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水的过冷温度比之前计算的高约100K。

Hypercooling Temperature of Water is about 100 K Higher than Calculated before.

作者信息

Buttersack Tillmann, Weiss Volker C, Bauerecker Sigurd

机构信息

Institute for Physical and Theoretical Chemistry, Technische Universität Braunschweig , Gaußstrasse 17, 38106 Braunschweig, Germany.

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic , Flemingovo nám. 2, 16610 Prague 6, Czech Republic.

出版信息

J Phys Chem Lett. 2018 Feb 1;9(3):471-475. doi: 10.1021/acs.jpclett.7b03068. Epub 2018 Jan 16.

Abstract

For deeply supercooled liquids the transition from a two-stage freezing process to complete solidification in just one freezing step occurs at the hypercooling temperature, a term that seems to be almost unknown in water research; to our knowledge, it has only been mentioned by Dolan et al. for high-pressure ice. The reason for the absence of this expression may be that the best estimate to be found in the literature for the hypercooling temperature of water is about -160 °C (113 K). This temperature is far below the limit of experimentally realizable degrees of supercooling near -40 °C (233 K), which marks the homogeneous nucleation temperature T of common pure water; in fact, it is even below the glass-transition temperature (133 K). Here we show that, surprisingly, a more thorough analysis taking into account the temperature dependence of the heat capacities of water and ice as well as of the enthalpy of freezing shows that the hypercooling temperature of water is about -64 °C or 209 K, almost 100 K higher than estimated before. One of the most exciting consequences is that existing experiments are already able to reach these degrees of supercooling, and it is our prediction that a transition in the freezing behavior occurs at these temperatures.

摘要

对于深度过冷液体,在过冷温度下会发生从两阶段冻结过程到仅在一个冻结步骤中完全凝固的转变,“过冷温度”这个术语在水的研究中似乎几乎无人知晓;据我们所知,只有多兰等人在研究高压冰时提到过它。这个术语未被提及的原因可能是,在文献中能找到的关于水的过冷温度的最佳估计约为-160°C(113K)。这个温度远低于实验可实现的过冷度极限,接近-40°C(233K),该温度标志着普通纯水的均匀成核温度T;实际上,它甚至低于玻璃化转变温度(133K)。在这里我们表明,令人惊讶的是,更全面的分析考虑了水和冰的比热容以及凝固焓的温度依赖性,结果表明水的过冷温度约为-64°C或209K,比之前估计的高出近100K。最令人兴奋的结果之一是,现有的实验已经能够达到这些过冷度,并且我们预测在这些温度下冻结行为会发生转变。

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