Water activities of NH₄NO₃/(NH₄)₂SO₄ solutions

Abstract

Water activities for mixed ammonium nitrate/ammonium sulfate solutions at relative humidities of 0.35–0.75 were measured using a spherical void electrodynamic balance. The concentrations of singly levitated droplets of nitrate to sulfate mole ratio of n = 1/5, 1/3, 1/2, 1, 2 and 4 in equilibrium with an ambient environment of prescribed relative humidity were measured. To avoid uncertainty in determining the composition of the solid particles, solution properties were determined relative to the known properties at about 80% relative humidity. The concentration of this reference state was estimated by three models of mixed electrolyte solutions, the Zdanovskii-Stokes-Robinson (ZSR), the Kusik and Meissner (KM) and the Pitzer models. The measured total mass fraction of solute of the mixed solutions differed by less than 0.5% when different models were used to calculate the reference state concentration. The water activity data were obtained at ionic strengths as high as 108 molal and used to evaluate predictions from these three models. For n = 1/5 and 1/3, deviations of model predictions from experimental data are within 2%. Generally, predictions of the ZSR model are most consistent with our data. Maximum deviations occur at n=2; 6% for ZSR, 8% for KM and 5% for Pitzer. The deviations can be attributed to binary and ternary solute-solute interactions that the ZSR, KM and elementary version of the Pitzer models do not consider. However, no simple characterization of the interaction parameters is possible; they seem to be strong functions of the fractional ionic strength of the solute and the total ionic strength of the solutions.