Molten salt mixtures. XI. Integral and partial molar volumes in the molten salt systems PbCl2 + NaCl, PbCl2 + RbCl, PbCl2 + CsCl, CdCl2 + RbCl, and CdCl2 + CsCl

1966 ◽  
Vol 19 (9) ◽  
pp. 1591 ◽  
Author(s):  
H Bloom ◽  
PWD Boyd ◽  
JL Laver ◽  
J Wong

The densities of molten PbCl2, CsCl, and RbCl and of the molten salt systems PbCl2 + NaCl, PbCl2 + RbCl, PbCl2 + CsCl, CdCl2 + RbCl, and CdCl, + CsCl have been measured to an accuracy of �0.1% by an Archimedean method over a considerable temperature range. Integral and partial molar volume isotherms have been constructed for the above binary systems and are interpreted to show that complex ions are formed in all but the PbCl2+NaCl system.

1980 ◽  
Vol 35 (11) ◽  
pp. 1186-1191 ◽  
Author(s):  
Chao-cheng' Yang ◽  
Ryuzo Takagi ◽  
Isao Okada

Abstract For the molten salt systems (Li-Na)NO3 and (Na-Cs)NO3, relative differences of internal mobilities have been measured with the Klemm method. The internal mobilities, b, are calculated from these data and the available conductivity data. In the mixtures of the former system, bNa is always greater than bLi. In the latter system, the Chemla crossing point occurs. It is found that bLi and bNa in the binary alkali nitrate systems so far investigated are well expressed, except at small molar volumes, by b = {A/(V - V0)} exp(- E/RT) with constant A and E, where V is the molar volume and F° a constant for bu and nearly a constant for The values of bCs at equal concentrations of CsNO3 in the systems (Li-Cs)NO3 and (Na-Cs)NO3 are practically equal. The internal mobilities obtained are discussed in terms of free space, mutual ionic attraction and thermal agitation.


1966 ◽  
Vol 19 (2) ◽  
pp. 187 ◽  
Author(s):  
H Bloom ◽  
SB Tricklebank

The enthalpy change on cooling molten and solid salts and their mixtures from temperatures as high as 850� down to 26.9� has been measured by means of a Bunsen-type fusion calorimeter. The enthalpy of formation of solid mixtures has also been measured using a water solution calorimeter. From the combined results, heats of mixing have been determined for the molten salt systems investigated. In each system, with the exception of CdCl2 + PbCl2, the process of mixing is exothermic and the relative magnitude of the results can be explained by the formation of complex ions in the systems CdC12 +NaCl, CdCl2 +KCl, PbCl2 +KCl, and CdI2 +KI. Complex ions have not been detected in the other systems.


1974 ◽  
Vol 27 (7) ◽  
pp. 1401
Author(s):  
H Bloom ◽  
MR Bendall ◽  
PDW Boyd ◽  
JL Laver

Densities of binary mixtures of ZnBr2 + KBr, CdI2 + NaI and CdI2 + CsI, have been measured by an Archimedian method over a wide range of temperature. Results have been expressed in terms of simple linear equations in temperature. Molar volumes for the systems have excess values in the ZnBr2 + KBr and CdI2 + CsI systems but not to such an extent in the CdI2+NaI system. The excess molar volumes are related to the possible formation of complex ions in the systems concerned.


2002 ◽  
Vol 80 (7) ◽  
pp. 753-760 ◽  
Author(s):  
Jianji Wang ◽  
Yang Zhao ◽  
Kelei Zhuo ◽  
Ruisen Lin

Apparent molar volumes (V2, ϕ ) and standard partial-molar volumes (V20, ϕ ) of LiClO4 and LiBr at 298.15 K have been determined from precise density measurements in solvent mixtures of propylene carbonate (PC) with dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile (AN), and methyl formate (MF). The scaled particle theory is used to calculate the contributions of the cavity formation and the electrolyte-solvent interactions to the standard partial-molar volumes. It is shown that V20, ϕ is strongly dependent on the nature of the solvents, and the trends in V20, ϕ with composition of the solvent mixtures are determined by the interaction volumes of electrolytes with solvents. The results are discussed in terms of ionic preferential solvation, packing effect of solvents in the solvation shell, and electrostriction of solvents by ion.Key words: partial-molar volume, scaled particle theory, lithium salts, propylene carbonate, solvent mixtures, lithium battery electrolytes.


2014 ◽  
Vol 2014 ◽  
pp. 1-13 ◽  
Author(s):  
Sk. Md Nayeem ◽  
M. Kondaiah ◽  
K. Sreekanth ◽  
D. Krishna Rao

Ultrasonic velocities (u), densities (ρ), and viscosities (η) of binary liquid mixtures of cyclohexanone with benzyl benzoate, including pure liquids, over the entire composition range have been measured at 308.15 K, 313.15 K, and 318.15 K. Using the experimental results, parameters such as molar volume (Vm), isentropic compressibility (ks), intermolecular free length (Lf), acoustic impedance (Z), internal pressure (πi), enthalpy (H), Gibbs free energy of activation of viscous flow (G*E), and excess/deviation properties of these including partial molar volumes (V-m,1 and V-m,2), excess partial molar volumes (V-m,1E and V-m,2E), partial molar volume of the components at infinite dilution (V-m,1∞, V-m,2∞), and excess partial molar volume at infinite dilution (V-m,1E,∞and V-m,2E,∞) have been computed. The observed negative values of VmE, Δks, LfE, and πiE and positive values of zE, HE, ΔG*E, Δη, and Δu for all the liquid mixtures studied clearly indicate the presence of strong dipole-dipole-type interactions, fitting of smaller molecules into bigger molecules. Further theoretical values of sound velocity and viscosity in the mixtures have been evaluated using various theories and have been compared with experimental values to verify the applicability of such theories to the systems studied.


1981 ◽  
Vol 34 (3) ◽  
pp. 479 ◽  
Author(s):  
H Bloom ◽  
MS White

The electromotive forces of galvanic cells for the formation of PbBr2 in the molten binary salt systems, PbBr2-KBr, PbBr2,-RbBr and PbBr2-CsBr, have been measured. Activities, activity coefficients and partial molar free energies have been calculated for each component of the three systems. Integral free energies of mixing have also been calculated. Various models of mixing of molten salts have been applied to the results. The systems contain complex ions, probably mixtures of PbBr42-, PbBr64- with some PbBr3-.


1983 ◽  
Vol 48 (8) ◽  
pp. 2327-2334
Author(s):  
Otakar Söhnel ◽  
Petr Novotný ◽  
Zdeněk Šolc

Two methods are given for assessment of density of binary aqueous solutions of electrolytes; one is based on partial molar volume of the dissolved electrolyte at infinite dilution, and the other is based on additivity of apparent molar volumes at a given concentration. The density estimates of aqueous solutions by means of the two methods are compared with experimental values for some electrolytes of the type 1-1 to 4 and 2-2. In all cases the estimates agree with experimental densities up to concentrations of the saturated solutions.


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