VOLTAIC CELLS IN FUSED SALTS: PART V. THE SYSTEMS Sn/SnCl2 (KCl–NaCl), Fe/FeCl2 (KCl–NaCI), and Mn/MnCl2 (KCl–NaCl)

1958 ◽  
Vol 36 (12) ◽  
pp. 1662-1667 ◽  
Author(s):  
S. N. Flengas ◽  
T. R. Ingraham
Keyword(s):  
Reference Electrode ◽  
Effect Of Temperature ◽  
Nernst Equation ◽  
Fused Salts ◽  
Electrode Potentials ◽  
Standard Electrode Potentials

Using a Ag/AgCl (KCl–NaCl) reference electrode, the standard electrode potentials of the systems Sn/SnCl2 (KCl–NaCl), Fe/FeCl2 (KCl–NaCl), and Mn/MnCl2 (KCl–NaCl) were determined at 700 °C and found to be 0.370 v, 0.520 v, and 1.205 v respectively. In each of the systems the Nernst equation was found to be applicable over the range of concentrations investigated.The effect of temperature on the electromotive forces of the above cells was measured and the heats of the cell reactions were calculated from the data.

VOLTAIC CELLS IN FUSED SALTS: PART IV. ELECTRODE POTENTIALS OF THE SYSTEMS: Tl/TlCl (KCl–NaCl), Cu/CuCl (KCl–NaCl), Cu/CuCl2 (KCl–NaCl), Cr/CrCl2 (KCl–NaCl), AND Cr/CrCl3 (KCl–NaCl). REDOX POTENTIALS OF THE SYSTEMS: Pt/CuCl, CuCl2 (KCl–NaCl), AND Pt/CrCl2, CrCl3 (KCl–NaCl)

1958 ◽  
Vol 36 (7) ◽  
pp. 1103-1115 ◽  
Author(s):  
S. N. Flengas ◽  
T. R. Ingraham
Keyword(s):  
Reference Electrode ◽  
Effect Of Temperature ◽  
Redox Potentials ◽  
Fused Salts ◽  
Electrode Potentials ◽  
Standard Electrode Potentials

Using a Ag/AgCl (KCl–NaCl) reference electrode, the standard electrode potentials of the systems Tl/TlCl (KCl–NaCl), Cu/CuCl (KCl–NaCl), Cu/CuCl2 (KCl–NaCl), Cr/CrCl2 (KCl–NaCl), and Cr/CrCl3 (KCl–NaCl) were measured and found to be: 0.650 volt at 680 °C, and 0.250, −0.175, 0.755, and 0.423 at 700 °C. respectively. The standard redox potentials of the systems Pt/CuCl2, CuCl (KCl–NaCl), and Pt/CrCl3, CrCl2 (KCl–NaCl) were also measured at 700 °C. and found to be 0.600 and 0.240 volt respectively. The effect of temperature on the electromotive forces of the above cells was measured and the heats of the cell reactions were calculated from the data.

VOLTAIC CELLS IN FUSED SALTS: PART II. THE SYSTEMS: (a) SILVER – SILVER CHLORIDE, LEAD – LEAD CHLORIDE; (b) SILVER – SILVER CHLORIDE, ZINC – ZINC CHLORIDE; AND (c) SILVER – SILVER CHLORIDE, NICKEL – NICKELOUS CHLORIDE

1957 ◽  
Vol 35 (11) ◽  
pp. 1254-1259 ◽  
Author(s):  
S. N. Flengas ◽  
T. R. Ingraham
Keyword(s):  
Zinc Chloride ◽  
Dissociation Constants ◽  
Silver Chloride ◽  
Reference Electrode ◽  
Lead Chloride ◽  
Effect Of Temperature ◽  
Fused Salts ◽  
Electrode Potentials ◽  
Silver Silver ◽  
Silver Silver Chloride

Using a reversible silver – silver chloride reference electrode, described in the first paper of this series, standard electrode potentials have been established for the systems lead – lead chloride, zinc – zinc chloride, and nickel – nickelous chloride, in melts containing equimolar quantities of KCl and NaCl. Deviations from ideality were observed, and these were attributed to the formation of complexes. Dissociation constants for the complexes were calculated. The effect of temperature on the electromotive forces of the voltaic cells was also measured, and the heats of the cell reactions were calculated from the data.

