Ближняя гидратация ионов в предельно разбавленных водных растворах галогеноводородов: влияние температуры и давления

Abstract

The calculation of attraction coefficient (ξаt) in water for proton, chloride- and bromide-ion was carried out over the temperature range from 273.15 to 473.15 K and pressure range from 1 to 8000 kg/cm² using the literary limiting electrical conductance of these ions. Negative hydration of proton was identified at all temperatures and pressures on the basis of the results we obtained. The transformation from negative to positive hydration was revealed for chloride- and bromide-ion. Temperature and pressure range,when this transition is observable, were determined. It is shown, that negative solvation is connected with prevailing influence of short-range intermolecular interactions as compared to ion-molecular. The scheme of the supposed mechanism of prototropictransfer of proton is offered. This scheme includes transfer of hydronium and structural diffusionof Zundel cation in volume of "free solvent".