Beyrich T, Stahlkopf W, Lichtnow K H, Schmidt W
Pharmazie. 1980;34(5-6):302-6.
Three selected model substances of varying activation energy (naphazoline, 109 kJ/mole; acetylsalicylic acid, 72 kJ/mole; and phenobarbital, 60 kJ/mole) were studied to determine the conditions under which the allothermal short-time test according to Zoglio (linear increase in temperature) will yield stability predictions which are consistent with those provided by the isothermal short- or long-time test. The error of the determination method should be less than or equal to 1%. It is advantageous to use for the calculation as many data as the analytical facilities will permit to obtain. The actual value for the respective temperature should differ from the desired value by < +/- 0.2%. The increase in temperature should be very slow 1-2 degrees C/h at best). This is particularly true for substances of low activation energy, because more the energy values calculated on the basis of the allothermal test differ from the isothermally determined values, the flatter is the curve provided by the arrhenius equation. The temperature range should be chosen as large as possible, from 30-90 degress C, and the experiment should be continued until at least a 10% decomposition is achieved. On calculating the collision factor A and the reaction-rate constant for any temperature, it has proved useful to continue the experiment isothermally at the final point of the allothermal test.
研究了三种具有不同活化能的选定模型物质（萘甲唑啉，109千焦/摩尔；乙酰水杨酸，72千焦/摩尔；苯巴比妥，60千焦/摩尔），以确定根据佐利奥方法（温度线性升高）进行的变温短时试验能够得出与等温短时或长时试验一致的稳定性预测结果的条件。测定方法的误差应小于或等于1%。在计算时，应尽可能多地使用分析设备所能提供的数据。各个温度的实际值与期望值的偏差应小于/±0.2%。升温应非常缓慢（最好为1 - 2℃/小时）。对于低活化能物质尤其如此，因为变温试验计算出的能量值与等温测定值的差异越大，阿累尼乌斯方程给出的曲线就越平缓。温度范围应尽可能大，为30 - 90℃，并且试验应持续进行至至少达到10%的分解率。在计算任何温度下的碰撞因子A和反应速率常数时，在变温试验的终点等温继续进行试验已证明是有用的。