ELECTROCHEMICAL STUDIES ON TITANIUM IN MOLTEN LiCl–KCl EUTECTIC

1965 ◽  
Vol 43 (1) ◽  
pp. 197-205 ◽  
Author(s):  
R. Baboian ◽  
D. L. Hill ◽  
R. A. Bailey
Keyword(s):  
Anodic Dissolution ◽  
Mole Fraction ◽  
Coulometric Titration ◽  
Reference Electrode ◽  
Electrochemical Studies ◽  
Reference Electrodes ◽  
Electrode Potentials ◽  
Standard Electrode Potentials

The methods of potentiometry and polarography have been used to study the Ti(II) and Ti(III) ions in solution in the LiCl–KCl eutectic at 450 °C and 550 °C. Solutions of Ti(II) were prepared by anodic dissolution of Ti metal, and Ti(III) solutions by coulometric titration of Ti(II) by Pt(II). Apparent standard electrode potentials were measured for the Ti(II)/Ti and Ti(III)/Ti(II) couples against the Pt(II)/Pt and Ag(I)/Ag reference electrodes. Values obtained on the mole fraction scale with a Pt(II)/Pt reference electrode were[Formula: see text]Polarographic waves for oxidation and reduction of Ti(II), and for reduction of Ti(III), were observed.

Pressure Dependence of the Electrode Potentials of Some Iron(III/II), Cobalt(III/II), and Ni(III/II) Couples in Aqueous Solution: Estimation of the Reaction Volumes for M(III)/M(II) Couples

1997 ◽  
Vol 52 (9) ◽  
pp. 1087-1093 ◽  
Author(s):  
Mitsuru Matsumoto ◽  
Toshiyasu Tarumi ◽  
Isao Takahashi ◽  
Shigenobu Funahashi ◽  
Toshiaki Noda ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Pressure Dependence ◽  
Reference Electrode ◽  
Partial Molar Volumes ◽  
Spherical Approximation ◽  
Mean Spherical Approximation ◽  
Nernst Equation ◽  
Electrode Potentials ◽  
The Mean ◽  
Reaction Volumes

Abstract Pressure dependence of the electrode potentials for various M 3+/2+ couples (M = Fe, Co, and Ni with o-phenanthroline, bipyridine, terpyridine, 1,4,7-triazacyclononane, and 1,4,7-tri-thiacyclononane) was measured by cyclic voltammetry in aqueous solution vs. a Ag/AgCl reference electrode. The reaction volume of the Ag/AgCl reference electrode was estimated from the change in the partial molar volumes of Feaq3+/2+ and Co(terpyridine)23+/2+ couples, and the volumes for the formation of M2+ from M3+ were determined. The electrostrictive component for the change in the oxidation state for the M3+/2+ couple was calculated on the basis of the Drude-Nernst equation and by the mean spherical approximation (MSA). The isolated volumes for the formation of M2+ from M3+ were compared with the values predicted by theory.

VOLTAIC CELLS IN FUSED SALTS: PART I. THE SILVER – SILVER CHLORIDE, COBALT – COBALTOUS CHLORIDE SYSTEM

1957 ◽  
Vol 35 (10) ◽  
pp. 1139-1149 ◽  
Author(s):  
S. N. Flengas ◽  
T. R. Ingraham
Keyword(s):  
Electromotive Force ◽  
Silver Chloride ◽  
Reference Electrode ◽  
Effect Of Temperature ◽  
Chloride System ◽  
Fused Salts ◽  
Silver Silver ◽  
The Right ◽  
Silver Silver Chloride ◽  
Voltaic Cell

A reversible silver − silver chloride reference electrode for use in melts at high temperatures has been developed. It was found that the solution of silver chloride in an equimolar mixture of KCl–NaCl melt is ideal for the range of concentrations studied, i.e. 1.0 × 10−3 to 6.0 × 10−2 mole fraction of AgCl.The electromotive force of the voltaic cell[Formula: see text]in which the half-cell to the right contains the above-mentioned reference electrode, was measured as a function of CoCl2 concentration. The applicability of the Nernst equation to this system was established. Deviation from ideality was observed in the case of the solution of CoCl2 in the melt solvent, and this was attributed to the formation of a complex. The dissociation constant of this complex was calculated as 4.50 × 10−2 at 710 °C.The effect of temperature on the electromotive force of this cell was also measured, and the heat of the cell reaction in the presence of solvent (Co + 2AgCl → CoCl2 + 2Ag) was calculated from the data as 22.8 ± 1.3 kcal.The thermodynamic significance of the standard electrode potential of the Co–Ag voltaic cell, derived experimentally as 0.324 volt, is discussed briefly.

