Frustration vs Prenucleation: Understanding the Surprising Stability of Supersaturated Sodium Thiosulfate Solutions.

Frustration vs Prenucleation: Understanding the Surprising Stability of Supersaturated Sodium Thiosulfate Solutions.
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挫败与预成核:了解过饱和硫代硫酸钠溶液令人惊讶的稳定性。

DOI:
10.1021/acs.jpcb.8b04112
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发表时间:
2018
期刊:
The journal of physical chemistry. B
影响因子:
--
通讯作者:
Reichenbach J
Reichenbach J
中科院分区:
--
文献类型:
--
作者:
Reichenbach J

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吉布斯经典成核理论预测,过饱和溶液将具有瞬时的核,这些核在存在和不存在之间快速移动。只有当这些晶核中的一个变得大于临界尺寸时,溶液才会结晶。最近,非经典的成核理论已经调用的prenuclei可能与液-液相分离的存在。然而,很少有这样的前核的实验观察。在这里,我们使用超快光学克尔效应光谱测量温度依赖的低频(亚千兆赫到太赫兹)各向异性拉曼光谱的过饱和硫代硫酸钠水溶液。在光谱中得到了明显的簇的证据。然而,根据这些团簇的推断稳定性,它们似乎阻碍而不是促进晶体的形成。这可以解释过饱和硫代硫酸钠和类似溶液令人惊讶的稳定性。
Gibbs classical nucleation theory predicts that a supersaturated solution will have transient nuclei that flitter in and out of existence. Only when one of these nuclei becomes larger than a critical size, will the solution crystalize. Recently, nonclassical nucleation theories have invoked the presence of prenuclei possibly associated with a liquid–liquid phase separation. However, there are few experimental observations of such prenuclei. Here, we use ultrafast optical Kerr-effect spectroscopy to measure the temperature-dependent low-frequency (sub-gigahertz to terahertz) anisotropic Raman spectra of supersaturated aqueous sodium thiosulfate solutions. Clear evidence of clusters is obtained in the spectra. However, on the basis of the inferred stability of these clusters, it appears that they frustrate rather than promote the formation of crystals. This would explain the surprising stability of supersaturated sodium thiosulfate and similar solutions.
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