Partitioning of oxygen isotopes during the aqueous solvation of nitric acid

Larson, Toti E.; Perkins, George B.; Williams, Robert F.; Fessenden, Julianna E.; Clegg, Samuel M.; Currier, Robert P.

doi:10.1016/j.fluid.2019.112364

Title: Partitioning of oxygen isotopes during the aqueous solvation of nitric acid

Journal Article · 17 October 2019 · Fluid Phase Equilibria

DOI: https://doi.org/10.1016/j.fluid.2019.112364 · OSTI ID:1572331

Larson, Toti E. ^[1];

^[2];

^[2]

Univ. of Texas at Austin, Austin, TX (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Mixtures of water and inorganic acids show differences in isotopic composition between the vapor and liquid phases, reportedly even at an azeotrope. A recent reactive azeotropy analysis rationalized this by allowing for differences in stable isotope composition between bound solvation complexes and the bulk liquid. In this study, a mixture of water and nitric acid was examined experimentally to determine whether or not significant differences in stable isotope composition exist between bound solvation complexes and the bulk solution. A Rayleigh distillation was conducted using a solution of nitric acid and water. During the distillation, it was expected that bulk water would be vaporized first while (bound) water involved with hydrating the acid would be vaporized at later times along with the acid. Samples of both distillate and residual liquid were collected over time intervals and analyzed to determine oxygen and nitrogen stable isotope composition using isotope ratio mass spectrometry. Comparative samples were collected from the distillation of water alone. The measured oxygen fractionation factors suggest that the acid is preferentially hydrated with ¹⁸O-enriched water, compared to the unbound, or bulk, water. Preferential coordination of ¹⁸O-enriched water with the dissolved acid is consistent with heavier water forming stronger bonds relative to light water. Here, the results imply that isotope-dependent partitioning between bulk solvent and dissolved complexes may prove necessary in developing accurate descriptions of isotope fractionation during vapor-liquid equilibrium.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite