Conductance and association behavior of the alkali metal perchlorates and tetraphenylborides in anhydrous acetonitrile

Abstract

Equivalent conductances of the alkali metal perchlorates and tetraphenylborides (Ph4B) in anhydrous acetonitrile at 25°are reported. The lithium salts were too unstable or too hygroscopic for precise measurements, although an estimated ionic mobility for the Li + ion is reported. All the perchlorates show some ion pair association, whereas the tetraphenylborides are all completely dissociated with the possible exception of cesium. The limiting ionic conductances, obtained from a Fuoss-Coplarr split for this solvent, are compared to similar data for methanol and ethanol solutions. For very large ions, the conductance-viscosity products are about the same.For ions of intermediate size, the dipole moment and size of the solvent molecules appear to be the mobility-determining factors, whereas for small ions, the relative acid-base strength of the solvent molecules rather than their dipole moments appears to be the important factor.

Conductometric Study on Higher Ion Aggregation of Lithium and Sodium Nitrophenolates in Aprotic Solvents

“…The specific conductances of MeCN, PhCN, acetone, and DMF were (0.3−1.1) × 10 -7 , (3.3−7.2) × 10 -3 , (0.2−1.1) × 10 -7 , and (0.9−4.3) × 10 -7 S cm -1 , respectively. The permittivities and viscosities (η/cP: 1 P = 0.1 Pa s) of the solvents at 25 °C are 35.95 and 0.3412 for MeCN, 25.2 and 1.22 for PhCN, 20.7 and 0.302 for acetone, and 36.71 and 0.796 for DMF, respectively.…”

A Critical Study of the Ph4AsPh4B Assumption for Single Ion Thermodynamics in Amphiprotic and Dipolar-Aprotic Solvents; Evaluation of Physical Parameters Relevant to Theoretical Consideration

“…The analytical procedures used in this work, i.e. The assumption is further supported by the experiment that the tetraphenylborates of alkalimetal ions are found to be completely dissociated in acetonitrile [62]. The experimental values presented in this paper are the averages of more than four separate determinations from the two different analytical methods.…”

Effect of Sodium Ions on the Electrochemical Reduction of Diethyl Fumarate in Dimethylsulfoxide and Acetonitrile

“…Tetra-n-butylammonium perchlorate (Matheson Coleman and Bell) was recrystallized from acetone-water and vacuum dried at room temperature. Anhydrous sodium perchlorate (Matheson Coleman and Bell) was found to contain less than 1 mole per cent (m/o) water by determining loss of weight after vacuum drying at 200°C (10). Diethyl fumarate (Aldrich) was used as received.…”