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开发一种使用蒸发结晶测量成核动力学的小瓶规模方法:以氯化钠为例的案例研究。

Developing a Vial-Scale Methodology for the Measurement of Nucleation Kinetics Using Evaporative Crystallization: A Case Study with Sodium Chloride.

作者信息

Chen Michele, Deck Leif-Thore, Bosetti Luca, Mazzotti Marco

机构信息

Institute of Energy and Process Engineering, ETH Zürich, 8092 Zürich, Switzerland.

出版信息

Cryst Growth Des. 2025 Apr 4;25(8):2498-2509. doi: 10.1021/acs.cgd.4c01722. eCollection 2025 Apr 16.

DOI:10.1021/acs.cgd.4c01722
PMID:40256756
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12006966/
Abstract

Understanding nucleation kinetics is vital for designing crystallization processes, yet traditional measurement methods based on cooling are unsuitable for compounds with temperature-independent solubility. This study introduces an experimental procedure to measure the nucleation kinetics based on evaporative crystallization and applies it to sodium chloride (NaCl) in water. By systematically varying the experimental conditions such as temperature and evaporation gas flow rate, we obtained a comprehensive data set for the nucleation of NaCl crystals that allowed estimating kinetic parameters using a rate expression derived from classical nucleation theory (CNT). This work demonstrates the robustness of evaporation as a method for measuring the nucleation kinetics that is applicable regardless of how the solubility of a compound depends on the temperature.

摘要

理解成核动力学对于设计结晶过程至关重要,但基于冷却的传统测量方法不适用于溶解度与温度无关的化合物。本研究介绍了一种基于蒸发结晶测量成核动力学的实验程序,并将其应用于水中的氯化钠(NaCl)。通过系统地改变温度和蒸发气体流速等实验条件,我们获得了一套关于NaCl晶体成核的综合数据集,从而能够使用从经典成核理论(CNT)推导的速率表达式来估计动力学参数。这项工作证明了蒸发作为一种测量成核动力学方法的稳健性,该方法适用于任何化合物的溶解度如何随温度变化的情况。

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本文引用的文献

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Rapid Assessment of Crystal Nucleation and Growth Kinetics: Comparison of Seeded and Unseeded Experiments.晶体成核与生长动力学的快速评估:接种实验与未接种实验的比较
Cryst Growth Des. 2023 Jun 20;23(7):4779-4790. doi: 10.1021/acs.cgd.2c01406. eCollection 2023 Jul 5.
2
Thermodynamics Explains How Solution Composition Affects the Kinetics of Stochastic Ice Nucleation.热力学解释了溶液组成如何影响随机冰核化的动力学。
J Phys Chem Lett. 2023 Jul 6;14(26):5993-6000. doi: 10.1021/acs.jpclett.3c01371. Epub 2023 Jun 22.
3
CNT effective interfacial energy and pre-exponential kinetic factor from measured NaCl crystal nucleation time distributions in contracting microdroplets.
基于收缩微滴中测得的氯化钠晶体成核时间分布得出的碳纳米管有效界面能和指前动力学因子。
J Chem Phys. 2023 May 21;158(19). doi: 10.1063/5.0143704.
4
Conceptual Validation of Stochastic and Deterministic Methods To Estimate Crystal Nucleation Rates.用于估算晶体成核速率的随机和确定性方法的概念验证
Cryst Growth Des. 2022 Dec 29;23(2):899-914. doi: 10.1021/acs.cgd.2c01133. eCollection 2023 Feb 1.
5
Stochastic ice nucleation governs the freezing process of biopharmaceuticals in vials.随机成核控制着小瓶中生物制药的冻结过程。
Int J Pharm. 2022 Sep 25;625:122051. doi: 10.1016/j.ijpharm.2022.122051. Epub 2022 Jul 28.
6
Evaporation Dynamics of Sessile Saline Microdroplets in Oil.油中静态盐微滴的蒸发动力学
Langmuir. 2022 Aug 9;38(31):9686-9696. doi: 10.1021/acs.langmuir.2c01269. Epub 2022 Jul 28.
7
Multiple pathways in NaCl homogeneous crystal nucleation.氯化钠均匀晶体成核中的多种途径。
Faraday Discuss. 2022 Jul 14;235(0):56-80. doi: 10.1039/d1fd00089f.
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