The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration

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• 作者：Alexander M. Smith ; Alpha A. Lee ; Susan Perkin
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：June 16, 2016
• 年：2016
• 卷：7
• 期：12
• 页码：2157-2163
• 全文大小：460K
• 年卷期：0
• ISSN：1948-7185

文摘

According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye–Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied—including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids—collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.