VOLTAIC CELLS IN FUSED SALTS: PART III. THE SYSTEM SILVER – SILVER CHLORIDE, CADMIUM – CADMIUM CHLORIDE

1958 ◽  
Vol 36 (5) ◽  
pp. 780-788 ◽  
Author(s):  
S. N. Flengas ◽  
T. R. Ingraham
Keyword(s):  
Activity Coefficients ◽  
Silver Chloride ◽  
Reference Electrode ◽  
Effect Of Temperature ◽  
Published Data ◽  
Cadmium Complex ◽  
Fused Salts ◽  
Cadmium Lead ◽  
Silver Silver ◽  
Silver Silver Chloride

Using a silver–silver chloride reference electrode, the standard electrode potential his been established for the equilibrium Cd|Cd++ in melts containing equimolar quantities of KCl and NaCl. The experimentally obtained standard potential was greater than that calculated from theoretical thermodynamic data. This difference was attributed to the formation of a cadmium complex in the melt. A dissociation constant for the complex was calculated.The effect of temperature on the electromotive force of the silver–cadmium voltaic cell was also measured, and the heat of the cell reaction was calculated from the data. To extend the temperature range of the cadmium data, a cadmium–lead alloy was used in the higher temperature experiments. To correlate these data with those for the pure cadmium system, the activity coefficients of cadmium in the alloy were determined electrometrically using the silver–silver chloride electrode as a reference. It was found that the activity coefficients were in agreement with previously published data obtained at lower temperatures using a pure cadmium reference electrode. The activity coefficients were virtually independent of temperature but showed large positive deviations from unity when the mole fraction of cadmium was decreased below about 0.8.

Reversible electrode potentials for formation of solid and liquid chlorozirconate and chlorohafnate compounds

1993 ◽  
Vol 71 (9) ◽  
pp. 1283-1289 ◽  
Author(s):  
G.J. Kipouros ◽  
S.N. Flengas
Keyword(s):  
Thermal Decomposition ◽  
Alkali Metal ◽  
Electrochemical Behaviour ◽  
Thermochemical Data ◽  
Dilute Solutions ◽  
Alkali Metal Chlorides ◽  
Metal Chlorides ◽  
Electrode Potentials ◽  
Standard Electrode Potentials

The standard electrode potentials for the formation of the pure solid and molten compounds Li2ZrCl6, Li2HfCl6, Na2ZrCl6, Na2HfCl6, K2ZrCl6, K2HfCl6, Cs2ZrCl6, and Cs2HfCl6 have been calculated from measured vapour pressures corresponding to their thermal decomposition at equilibrium and from available thermochemical data. Reversible potentials for the formation of Na2ZrCl6 and of K2ZrCl6 in solution according to the reaction[Formula: see text]where A is Na or K, have been calculated from available equilibrium vapour pressures as functions of the mole fractions of the alkali hexachlorocompounds. Standard potentials for the above reaction and "formal" potentials are also given. The latter are useful in predicting the electrochemical behaviour of dilute solutions of the hexachlorozirconates in alkali metal chlorides.

ELECTRODE POTENTIALS OF THORIUM TETRACHLORIDE IN ALKALI CHLORIDE MELTS

1964 ◽  
Vol 42 (6) ◽  
pp. 1315-1322 ◽  
Author(s):  
R. Srinivasan ◽  
S. N. Flengas
Keyword(s):  
Silver Chloride ◽  
Gravimetric Method ◽  
Reference Electrode ◽  
The Other ◽  
Alkali Chloride ◽  
Electrode Potentials ◽  
Silver Chloride Reference Electrode ◽  
Chloride Melts ◽  
Silver Silver ◽  
Silver Silver Chloride

The electrode potentials of the system Th, ThCl4 (KCl, NaCl) were measured at various concentrations of thorium chloride, and at temperatures between 670 °C and 850 °C, using a silver – silver chloride reference electrode. It was shown by a direct gravimetric method that the reaction,Th(metal) + ThCl4(melt) = 2ThCl2(in melt),postulated by previous investigators, did not take place.The activity coefficients, and the other partial molal properties of the solutions of ThCl4, in the equimolar mixture of potassium and sodium chlorides, were calculated as a function of temperature from the e.m.f. measurements.

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