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<p>The temperature-dependent molar volumes of 14 neat alcohols, including the homologous set of straight-chain primary alcohols, selected secondary alcohols, ethylene glycol, and selected alcohols with deuterated hydroxyl groups were measured in anticipation of uncovering systematic properties applicable to other neat liquids. For example, the addition of a single methylene group sequentially from ethanol to n-heptanol increases the molar volume by the nearly constant value of 16.385 ± 0.019 cm<sup>3</sup>·mol<sup>−1</sup> at 0&#xa0;°C. This linear behavior is exhibited at all temperatures studied. This constitutive property of molar volumes was reported previously for the partial molar volumes of aqueous alcohols, poly[vinyl alcohol], and organo-metallic complexes. Moreover, a method is proposed to partition the molar volumes into portions dependent upon intermolecular interactions, both attractive and repulsive (herein referred to as <i>V</i><sub>int</sub>, the apparent intrinsic volume), as well as a portion reflecting the tendency for molecules to separate due to <b>thermal</b> kinetic energy (herein referred to as <i>V</i><sub>exp</sub>, the expansive volume).</p>

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A Volumetric Study of Several Neat Alcohols as a Function of Temperature

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月22日

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  • Anthony F. Fucaloro,
  • Andrew Zanella,
  • Christine Hu,
  • Andrew Meehan,
  • Lily Nguyen,
  • Derek Peng,
  • Michael Scarlett,
  • Chris Wan

摘要

The temperature-dependent molar volumes of 14 neat alcohols, including the homologous set of straight-chain primary alcohols, selected secondary alcohols, ethylene glycol, and selected alcohols with deuterated hydroxyl groups were measured in anticipation of uncovering systematic properties applicable to other neat liquids. For example, the addition of a single methylene group sequentially from ethanol to n-heptanol increases the molar volume by the nearly constant value of 16.385 ± 0.019 cm3·mol−1 at 0 °C. This linear behavior is exhibited at all temperatures studied. This constitutive property of molar volumes was reported previously for the partial molar volumes of aqueous alcohols, poly[vinyl alcohol], and organo-metallic complexes. Moreover, a method is proposed to partition the molar volumes into portions dependent upon intermolecular interactions, both attractive and repulsive (herein referred to as Vint, the apparent intrinsic volume), as well as a portion reflecting the tendency for molecules to separate due to thermal kinetic energy (herein referred to as Vexp, the expansive volume).