Abstract
Limiting partial molar volumes V ∞ of nine solutes [water, methanol, carbon disulfide, acetic acid, acetone, dimethyl sulfoxide, pyridine, benzene, and carbon tetrachloride] dissolved in various solvents have been measured using a pycnometer at 30.00 ± 0.05 °C. The V ∞ of water apparently decreases with increasing volume-% of void, i.e. empty space, in a solvent. From this result, we were able to experimentally demonstrate that small water molecules can easily enter into the voids existing in various solvents; however, the other larger solute molecules cannot enter easily into them. On the other hand, V ∞ of all the nine solutes increases with increasing mixing enthalpy, ΔH mix, for each solute (mole fraction after mixing x 2 = 0.05) with various solvents. Generally, the repulsive solute–solvent interaction increases as ΔH mix increases. Therefore, we were able to experimentally demonstrate that V ∞ tends to increase with increasing repulsive solute–solvent interaction. It is considered that the repulsive interaction may lengthen the average neighboring solute–solvent distance and play an important role in affecting V ∞ as well as the void effect.
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Acknowledgments
The authors wish to thank Professor Takayoshi Kimura, Kinki University, for lending us Handbook of Heats of Mixing (reference 24). Also, the authors thank many students of Shimane University for their experimental assistance.
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Inamura, I., Jinbo, Y. & Saiko, T. Effects of Volume-% of Voids in a Solvent and Repulsive Solute–Solvent Interactions, on Limiting Partial Molar Volumes (V ∞) in Solvent (1)–Solute (2) Systems. J Solution Chem 44, 1777–1797 (2015). https://doi.org/10.1007/s10953-015-0374-5
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DOI: https://doi.org/10.1007/s10953-015-0374-5