Liquid-junction potentials, and relative activity coefficients of chloride ions, in concentrated mixed chlorides and nitrates at 25 degrees C

1944 ◽  
Vol 33 (4) ◽  
pp. 273 ◽  
Author(s):  
G.G. Manov ◽  
N.J. DeLollis ◽  
S.F. Acree
Keyword(s):  
Activity Coefficients ◽  
Relative Activity ◽  
Chloride Ions ◽  
Liquid Junction ◽  
Liquid Junction Potentials

A New Method for the Estimation of Transfer Activity Coefficients of Ions From the E.M.F. of Cells With Liquid Junction

1988 ◽  
Vol 41 (10) ◽  
pp. 1523 ◽  
Author(s):  
A Berne ◽  
O Popovych
Keyword(s):  
Concentration Dependence ◽  
Activity Coefficients ◽  
Salt Bridge ◽  
Liquid Junction ◽  
Transfer Activity ◽  
Liquid Junction Potentials ◽  
Solvent Component ◽  
Calculated Liquid ◽  
Dipolar Aprotic Solvents ◽  
Junction Potential

Transfer activity coefficients of the tetraalkylammonium ions, logmγR, where R+ = Me4N+, Et4N+, Pr4N+ and Bu4N+, and of the picrate ion, logmγPic, between pairs of dipolar aprotic solvents, S1 → S2, were evaluated by combining the e.m.f . of cells Ag(cryst.)|AgClO4|RX|AgClO4|Ag( cryst .)�������������������������������� S1 ������ S2with the calculated liquid-junction potentials, Ej. The salt-bridge electrolyte RX was RClO4 and R Pic for the determinations of logmγR and logmγPic, respectively, and the solvents were: acetonitrile ( MeCN ), N,N- dimethylformamide (HCONMe2), dimethyl sulfoxide (Me2SO) and propylene carbonate ( pcar ). The logmγR values showed a systematic variation with the AgClO4 concentration, apparently caused by the concentration dependence of the solvent component of the liquid-junction potential, Ej,s, neglected in the calculations. However, the above concentration dependence was virtually eliminated from the values of logmγPic when they were calculated with the aid of our concentration-dependent logmγR data. For a number of our cells it was possible to evaluate the Ej,s, with the aid of literature data. The solvent component of Ej was found to be appreciable and varied both with the AgClO4 and the RX concentration. The Ej,s, was particularly large for cells containing pcar , with a maximum of -172 mV for the pcar | MeCN junction.

A contribution to the knowledge of the liquid junction potentials. Part I

1933 ◽  
Vol 5 ◽  
pp. 469-478 ◽  
Author(s):  
J. B. Chloupek ◽  
Vl. Z. Daneš ◽  
B. A. Danešová
Keyword(s):  
Liquid Junction ◽  
Liquid Junction Potentials

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.

scholarly journals LIQUID JUNCTION POTENTIALS.

1915 ◽  
Vol 37 (10) ◽  
pp. 2301-2307 ◽  
Author(s):  
Duncan A. MacInnes
Keyword(s):  
Liquid Junction ◽  
Liquid Junction Potentials

ChemInform Abstract: CALCULATION OF LIQUID JUNCTION POTENTIALS

1973 ◽  
Vol 4 (29) ◽  
pp. no-no
Author(s):  
E. C. MORENO ◽  
R. T. ZAHRADNIK
Keyword(s):  
Liquid Junction ◽  
Liquid Junction Potentials

Liquid Junction Potentials for Certain Complex Systems

1937 ◽  
Vol 72 (1) ◽  
pp. 71
Author(s):  
A. L. Ferguson ◽  
Richard Hitchens ◽  
Kenneth Van Lente
Keyword(s):  
Complex Systems ◽  
Liquid Junction ◽  
Liquid Junction Potentials
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