Ionization of a nonpolar liquid with an alcohol.
Nonpolar liquids whose dielectric permittivities are close to 2 have very low conductivities, usually below 10 × 10(-10) S/m. Their ionization is suppressed by the lack of solvation resulting from the negligible dipole moment of such liquids' molecules. Ionization could be enhanced by the addition of other substances that could serve as solvating agents, creating inverse micelles around ions and preventing them from reassociating into ion pairs and neutral molecules. Surfactants are normally used for this purpose, but we show here that alcohols could perform a similar function. However, the mechanism of ionization by alcohols turns out to be quite different compared to the mechanism of ionization by surfactant. For instance, the conductivity of poly-α-olefin oil (PAO) depends on the concentration of added octanol (alcohol) as an exponential function above 10% of the octanol content. At concentrations below approximately 10%, octanol does not affect the conductivity at all. This phenomenon has never been observed for surfactant solutions. Apparently, octanol is completely dissolved at concentrations below 10% and forms micelles only above this concentration, which is the cmc for octanol-PAO mixtures. Below the cmc, octanol molecules do not dissociate, despite being able to dissociate in pure octanol, which has a conductivity of about 10 × 10(-7) S/m. This again stresses the importance of the solvating factor in the ionization of liquids. Above 10% concentration, octanol molecules form micelles, which become charged by the disproportionation mechanism when they collide. To explain the exponential dependence of conductivity on octanol content, we assume that charged micelles grow in volume with increasing octanol content faster than neutral ones. Ion-dipole interactions are responsible for the preferential adsorption of octanol molecules onto charged micelles. Additional ionization occurs in such larger micelles, which then break down into smaller ones carrying individual electric charges.
Universidade Federal de Itajubá/IFQ , Av. BPS 1303, Itajubá - MG, 37500-903, Brazil.
Antonio J F
AJ
Bombard
Andrei
A
Dukhin