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

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Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. / Zeebe, Richard; Rae, James W. B.

In: Chemical Geology, Vol. 550, 119693, 20.09.2020.

Research output: Contribution to journalArticlepeer-review

Harvard

Zeebe, R & Rae, JWB 2020, 'Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system', Chemical Geology, vol. 550, 119693. https://doi.org/10.1016/j.chemgeo.2020.119693

APA

Zeebe, R., & Rae, J. W. B. (2020). Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. Chemical Geology, 550, [119693]. https://doi.org/10.1016/j.chemgeo.2020.119693

Vancouver

Zeebe R, Rae JWB. Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. Chemical Geology. 2020 Sep 20;550. 119693. https://doi.org/10.1016/j.chemgeo.2020.119693

Author

Zeebe, Richard ; Rae, James W. B. / Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. In: Chemical Geology. 2020 ; Vol. 550.

Bibtex - Download

@article{7b62612fa7194397b2a4d6e064fd620f,
title = "Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system",
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.",
keywords = "Isotopic and elemental geochemistry, Boron isotopes, pH proxy, Analytical and theoretical advances, Aqueous boric acid-hydrofluoric acid system",
author = "Richard Zeebe and Rae, {James W. B.}",
note = "REZ is grateful to Lance Agavulin and Glen Morangie for their spiritual support. JWBR was supported by the European Research Council (ERC Grant 805246) and the Natural Environment Research Council (NERC grant NE/N011716/1).",
year = "2020",
month = sep,
day = "20",
doi = "10.1016/j.chemgeo.2020.119693",
language = "English",
volume = "550",
journal = "Chemical Geology",
issn = "0009-2541",
publisher = "Elsevier",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Equilibria, kinetics, and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system

AU - Zeebe, Richard

AU - Rae, James W. B.

N1 - REZ is grateful to Lance Agavulin and Glen Morangie for their spiritual support. JWBR was supported by the European Research Council (ERC Grant 805246) and the Natural Environment Research Council (NERC grant NE/N011716/1).

PY - 2020/9/20

Y1 - 2020/9/20

N2 - 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.

AB - 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.

KW - Isotopic and elemental geochemistry

KW - Boron isotopes

KW - pH proxy

KW - Analytical and theoretical advances

KW - Aqueous boric acid-hydrofluoric acid system

U2 - 10.1016/j.chemgeo.2020.119693

DO - 10.1016/j.chemgeo.2020.119693

M3 - Article

VL - 550

JO - Chemical Geology

JF - Chemical Geology

SN - 0009-2541

M1 - 119693

ER -

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