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Journal of Structural Chemistry

2014 year, number 3

BULK PROPERTIES AND HYDRATION NUMBERS OF AMMONIUM NITRATE AND AMMONIUM CHLORIDE IN SOLUTION: A STRUCTURAL AND THERMODYNAMIC ANALYSIS

V. P. Korolev
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: apparent and partial volumes, hydration numbers, ammonium chloride, ammonium nitrate

Abstract

The apparent volumes of the salts in the systems H2O - NH4Cl (298 K) and H2O - NH4NO3 (273, 298, and 323 K) are reproduced with an accuracy of 0.03-0.01 cm 3/mol by the equation φ = φ0 + Aw20,5 + Вw2, where w2 is the salt content (mass fractions). The study shows that there is a correspondence between the critical (for determining the hydration number) structural parameters-the intrinsic volume of the electrolyte and the volume of water in ion hydration shells-and the limiting (at w2 = 1) partial molar volumes of the components. The hydration numbers at infinite dilution are 6.9 for NH4Cl at 298 K and 9.1, 6.7, and 6.4 for NH4NO3 at 273, 298, and 323 K. The water volume in ion hydration shells decreases in the sequence: NO3¯ Cl-, and NH4+ The hydration numbers decrease with increasing salt concentration. The study shows that within a simpler model φ = φ0 + aw20,5, the hydration numbers are temperature independent.