶然的实验误差引起的变形

众所周知，在某些情况下，随机的实验误差会引起错误的等速焓-熵关系。在此贡献中，表明了观察到由假错误引起的等速运动图，其斜率接近平均工作温度（T _m），并不一定排除实际等速运动温度（T _ik）的发生。对于那个特定的同源反应序列，与T _m有很大的不同。但是，由于意外错误导致参数T _ik的值向T _m的值偏移不同的数值模拟方法已经被试着折扣这种效果，因此得到最可能的（外推）的值Ť _IK。导致最佳结果的方法是移动每个反应系列的最大概率曲线，直到与实验点匹配（由T _ik值和活化焓平均拟合误差定义）。最后，该方法适用于从化学书目来源中选择的17个反应族。根据本研究的结果，当实验等速温度高于平均工作温度时（T _ik，exp  >  T _m）应该在高温范围（T _ik，sim  >  T _ik，exp）中寻找最可能的值，并且当T _ik，exp  <  T _m在低温范围（T _ik，sim  <  T _ik，exp）。此外，最好的参数来预测必须允许相对误差Ť _IK，SIM是实验补偿曲线的相关系数。

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