Boiling points and vapor–liquid equilibrium (VLE) data are crucial for improving modeling and process design. Therefore, considering the experimental determination of these primary thermodynamic properties, a nontraditional technique that has been under study and has shown some advantages is the differential scanning calorimetry (DSC) technique and its variations. Following a previous work focused only on pure compounds, in this work a set of experiments was performed to evaluate in a systematic way the suitability of its suggested variation of the DSC technique for binary mixtures. Its optimized condition for heating rate (24.52 K·min^–1) and sample size (4.6 ± 0.5) mg was used at 4.97 kPa with u(P) = 0.12 kPa for 15 different combinations of n-paraffins and/or fatty alcohols (1-alcohols) in binary mixtures (n-paraffin + n-paraffin, 1-alcohol + 1-alcohol, and n-paraffin + 1-alcohol), taking into account the difference between the boiling points (T_b) of the pure compounds at the selected pressure (7 to 63 K). Experiments were configured using the equimolar condition, and pursued effects of this difference on the measured extrapolated onset temperature, that is, the measured boiling point. For four of these mixtures other molar fractions were also tested. Estimations of the boiling points followed the appropriate thermodynamic approach. The results revealed that the optimized condition may fail in some situations for binary mixtures, and that this fail could not always be related to the difference in the boiling points of their pure compounds. Further work is necessary in this direction.

中文翻译：

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差示扫描量热技术在低于大气压下测量二元混合物沸点的变化评估

沸点和气液平衡（VLE）数据对于改善建模和过程设计至关重要。因此，考虑到对这些主要热力学性质的实验确定，一种正在研究并显示出一定优势的非传统技术是差示扫描量热法（DSC）及其变化。在先前仅关注纯化合物的工作之后，在这项工作中进行了一组实验，以系统的方式评估了其建议的DSC技术变化对二元混合物的适用性。对于n的15种不同组合，其加热速率（24.52 K·min ^–1）和样品大小（4.6±0.5）mg的优化条件用于4.97 kPa，u（P）= 0.12 kPa。考虑到沸腾之间的差异，在二元混合物（n-石蜡+ n-石蜡，1-醇+ 1-醇和n-石蜡+ 1-醇）中混合使用-石蜡和/或脂肪醇（1-醇）点（T _b）在选定压力（7至63 K）下的纯化合物）。实验是在等摩尔条件下进行的，该差异对所测外推起始温度即所测沸点的影响。对于这些混合物中的四种，还测试了其他摩尔分数。沸点的估算遵循适当的热力学方法。结果表明，优化条件在某些情况下对于二元混合物可能会失败，并且这种失败可能并不总是与其纯化合物沸点的差异有关。在这个方向上需要进一步的工作。