Phenomenon of “negative partial molar expansibility” of water in tetrahydrofuran: How plausible is it?: Discussion on the paper “Volumetric properties on the (tetrahydrofuran + water) and (tetra-n-butylammonium bromide + water) systems: Experimental measurements and correlations” by Veronica Belandria, Ammir H. Mohammadi and Dominique Richon [J. Chem. Thermodyn. 41 (2009) 1382−1386]

doi:10.1016/j.jct.2010.08.006

The Journal of Chemical Thermodynamics

Volume 43, Issue 1, January 2011, Pages 58-62

https://doi.org/10.1016/j.jct.2010.08.006 Get rights and content

Abstract

In order to answer the question: is a solute water “negatively expansible” in tetrahydrofuran or not (?), a comparative analysis of own and literature data on the temperature-dependent partial volumes at the infinite dilution of water isotopologues in tetrahydrofuran have been carried out. Used for computing the limiting partial (apparent) volumes of water isotopologues, densities of H₂O and D₂O solutions in the solvent studied, with the solute mole fractions ranging up to ∼0.043, were measured with an error of 1.5 · 10⁻⁵ cm³ · mol⁻¹ at (278.15, 288.15, 298.15, 308.15, and 318.15) K and atmospheric pressure using a vibrating tube densimeter. It has been shown that the partial molar volume of H₂O or D₂O at infinite dilution increases with rising temperature; that is, the isotopically distinguishable solutions of water in tetrahydrofuran do not have the unusual structure-packing behavior being characteristic of the water-containing system with the so-called phenomenon of “negative partial molar expansibility”.

Introduction

Recently my attention has been drawn to the above-mentioned article [1] in which Richon and co-authors estimated the partial molar volumes of water at the infinite dilution, ${\bar{V}}_{w}^{\infty}$ in tetrahydrofuran (THF) at nine temperatures from (293.15 to 333.15) K. The ${\bar{V}}_{w}^{\infty}$ values were obtained using the Redlich–Kister adjusting coefficients relating to the excess molar volumes, V^E(x_w), for (THF + water) mixtures with the initial water content in the THF-rich region being x_w = 0.307 m.f. at each temperature. Proceeding from this, authors [1] had concluded that ${\bar{V}}_{w}^{\infty}$ decreases from 14.22 to 10.51 cm³ · mol⁻¹ when temperature increases (in the interval studied). Herewith the specified quantities are found to be smaller than the corresponding molar volumes of pure water, V_w, by (8.6 to 40.0) cm³ · mol⁻¹ (!). In other words, V_w value is to be catastrophically ascending, whereas the ${\bar{V}}_{w}^{\infty}$ one undergoes alterations being characteristic of water-containing binary systems with the so-called phenomenon of “negative partial molar expansibility” (hereinafter, briefly NPME), as the temperature increased.

Here, it should be noted that the above phenomenon (i.e., a decrease in the partial molar volume of solute with increasing temperature) was the first disclosed by Hamilton and Stokes, almost four decade ago, when studying the infinitely dilute solutions of urea in methanol (MeOH) [2]. However, they claimed this fact was questionable and might have been caused by a purely combinatorial volume-related effect of some water traces absorbed in a methanol medium that were unaccounted for [2]. Further investigations have shown this conclusion to be wrong and have given grounds to treat NPME as a physically justified thermodynamic effect with a structural nature. At the present time, it has been experimentally established that negative values of $(\partial {\bar{V}}_{w}^{\infty} / \partial T)_{p} = {\bar{E}}_{p,w}^{\infty}$ are typical of dilute solutions of water in MeOH [3], [4], [5], [6], [7], tert-butanol (t-BuOH) [6], [7], [8], [9], and tert-pentanol (up to 298.15 K only) [10] as well, too.¹

Up to now, no information is available on the nature of this phenomenon except for results of studying the structural “peculiarities” of water solutions in MeOH and t-BuOH [6], [7]. It was concluded that a physical prerequisite for NPME in these cases is the lack of intermediate alkyl moieties in solvent molecules. At the macroscopic level, this is manifested in additional volume and energy changes, or the so-called “boundary effects”, their extent and direction being explicitly related to specific features of local structures forming in the alkanols considered [7].

As regards the infinitely dilute solutions of water in aprotic dipolar solvents, including the (THF + H₂O) system, such an unusual temperature-dependent behavior of ${\bar{V}}_{w}^{\infty}$ did not observe earlier. Therefore, one should be concerned about two aspects of the discussed results. Firstly, are the experimental data [1] (including a solvent quality and density measurements) reliable? Secondly, although there is certain agreement between the experimental and smoothed data on V^E(x_w), is a use of the Redlich–Kister adjusting procedure to obtain ${\bar{V}}_{w}^{\infty}$ correct? If this is true, how may one interpret the “unique” results [1]? Unfortunately, published data on ${\bar{V}}_{w}^{\infty} (T)$ , which could resolve these questions, are lacking.

Based on the above reasonings, we have carried out carefully the densimetric investigation of high-diluted (relative to water) solutions of H₂O and D₂O in THF at five temperatures from (278.15 to 318.15) K and at atmospheric pressure to find the temperature-dependent changes in ${\bar{V}}_{w}^{\infty}$ for the systems compared. Replacement of H₂O by D₂O was dictated by the fact that a deuteration makes it possible to estimate the role of hydrogen-bonding on the background of structure-packing transformations as well as exclude from consideration a number of effects on the protiated system [6], [7], [15]. Of special interest are reasons for the appearing discrepancy between the limiting partial volume properties of solute H₂O and D₂O in the THF medium.

Section snippets

Experimental

THF (Fluka, assay ⩾ .99.5 wt%) was purified according to the procedure [16]: the solvent sample was originally kept several days over KOH, then refluxed for 24 h and fractionally distilled over metal sodium under dry nitrogen; the middle fraction of the distillate was finally collected and treated with 0.3-nm molecular sieves (activated by heating at ∼520 K for 24 h) at the presence of gaseous N₂. The freshly prepared THF sample was stored in a dark place and redistilled immediately before use. Gas

Results and discussion

Experimental density ρ and cubic expansion coefficient α_p values of pure THF at each of temperatures employed are given in table 1 together with the literature findings. A survey of the presented results shows that our data on both ρ and α_p are in very good agreement with the precise values reported by Kiyohara et al. [25] at T = (288.15, 298.15, and 308.15) K. As regards other sources, the quantities considered agree rather satisfactory with ours only at 298.15 K (except for data [1], [27], [28]).

Concluding remarks

This work can be concluded with a main question that was the start for present research: whether the phenomenon of the so-called “negative partial molar expansibility” (or NPME) is a peculiarity of the infinitely dilute solution of water in THF? In other words, may we agree with findings [1] about decreasing the limiting partial molar volume of water as a solute in the given aprotic dipolar medium when the temperature is rising, or not? The results obtained here answer the questions formulated,

Acknowledgment

The author is grateful to Dr. E. Yu. Lebedeva for help in densimetric measurements.

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Abstract

Introduction

Section snippets

Experimental

Results and discussion

Concluding remarks

Acknowledgment

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Thermochim. Acta

Fluid Phase Equilibr.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Solution Chem.

J. Solution Chem.

Dokl. Phys. Chem.

Can. J. Chem.

Bull. Chem. Soc. Jpn.

J. Solution Chem.

J. Solution Chem.

Thermodynamic Properties of Aqueous Solutions of Organic Substances

J. Struct. Chem.

J. Struct. Chem.

Pure Appl. Chem.

Can. J. Chem.

J. Solution Chem.

J. Phys. Chem. B