Standard potentials of the cesium amalgam electrode, and thermodynamic functions for dilute cesium amalgams and for aqueous cesium chloride

Potential Differences Between the Alkali Metals and Their Amalgams

“…The cesium amalgam mole fraction in the present work was 0.004551, higher than the composition of the cesium amalgam used by Bent et al (8), Xcs --0.002827. The value of 1.107V obtained in the present work is indeed lower than the value of 1.121V measured by Bent et al (8) for a more dilute amalgam, and agrees reasonably with the calculated value of 1.100V after Mussini, Longhi, and Riva (17).…”

Re-Evaluation of the Thermodynamic Activity Quantities in Aqueous Rubidium and Cesium Chloride Solutions at 25 °C

“…The results of these tests are shown in Figure 11. All isopiestic data of Bahia et al 13 and Kirgintsev and Luk'yanov 15,16 support well the suggested Hu ¨ckel parameter values, but the isopiestic data of Robinson and Sinclair, 3 19 in CsCl solutions on cell 16 as a function of molality m. The predicted cpd was calculated by using eq 17 where eq 1 with B ) 0.84 (mol • kg -1 ) -1/2 and b 1 ) 0.0341 was used for the activity coefficients and the following values were used for the standard cpds: b, x ) 0.0006650, E o ) 1.98538 V; O, 0.001289, 2.00473; 1, 0.005521, 2.05169; 3, 0.006073, 2.05607; 9, 0.009942, 2.07742; 0, 0.01337, 2.09347. ; and in the isotonic LiCl (x) and CsCl (y) solutions reported 3, by Kirgintsev and Luk'yanov. 16 The vapor pressures have been calculated by eqs 3 and 4 using eq 6 with the suggested parameter values for NaCl, 12 KCl, 12 and LiCl 23 and with B ) 0.84 (mol • kg -1 ) -1/2 , b 1 ) 0.03234, and b 2 ) 0.00057 for CsCl.…”

“…Deviation, e E in eq , between the observed and predicted cell potential difference (cpd) from the data measured by Mussini et al in CsCl solutions on cell 16 as a function of molality m . The predicted cpd was calculated by using eq where eq with B = 0.84 (mol·kg −1 ) −1/2 and b 1 = 0.0341 was used for the activity coefficients and the following values were used for the standard cpds: ●, x = 0.0006650, E o = 1.98538 V; ○, 0.001289, 2.00473; ▼, 0.005521, 2.05169; ▽, 0.006073, 2.05607; ◼, 0.009942, 2.07742; ◻, 0.01337, 2.09347.…”

“…The new estimated Hu ¨ckel parameters for CsCl can then be tested with cpd data. Mussini et al 19 measured at 25 °C CsCl solutions on amalgam cells of the type 16 where M is Cs + (or Cs). The data consist of six series of measurements where the mole fraction (x) of cesium in the amalgam is constant, and in each series the molality of CsCl (m) varied from (0.05 to 0.6) mol • kg -1 or from (0.1 to 0.7) mol • kg -1 .…”

“…The resulting parameters for the Hückel equation ( B and b 1 ) and for the extended Hückel equation ( B , b 1 , and b 2 ) for RbCl and CsCl solutions were tested with the data used in the parameter estimations , and, additionally, with the following data: with the isopiestic data of Robinson and Sinclair for both RbCl and CsCl solutions, of Robinson for CsCl solutions, of Bahia et al for CsCl solutions (the reference electrolyte in these four studies is KCl), of Frolov et al for CsCl solutions (against NaCl solutions), and of Kirgintsev and Luk’yanov for CsCl solutions (against NaCl, , LiCl, and KCl solutions); with the osmotic coefficients reported by Robinson for RbCl solutions and by Makarov et al for concentrated RbCl and CsCl solutions; with the cell potential differences (cpd) measured by Longhi et al or Mussini et al for RbCl or CsCl solutions on cells containing a rubidium or cesium amalgam electrode, respectively, and a Ag−AgCl electrode; and with the cpd data measured by Harned and Schupp and Caramazza on concentration cells with two Ag−AgCl electrodes and one cesium amalgam electrode.…”