A partial-molar volume study of electrolytes in propylene carbonate-based lithium battery electrolyte solutions at 298.15 K

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.

2003 ◽  
Vol 81 (4) ◽  
pp. 307-314 ◽  
Author(s):  
Yang Zhao ◽  
Jianji Wang ◽  
Xiaopeng Xuan ◽  
Ruisen Lin

Apparent molar volumes V2,ϕ and standard partial molar volumes V°2,ϕ for tetraethylammonium bromide (Et4NBr), tetrapropylammonium bromide (Pr4NBr), tetrabutylammonium bromide (Bu4NBr), and tetrahexylammonium bromide (Hex4NBr) have been determined at 298.15 K from precise density measurements in solvent mixtures of propylene carbonate (PC) with N,N-dimethylformamide (DMF). Combined with our previous data for LiClO4 and LiBr in the same solvents, ionic molar volumes of Li+, Et4N+, Pr4N+, Bu4N+, Hex4N+, and related anions have been deduced from the extrapolation method suggested by Conway and co-workers. It is shown that the molar volumes of these cations are quite independent of the nature of the solvent and the composition of the solvent mixtures, in contrast to those of ClO4– and Br– anions. This suggests that the Lewis-base-type solvents with similar molecular volumes have similar interactions with Li+. The constancy in partial molar volume for tetraalkylammonium ions provides helpful evidence for the lack of solvation of large tetraalkylammonium cations in organic solvents. These findings have been interpreted using scaled-particle theory. The results are discussed in terms of ion solvation, packing effects of solvent molecules in the solvation shell, and the electrostriction of solvents.Key words: ionic volumes, propylene carbonate, N,N-dimethylformamide, solvent mixtures, solvation, lithium batteries.


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.


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.


2001 ◽  
Vol 79 (10) ◽  
pp. 1460-1465 ◽  
Author(s):  
Miguel Angel Sánchez ◽  
Ana María Mainar ◽  
Juan Ignacio Pardo ◽  
María Carmen López ◽  
José Santiago Urieta

Solubilities, expressed as mol fractions, of 14 nonpolar gases (He, Ne, Ar, Kr, Xe, H2, N2, O2, CH4, C2H4, C2H6, CO2, CF4, and SF6) in 2,2,2-trifluoroethanol (TFE) at 268.15 and 283.15 K and 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) at 273.15 and 283.15 K, with the partial pressure of gas being 101.33 kPa for all measurements, are reported. Standard changes in the thermodynamic functions (enthalpy and entropy) have been calculated from the solubilities and their variation with temperature. The Scaled Particle Theory (SPT) model has been used to determine these thermodynamic functions and also the partial molar volumes of the gases in the formed solutions.Key words: gas solubilities, nonpolar gases, fluoroalcohols, Scaled Particle Theory.


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