Enthalpies of dilution of aqueous solutions of aliphatic 6,12- and 12,12-ionene bromides and fluorides and enthalpies of mixing with low molecular-weight salts, such as Naf and NaBr, are determined. The comparison with theoretical results, based on the Poisson–Boltzmann cell model, is presented. The theory predicts for the enthalpy of dilution to be exothermic and the enthalpy of mixing endothermic, while experiments show that signs of the heat effects depend on the nature of the counterion of the added salt, as also on the hydrophobicity (numbers x, y of methylene groups) of the ionene. We show that the salts when ordered by heat effects produced by mixing of NaF and NaBr with 3,3-, 6,9-, or 6,12-ionene fluorides and bromides follow the opposite ordering than in the case when the same alkali halide salts are mixed with more hydrophobic 12,12-ionene salts.
COBISS.SI-ID: 36662021
Simulations and integral equation results are presented for a model partly quenched system composed of monovalent ions. Static and dynamic properties of the system are explored using the replica Ornstein–Zernike theory in the hypernetted chain approximation and Brownian dynamic simulations. The model system consists of two subsystems: one is a collection of charged obstacles (matrix), and the other is an invading electrolyte. The overall system is electroneutral, while the subsystems are not. Charged species are represented by Lennard–Jones spheres of equal size, with either positive or negative charge in the center. The solvent is treated as a continuous dielectric. The purpose of this study is to correlate the mobility of ions (self-diffusion coefficients) with their individual activity coefficients.
COBISS.SI-ID: 36498181
Transport and binding capabilities in aqueous solutions of 3,3-, 6,6-, and 6,9-ionene fluorides and bromides at 298 Kwere explored through the experimentally determined values for transport numbers of counterions and polyion constituents, along with the data for electrical conductivity in these solutions. Within the association theory, the fractions of free counterions and the effective linear charge densities of polyions were calculated. It was determined that binding of the counterions to the polyion critically depends (i) on charge density of the polyion and (ii) on the chemical nature of the counterion in question. The effects of the charge density are the strongest in solutions of ionene bromides. Differences in the behavior of solutions of ionene fluorides and bromides are the consequence of different hydration capabilities of these ions. The effective linear charge density was found to be much lower than predicted from structural parameters of ionenes.
COBISS.SI-ID: 36602373