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Ion Association in Lanthanide Chloride Solutions.

ABSTRACT: A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of Ln^III association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl₃ (aq) solutions. The force field accurately reproduces the structure and dynamics of Nd³⁺ , Gd³⁺ and Er³⁺ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of Ln^III -Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere LnCl x ( 3 - x ) + coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water.

SUBMITTER: Finney AR

PROVIDER: S-EPMC6619345 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Ion Association in Lanthanide Chloride Solutions.

Finney Aaron R AR Lectez Sébastien S Freeman Colin L CL Harding John H JH Stackhouse Stephen S

Chemistry (Weinheim an der Bergstrasse, Germany) 20190530 37

A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of Ln<sup>III</sup ...[more]

PMID: 31017723

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Project description:ObjectivesDerangements of chloride ion concentration ([Cl-]) have been shown to be associated with acute kidney injury and other adverse outcomes. For a physicochemical approach, however, chloride ion concentration should be considered with sodium ion concentration. This study aimed to examine the association of chloride ion concentration and the main strong ion difference (difference between sodium ion concentration and chloride ion concentration) during the first 24 hours after admission into ICU with the development of acute kidney injury and mortality.DesignRetrospective analyses using the eICU Collaborative Research Database.SettingICUs in 208 hospitals across the United States between 2014 and 2015.PatientsCritically ill patients who were admitted into the ICU.InterventionsNone.Measurements and main resultsA total of 34,801 patients records were analyzed. A multivariable logistic regression analysis for the development of acute kidney injury within 7 days of ICU admission shows that, compared with main strong iron difference 32-34 mEq/as a reference, there were significantly high odds for the development of acute kidney injury in nearly all groups with main strong iron difference more than 34 mEq/L (main strong iron difference = 34-36 mEq/L, odds ratio = 1.17, p = 0.02; main strong iron difference = 38-40 mEq/L, odds ratio = 1.40, p < 0.001; main strong iron difference = 40-42 mEq/L, odds ratio = 1.46, p = 0.001; main strong iron difference > 42 mEq/L, odds ratio = 1.56, p < 0.001). With chloride ion concentration 104-106 mEq/L as a reference, the odds for acute kidney injury were significantly higher only in chloride ion concentration less than or equal to 94 mEq/L and chloride ion concentration 98-100 mEq/L groups. Analyses conducted using inverse probability weighting showed significantly greater odds for ICU mortality in all groups with main strong iron difference greater than 34mEq/L other than the 36-38mEq/L group, as well as in the less than 26-mEq/L group.ConclusionsMain strong iron difference measured on ICU presentation to the ICU predicts acute kidney injury within 7 days, with low and, in particular, high values representing increased risk. The association between the chloride levels and acute kidney injury is statistically insignificant in models incorporating main strong iron difference, suggesting main strong iron difference is a better predictive marker than chloride on ICU admission.

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Ion Association in Lanthanide Chloride Solutions.

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Ion Association in Lanthanide Chloride Solutions.

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