Ion-pair formation in aqueous strontium chloride and strontium hydroxide solutions under hydrothermal conditions by AC conductivity measurements

Literature Information

Publication Date 2014-06-24
DOI 10.1039/C4CP01703J
Impact Factor 3.676
Authors

H. Arcis, G. H. Zimmerman, P. R. Tremaine


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Abstract

Frequency-dependent electrical conductivities of solutions of aqueous strontium hydroxide and strontium chloride have been measured from T = 295 K to T = 625 K at p = 20 MPa, over a very wide range of ionic strength (3 × 10−5 to 0.2 mol kg−1), using a high-precision flow AC conductivity instrument. Experimental values for the concentration-dependent equivalent conductivity, Λ, of the two electrolytes were fitted with the Turq–Blum–Bernard–Kunz (“TBBK”) ionic conductivity model, to determine ionic association constants, KA,m. The TBBK fits yielded statistically significant formation constants for the species SrOH+ and SrCl+ at all temperatures, and for Sr(OH)02 and SrCl02 at temperatures above 446 K. The first and second stepwise association constants for the ion pairs followed the order KA1(SrOH+) > KA1(SrCl+) > KA2[Sr(OH)02] > KA2[SrCl02], consistent with long-range solvent polarization effects associated with the lower static dielectric constant and high compressibility of water at elevated temperatures. The stepwise association constants to form SrCl+ agree with previously reported values for CaCl+ to within the combined experimental error at high temperatures and, at temperatures below ∼375 K, the values of log10 KA1 for strontium are lower than those for calcium by up to ∼0.3–0.4 units. The association constants for the species SrOH+ and Sr(OH)02 are the first accurate values to be reported for hydroxide ion pairs with any divalent cation under these conditions.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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