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Apparent Molar Heat Capacities of n-Alcohols (C2 to C4) and Symmetric Tetraalkylammonium Bromides (C2 to C5) in Water–N,N-Dimethylformamide Mixtures: Methylene Group Contribution and Hydrophobic Hydration

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Abstract

The apparent molar heat capacities, ϕ C p , of ethanol, n-propanol, n-butanol, and tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium and tetra-n-pentylammonium bromides have been measured measured using a Picker flow calorimeter (Sodev, Canada, Model CP-Cpr) at 298.15 K in water–N,N-dimethylformamide (DMF) mixtures. The contribution of the CH2 moiety, ϕ C p (CH2), was estimated from these data as the change in ϕ C p per additional CH2 unit. The values of ϕ C p (CH2) in water (ca. 100 J·K−1·mol−1) are two to three times those in neat organic solvents (ca. 30–40 J·K−1·mol−1), consistent with a substantial contribution from hydrophobic solvation in water. In water-rich aqueous DMF solutions, ϕ C p (CH2) decreases monotonically with increasing DMF concentration, the decrease being more rapid for the n-alcohols. This trend differs significantly from that reported in the literature for highly aqueous mixtures of t-butanol, where ϕ C p (CH2) passes through a maximum.

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Authors and Affiliations

  1. UCD School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

    W. Earle Waghorne

  2. Laboratorio de Termodinámica de Soluciones, Departamento de Química, Facultad de Ciencias, Universidad de los Andes, Bogotá, D.C, Colombia

    Diana C. Riveros & Edgar F. Vargas

  3. Chemistry Department, Murdoch University, Murdoch, WA, 6150, Australia

    Glenn Hefter

Authors
  1. W. Earle Waghorne
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  2. Diana C. Riveros
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  3. Edgar F. Vargas
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  4. Glenn Hefter
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Correspondence to W. Earle Waghorne.

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Waghorne, W.E., Riveros, D.C., Vargas, E.F. et al. Apparent Molar Heat Capacities of n-Alcohols (C2 to C4) and Symmetric Tetraalkylammonium Bromides (C2 to C5) in Water–N,N-Dimethylformamide Mixtures: Methylene Group Contribution and Hydrophobic Hydration. J Solution Chem 45, 1303–1312 (2016). https://doi.org/10.1007/s10953-016-0498-2

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