0000000000170836
AUTHOR
Raymond M. Fuoss
Conductance in isodielectric mixtures. III.i-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dichlorobenzene, 1,2-dichloroethane, andn-pentanol
The conductance of tetrabutylammonium tetraphenylboride, picrate, perchlorate, and nitrate has been measured at 25°C in mixtures ofi-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dicholorobenzene, 1,2-dichloroethane, andn-pentanol covering the range of dielectric constants 10≤D≤20. In these mixtures of polar solvents, both association constants and ionic mobilities depend on ion-solvent interaction energies and on free volume in a manner that is specific for each system. This failure of the primitive model (rigid charged spheres in a continuum) is shown to be the consequence of short-range spatial and energetic interactions between ions and adjacent solvent molecules.
Conductance in isodielectric mixtures. I.n-butyronitrile with dioxane, benzene, and carbon tetrachloride
The conductance of tetrabutylammonium tetraphenylboride, picrate, nitrate, and bromide has been measured at 25°C inn-butyronitrile and in mixtures of this solvent with dioxane, benzene, and carbon tetrachloride covering the range of dielectric constants from 10–24.26. For the picrate, nitrate, and bromide, the association constants at a given dielectric constant are independent of the chemical composition of the solvent. The changes of Walden products with solvent composition, however, are different, depending on which other solvent is mixed with the butyronitrile.
Conductance of potassium lodide in mixed solvents
The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants KA are in the range 0.3–2.0; no correlation between KA and solvent properties could be established. For lower dielectric constants, KA increases exponentially with decreasing dielectric constant. Addition of a pro…
The conductance of lithium-7 fluoride in dioxane-water mixtures at 25�C
Conductance data for lithium-7 fluoride in dioxane-water mixtures covering the range 78.35>D>36 in dielectric constant are presented. These data and other previous data on lithium-7 chloride and lithium-7 iodide were analyzed by the Fuoss 1980 conductance equation in order to find the limiting conductance Δo, the pairing distance R and the conductometric association constant Kλ. Setting Ka=Kλ/VM (where VM is the molar volume of the solvent), the thermodynamic pairing constant and the corresponding change of the free energy Δg were calculated. Correlation among the values found for R and Δg=Δh−TΔs and the properties characteristic of the ions and solvents are discussed.