Densities and Viscositiesof Aqueous Solutions ofTributylmethylphosphonium Dimethylphosphate

Densities and viscosities of aqueous solutions of tributylmethylphosphonium dimethylphosphate, [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>], were measured over an entire range of compositions at atmospheric pressure at temperatures between 278.15 and 363.15 K. The isobaric thermal expansivities and partial molar volumes were derived at different compositions and temperatures. The density and expansivity showed maxima in the dilute aqueous solutions at the mole fraction of [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>], <i>x</i><sub>2</sub> ≈ 0.1. The experimental viscosities were well reproduced by the Vogel–Fulcher–Tammann (VFT) equation, with parameters that also indicate the minima (<i>B</i> and <i>D</i>) and maxima (ln <i>A</i> and <i>T</i><sub>0</sub>) in the dilute aqueous solutions at <i>x</i><sub>2</sub> < 0.05. The volumetric and viscosity behaviors have been analyzed in terms of dilute electrolyte solution theory, suggesting that [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>] can behave as a so-called structure-making salt. The excess molar volumes and deviation viscosities were all negative over an entire range of compositions with the minima at <i>x</i><sub>2</sub> ≈ 0.3 and 0.6, respectively, and increased with increasing temperature. The excess molar volumes and deviation viscosities for the aqueous solutions of [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>] were quantitatively compared to those for the aqueous solutions of ionic liquids composed of similar cations and/or anions.

Publication Details

Journal
Figshare
Published
2025-02-19
DOI
https://doi.org/10.1021/acs.jced.4c00565.s001
Primary Topic
Thermodynamic properties of mixtures
Type
article
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article

Densities and Viscositiesof Aqueous Solutions ofTributylmethylphosphonium Dimethylphosphate

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Thermodynamic properties of mixtures
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Densities and Viscositiesof Aqueous Solutions ofTributylmethylphosphonium Dimethylphosphate

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Abstract

Densities and viscosities of aqueous solutions of tributylmethylphosphonium dimethylphosphate, [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>], were measured over an entire range of compositions at atmospheric pressure at temperatures between 278.15 and 363.15 K. The isobaric thermal expansivities and partial molar volumes were derived at different compositions and temperatures. The density and expansivity showed maxima in the dilute aqueous solutions at the mole fraction of [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>], <i>x</i><sub>2</sub> ≈ 0.1. The experimental viscosities were well reproduced by the Vogel–Fulcher–Tammann (VFT) equation, with parameters that also indicate the minima (<i>B</i> and <i>D</i>) and maxima (ln <i>A</i> and <i>T</i><sub>0</sub>) in the dilute aqueous solutions at <i>x</i><sub>2</sub> < 0.05. The volumetric and viscosity behaviors have been analyzed in terms of dilute electrolyte solution theory, suggesting that [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>] can behave as a so-called structure-making salt. The excess molar volumes and deviation viscosities were all negative over an entire range of compositions with the minima at <i>x</i><sub>2</sub> ≈ 0.3 and 0.6, respectively, and increased with increasing temperature. The excess molar volumes and deviation viscosities for the aqueous solutions of [P<sub>4441</sub>][(CH<sub>3</sub>O)<sub>2</sub>PO<sub>2</sub>] were quantitatively compared to those for the aqueous solutions of ionic liquids composed of similar cations and/or anions.

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