Stanford Victoria L, McCulley Calla M, Vyazovkin Sergey
Department of Chemistry, University of Alabama at Birmingham , 901 South 14th Street, Birmingham, Alabama 35294, United States.
J Phys Chem B. 2016 Jun 30;120(25):5703-9. doi: 10.1021/acs.jpcb.6b03860. Epub 2016 Jun 16.
In this study, differential scanning calorimetry (DSC) has been applied to measure the kinetics of nonisothermal crystallization of potassium nitrate and ammonium perchlorate from unsaturated and saturated aqueous solutions. DSC data have been analyzed by an advanced isoconversional method that demonstrates that the process is represented by negative values of the effective activation energy, which varies with the progress of crystallization. The classical nucleation model can be used to predict and understand the experimentally observed variation in the effective activation energy. The saturated and unsaturated solutions have demonstrated distinctly different crystallization kinetics. It is suggested that the unsaturated solutions undergo a change in crystallization mechanism from homogeneous to heterogeneous nucleation.
在本研究中,差示扫描量热法(DSC)已被用于测量硝酸钾和高氯酸铵从不饱和及饱和水溶液中进行非等温结晶的动力学。通过一种先进的等转化率方法对DSC数据进行了分析,该方法表明该过程由有效活化能的负值表示,有效活化能随结晶进程而变化。经典成核模型可用于预测和理解实验观察到的有效活化能变化。饱和溶液和不饱和溶液表现出明显不同的结晶动力学。有人认为,不饱和溶液的结晶机制会从均相成核转变为异相成核。