Conrad Jacy K, Arcis Hugues, Ferguson Jane P, Tremaine Peter R
Department of Chemistry, University of Guelph, Guelph, ON, N1G 2W1, Canada.
Phys Chem Chem Phys. 2023 Jan 18;25(3):1659-1676. doi: 10.1039/d2cp01761j.
A custom-built flow-through AC conductivity instrument was used to measure the deuterium isotope effect on the ionization quotient of bisulfate from 150 to 300 °C, at = 11.5 MPa. Standardized solutions of KCl, HCl, KOH, KHSO, KSO, and HSO were prepared in light and heavy waters and their conductivities were measured and fitted with the Quint-Viallard conductivity model to obtain single ion conductivities at infinite dilution for K, Cl, H, OH, HSO, and SO. These are the first conductivities of DSO and SO measured in heavy water at any temperature, and the first ionization constants for bisulfate reported in heavy water above 225 °C. The deuterium isotope effect on the chemical equilibrium constant, Δp = p - p, was found to increase with temperature, in contrast to the behaviour seen for other simple oxyacids.
使用一台定制的流通式交流电导率仪，在11.5 MPa压力下，测量了150至300 °C温度范围内重水对硫酸氢根电离常数的氘同位素效应。在轻水和重水中制备了KCl、HCl、KOH、KHSO₄、K₂SO₄和H₂SO₄的标准溶液，并测量其电导率，然后用Quint-Viallard电导率模型进行拟合，以获得K⁺、Cl⁻、H⁺、OH⁻、HSO₄⁻和SO₄²⁻在无限稀释时的单离子电导率。这些是在任何温度下重水中首次测量的DSO₄和SO₄²⁻的电导率，也是225 °C以上重水中首次报道的硫酸氢根的电离常数。与其他简单含氧酸的行为相反，发现氘同位素对化学平衡常数的影响Δp = p₁ - p₂随温度升高而增加。
