鹽誘導液-液相分離:水-乙腈-鹽混合物的實驗和理論研究
作者:
小柯機器人發布時間:2021/1/13 15:37:58
中科院長春應化所的Yuyuan Lu課題組和美國加州理工學院Zhen-Gang Wang等合作,通過實驗和理論研究準確描繪了水-乙腈-鹽混合物的相圖。相關論文發表在2021年1月8日出版的《美國化學會志》上。
該研究通過結合實驗和理論系統性地考察了水-乙腈-鹽混合物的相行為。通過雲點和組分分析,研究人員繪製出九種代表性的鹽在水-乙腈混合物中的完整三元相圖。研究人員還建立了一個熱力學自由能模型,其中考慮了液體非理想混合、離子水合、靜電相互作用和波恩能等因素。研究表明,理論預測產生的相圖與實驗數據非常相符。
通過比較靜電相互作用、波恩能和水合作用的貢獻,研究人員發現,水合作用是促進液-液相分離的主要推動力,也是導致特定離子效應的主要原因。這一理論強調了熵在水合驅動力中的重要性。最後,研究人員還討論了這些發現在鹽析輔助液-液萃取中的意義,並為優化分離效率給出了選擇鹽離子的建議。
據了解,液體混合物中鹽誘導的液-液相分離是一種在自然界和應用場合中常見的現象,例如在化合物的分離和萃取中。
附:英文原文
Title: Salt-Induced Liquid–Liquid Phase Separation: Combined Experimental and Theoretical Investigation of Water–Acetonitrile–Salt Mixtures
Author: Minglun Li, Bilin Zhuang, Yuyuan Lu, Lijia An, Zhen-Gang Wang
Issue&Volume: January 8, 2021
Abstract: Salt-induced liquid–liquid phase separation in liquid mixtures is a common phenomenon in nature and in various applications, such as in separation and extraction of chemicals. Here, we present results of a systematic investigation of the phase behaviors in water–acetonitrile–salt mixtures using a combination of experiment and theory. We obtain complete ternary phase diagrams for nine representative salts in water–acetonitrile mixtures by cloud point and component analysis. We construct a thermodynamic free energy model by accounting for the nonideal mixing of the liquids, ion hydration, electrostatic interactions, and Born energy. Our theory yields phase diagrams in good agreement with the experimental data. By comparing the contributions due to the electrostatic interaction, Born energy, and hydration, we find that hydration is the main driving force for the liquid–liquid separation and is a major contributor to the specific ion effects. Our theory highlights the important role of entropy in the hydration driving force. We discuss the implications of our findings in the context of salting-out assisted liquid–liquid extraction and make suggestions for selecting salt ions to optimize the separation performance.
DOI: 10.1021/jacs.0c09420
Source: https://pubs.acs.org/doi/10.1021/jacs.0c09420