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.

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.

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.

ELECTRODE POTENTIALS OF THE URANIUM CHLORIDES IN FUSED ALKALI CHLORIDE SOLUTIONS

1961 ◽  
Vol 39 (4) ◽  
pp. 773-784 ◽  
Author(s):  
S. N. Flengas
Keyword(s):  
Activity Coefficients ◽  
Electrode Potential ◽  
Silver Chloride ◽  
Reference Electrode ◽  
Redox Potentials ◽  
Alkali Chloride ◽  
Electrode Potentials ◽  
Silver Chloride Reference Electrode ◽  
Silver Silver ◽  
Silver Silver Chloride

Using a silver – silver chloride reference electrode, the electrode potentials of the system U, UCl3(KCl, NaCl) and the redox potentials of the system Pt, UCl3, UCl4(KCl, NaCl) were measured at various concentrations of the uranium chlorides and at temperatures between 650 and 850 °C.From the results, the electrode potential of the system U, UCl4(KCl, NaCl) was calculated. In addition, the activity coefficients and partial molal properties of dilute solutions of UCl3 and UCl4 in the equimolar mixture of potassium and sodium chlorides were calculated.

Thermodynamics of electrolyte solutions: activity coefficients of NaCl in the NaCl–NiCl2–H2O system at 25, 35, and 45 °C

1990 ◽  
Vol 68 (2) ◽  
pp. 294-297 ◽  
Author(s):  
Ch. Venkateswarlu ◽  
J. Ananthaswamy
Keyword(s):  
Activity Coefficients ◽  
Silver Chloride ◽  
Osmotic Coefficients ◽  
Reference Electrode ◽  
Nickel Chloride ◽  
Electrolyte Solutions ◽  
Pitzer Formalism ◽  
Harned Coefficients ◽  
Silver Silver ◽  
Silver Silver Chloride

The activity coefficients of NaCl in the NaCl–NiCl2–H2O system were estimated at 25, 35, and 45 °C and total ionic strengths of 0.5, 1.0, 2.0, and 3.0 m by an EMF method using a Na-ion selective electrode and a silver–silver chloride reference electrode. The Harned coefficients were calculated at all the temperatures studied. At 25 °C the data were analysed using the Pitzer formalism. The osmotic coefficients and the excess free energies of mixing were also calculated at 25 °C. Keywords: activity coefficients, sodium chloride, nickel chloride, Pitzer equations, thermodynamics.

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