Dataset Information

Mass action model of solution activity via speciation by solvation and ion pairing equilibria.

ABSTRACT: Solutes and their concentrations influence many natural and anthropogenic solution processes. Electrolyte and solution models are used to quantify and predict such behavior. Here we present a mechanistic solution model based on mass action equilibria. Solvation and ion pairing are used to model speciated solute and solvent concentrations such that they correlate to a solution's vapor pressure (solvent activity) according to Raoult's law from dilute conditions to saturation. This model introduces a hydration equilibrium constant (K_ha) that is used with either an ion dissociation constant (K_id) or a hydration modifier (m) with an experimentally determined ion dissociation constant, as adjustable parameters to fit vapor-liquid equilibrium data. The modeled solvation equilibria are accompanied by molecular dynamics (MD) studies that support a decline in the observed degree of solvation with increased concentration. MD calculations indicate this finding is a combination of a solvent that solvates multiple solutes, and changes in a solute's solvation sphere, with the dominant factor changing with concentration. This speciation-based solution model is lateral to established electrostatics-based electrolyte theories. With its basis in mass action, the model can directly relate experimental data to the modeled solute and solvent speciated concentrations and structures.

SUBMITTER: Wilson AD

PROVIDER: S-EPMC9814931 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Mass action model of solution activity via speciation by solvation and ion pairing equilibria.

Wilson Aaron D AD Lee Hyeonseok H Stetson Caleb C

Communications chemistry 20211126 1

Solutes and their concentrations influence many natural and anthropogenic solution processes. Electrolyte and solution models are used to quantify and predict such behavior. Here we present a mechanistic solution model based on mass action equilibria. Solvation and ion pairing are used to model speciated solute and solvent concentrations such that they correlate to a solution's vapor pressure (solvent activity) according to Raoult's law from dilute conditions to saturation. This model introduces ...[more]

PMID: 36697558

Similar Datasets

Project description:Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+ [OAc]- in protic (D2 O) and aprotic (DMSO-d6 ) solvents has been studied by means of concentration-dependent 1 H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d6 , the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent-shared ion pair (SIP) configuration was assigned. For [Ch]+ [OAc]- in D2 O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, ∼ 40 % of the cations in DMSO-d6 and ∼ 10 % in D2 O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d6 , both ions were found to be almost equally solvated, whereas in D2 O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+ [OAc]- in DMSO-d6 , the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3-1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes.

Dataset Information

Mass action model of solution activity via speciation by solvation and ion pairing equilibria.

Publications

Mass action model of solution activity via speciation by solvation and ion pairing equilibria.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets