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Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system

Research output: Contribution to journalArticlepeer-review

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  • Embargoed (until 5/06/21)

Abstract

The aqueous boric, hydrofluoric, and fluoroboric acid systems are key to a variety of applications, including boron measurements in marine carbonates for CO2 system reconstructions, chemical analysis and synthesis, polymer science, sandstone acidizing, fluoroborate salt manufacturing, and more. Here we present a comprehensive study of chemical equilibria and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. We work out the chemical speciation of the various dissolved compounds over a wide range of pH, total fluorine (FT), and total boron (BT) concentrations. We show that at low pH (0 ≤ pH ≤ 4) and FT ≫ BT, the dominant aqueous species is BF4, a result relevant to recent advances in high precision measurements of boron concentration and isotopic composition. Using experimental data on kinetic rate constants, we provide estimates for the equilibration time of the slowest reaction in the system as a function of pH and [HF], assuming FT ≫ BT. Furthermore, we present the first quantum-chemical (QC) computations to determine boron isotope fractionation in the fluoroboric acid system. Our calculations suggest that the equilibrium boron isotope fractionation between BF3 and BF4 is slightly smaller than that calculated between B(OH)3 and B(OH)4. Based on the QC methods X3LYP/6-311+G(d,p) (X3LYP+) and MP2/aug-cc-pVTZ (MP2TZ),  α(BF3−BF4) ≃ 1.030 and 1.025, respectively. However, BF4 is enriched in 11B relative to B(OH)4, i.e., α(BF4−B(OH)4) ≃ 1.010 (X3LYP+) and 1.020 (MP2TZ), respectively. Selection of the QC method (level of theory and basis set) represents the largest uncertainty in the calculations. The effect of hydration on the calculated boron isotope fractionation turned out to be minor in most cases, except for BF4 and B(OH)3. Finally, we provide suggestions on best practice for boric acid–hydrofluoric acid applications in geochemical boron analyses.
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Details

Original languageEnglish
Article number119693
JournalChemical Geology
Volume550
Early online date5 Jun 2020
DOIs
Publication statusPublished - 20 Sep 2020

    Research areas

  • Isotopic and elemental geochemistry, Boron isotopes, pH proxy, Analytical and theoretical advances, Aqueous boric acid-hydrofluoric acid system

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