Critical study involving water, methanol, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide of medium ion activity coefficients, .gamma., on the basis of the .gamma.AsPh4+ = .gamma.BPh4- assumption

1972 ◽  
Vol 76 (14) ◽  
pp. 2024-2034 ◽  
Author(s):  
I. M. Kolthoff ◽  
M. K. Chantooni
Keyword(s):  
Dimethyl Sulfoxide ◽  
Activity Coefficients ◽  
Critical Study ◽  
Ion Activity

scholarly journals Towards the Understanding of Water-in-Salt Electrolytes: Individual Ion Activities and Liquid Junction Potentials in Highly Concentrated Aqueous Solutions

2021 ◽  
Author(s):  
Damien Degoulange ◽  
Nicolas Dubouis ◽  
Alexis Grimaud
Keyword(s):  
Activity Coefficients ◽  
Operating Voltage ◽  
Redox Potentials ◽  
Liquid Junction ◽  
Nernst Potential ◽  
Concentrated Electrolytes ◽  
Ion Activity ◽  
Ion Activities ◽  
Single Ion Activity ◽  
Increased Activity

Highly concentrated electrolytes were recently proposed to improve the performances of aqueous electrochemical systems by delaying the water splitting and increasing the operating voltage for battery applications. While advances were made regarding their implementation in practical devices, debate exists regarding the physical origin for the delayed water reduction occurring at the electrode/electrolyte interface. Evidently, one difficulty resides in our lack of knowledge regarding ions activity arising from this novel class of electrolyte, it being necessary to estimate the Nernst potential of associated redox reactions such as Li<sup>+</sup> intercalation or the hydrogen evolution reaction. In this work, we first measured the potential shift of electrodes selective to either Li<sup>+</sup>, H<sup>+</sup> or Zn<sup>2+</sup> ions from diluted to highly concentrated regimes in LiCl or LiTFSI solutions. Observing similar shifts for these different cations and environments, we establish that shifts in redox potentials from diluted to highly concentrated regime originates in large from an increase junction potential, it being dependent on the ions activity coefficients that increase with concentration. While our study shows that single ion activity coefficients, unlike mean ion activity coefficients, cannot be captured by any electrochemical means, we demonstrate that protons concentration increases by approximatively two orders of magnitude from 1 mol.kg<sup>-1</sup> to 15-20 mol.kg<sup>-1</sup> solutions. Combined with the increased activity coefficients, this increases the activity of protons and thus the pH of highly concentrated solutions which appears acidic.

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