(Digital Presentation) Experimental Results on the Determination of the Billiter Potential
Authors: Chernomorskii Alexandr I. 
Published: September 2023

The experimental effects at the Billiter potential are measured in narrow intervals of the equilibrium potentials (A, B).

The Billiter potential + 0.475 V SHE [1-3] is confirmed by the following experimental results [4,5,7- 9].

The change in the direction of the current between a dropping mercury and a mercury bottom in solutions of redox systems Fe(CN)6
3
- - Fe(CN)6
4
- and quinone-hydroquinone at a given potential
E

equil
. = + 475 V SHE has been established with exactness ± 1-2 mV [4, 5]. This result was confirmed in [6]. At
E

equil. > +0.475 V SHE, the current flows from a mercury bottom to dropping electrode and at
E

equil. < +0.475 V SHE - in the opposite direction. Electrocapillary curves have been found by drop-weight method in these solutions in narrow range
E

equil. ~+0.4 ÷+0.55 V SHE with a maximum at
E

equil. ~ + 0.475 V SHE [4].

A self-recording galvanometer was used to record the reversal of the current between a mercury bottom and a dropping electrode in solutions of redox systems [7-9]. In a solution of quinone-hydroquinone redox system, a recorded positive current decreases exactly to zero at
E

= + 228 mV SCE (+ 475 mV SHE), and then a negative current increases with continuous dropping of mercury.
E

equil. changes by itself since an adsorbed quinone on mercury drops are removed from solution onto mercury bottom (A).

The current reversal at
E

~+ 0.22 ÷ + 0.23 V SCE (~+0.475 V SHE) has been recorded by a recorder between a mercury bottom and a dropping electrode in acidified Hg2(NO3)2 solutions with the addition of complexing agents (triethanolamine, sodium ethylenediaminetetraacetate, thiocarbamide, others) [7-9].

The electrocapillary curves (ECC) have been measured by weight-drop method in these solutions (B; with sodium ethylenediaminetetraacetate). After passing the electrocapillary maximum for reversible Hg2
2+/ Hg electrode at
E

~ + 0.22 ÷ + 0.23 V SCE, we have obtained an ascending branch of ECC of an ideally polarizable electrode at
E

equil. < ~+0.190 ÷ +0.210 V SCE. A registered second current reversal at these
E

equil. corresponds to the transition from a small descending branch of ECC of Hg2
2+/Hg electrode to an ascending branch of ECC of an ideally polarizable electrode. The electrocapillary maximum was also obtained using diluted acidified solutions of Hg2(NO3)2.

An increase in a polarization resistance and a change in polarization capacitance have been detected when impedance measuring with reversible electrodes at
Ee

~ +0.475 V SHE. These effects were also measured on mercury drops in the diluted 10-10 N solution of Hg2(NO3)2 + 0.1÷ 0.001 N KNO3 The increase in polarization resistance was explained by the achievement of chemical equilibrium of half-reactions at
Ee

quil. ~ +0.475 V SHE [6,7,16].

Measurements by the immersion method with redox systems and solid electrodes of the second kind confirm the reversal of the current at
E

~+ 475 V SHE. Submersible small solid electrodes must be absolutely clean and dry [5]. This method is under development.

According to [8 - 10], Billiter potential corresponds to some electrode with zero chemical activity (transitional from metals to non-metals with the intermediate electron work function 5.19 eV). The same zero activity is obtained at chemical equilibrium of half-reactions when the sum of changes of chemical potentials of electrons and ions Δμion + Δμelectron = 0, and potential drops in double - electric layers are compensated. The components Δμion= 0 and Δμelectron≠ 0 correspond to potentials of zero charge
Ep.

z.c. For mercury, the electron work function is 4.52 eV and Δμelectron = 4.52 eV - 5.19 eV = - 0.67 eV. In order Δμion + Δμelectron = 0, Δμion should be equal + 0.67 eV. Indeed, if
E

p.z.c. = - 0.193 V SHE for mercury is changed by + 0.67 V we obtain the chemical equilibrium of half-reactions at ~ +0.475 V SHE.

REFERENCES

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The Encyclopedia of Electrochemistry, C.A. Hampel (ed.), (Reinhold,New York, NY) (1964).

H.J.Oel, H Strelow,Z. Electrochem, 1954,58,665.

A.I.Chernomorskii, Soviet Electrochemistry, 1981, 17, 874.

A.I.Chernomorskii, Russian Journal of Physical Chemistry,1981, 55, p.206.

Ya.I.Tur’yan, Redox Reactions and Potentials in Analytical Chemistry, Khimiya, Moscow, 1989.

A.I. Chernomorskii,N.S.Polizan, Reports of Academy of Sciences of the Uzbekistan,1990, 6, 35.

A.I.Chernomorskii, Thernodynamics of Electrodes, FAN, Tashkent, 1993.

A.I.Chernomorskii, The Intermediate Electron Bond and Half-reactions, Scientific Resources, New York, 1999.

A.I. Chernomorskii, Journal of The Electrochemical Society, 2021, 168,116514.

Figure 1