A structural study of saturated aqueous solutions of some alkali halides by X-ray diffraction

Abstract

The structure of nearly saturated or supersaturated aqueous solutions of NaCI [6.18 mol (kg H₂O)⁻¹], KCI [4.56 mol (kg H₂O)⁻¹], KF [16.15 mol (kg H₂O)⁻¹] and CsF [31.96 mol (kg H₂O)⁻¹] has been investigated by means of solution X-ray diffraction at 25°C. In the NaCI and KCI solutions about 30% and 60%, respectively, of the ions form ion pairs and the Na⁺−Cl⁻ and K⁺−Cl⁻ distances have been determined to be 282 and 315 pm, respectively. The average hydration numbers of Na⁺ and Cl⁻ ions are 4.6 and 5.3, respectively, in the NaCI solution and those of K⁺ and Cl⁻ ions in the KCI solution are both 5.8. In the KF solution, clusters containing some cations and anions, besides 1:1 (K⁺−F⁻) ion pairs, are formed. The K⁺−F⁻ interatomic distance has been determined to be 269 pm, and nonbonding K⁺...K⁺ and F⁻...F⁻ distances in the clusters are 388 and 432 pm, respectively, and the average coordination numbers n _KF , n _KK and n _FF have been estimated to be 2.3, 1.9, and 1.6, respectively. In the highly supersaturated CsF solution an appreciable amount of clusters containing several caesium and fluoride ions are formed. The Cs⁺−F⁻ distance in the cluster has been determined to be 312 pm, while the nonbonding Cs⁺...Cs⁺ and F⁻...F⁻ distances are estimated to be 442 and 548 pm, respectively, the distances being about$\sqrt 2$ and$\sqrt 3$ times the Cs⁺−F⁻ distance, respectively. The coordination numbers n _CsF , n _CsCs , and n _FF in the first coordination sphere of each ion are 3.3, 2.3 and 5.3, respectively, and the result shows the formation of clusters of higher order than 1:1 and 2:2 ion pairs. These ion pairs and clusters may be regarded as embryos for the formation of nuclei of crystals and the results obtained in the present diffraction study support observations for the nucleation of the alkali halide crystals studied by molecular dynamics simulations previously examined.