Thermodynamic properties of aqueous organic solutes in relation to their structure. Part III. Apparent molal volumes and heat capacities of low molecular weight alcohols and polyols at 25 °C

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Abstract

The density and specific heat of dilute aqueous solutions of various alcohols and polyols have been measured at 25 °C. Such measurements have been carried out for the following solutes: methanol, ethanol, n-propanol, n-butanol, isobutanol, s-butanol, tert-butyl alcohol, n-pentanol. 3-pentanol, neo-pentanol, ethyleneglycol, 1,4-butanediol, 1,6-hexanediol, dimethyl-2,2-propanediol, 1,1,1-tris(hydroxymethyl)ethane, and pentaerythritol.The limiting apparent molal volume [Formula: see text] and heat capacities [Formula: see text] derived from these data exhibit some variations among the properties of isomers (e.g. branched vs. normal alkyl groups), but these variations cannot be conclusively attributed to specific effects in the hydration of the alkyl groups. On the other hand, the data allows one to derive group contributions to [Formula: see text] and [Formula: see text] namely [Formula: see text] for the methylene group, [Formula: see text] for the OH functional group and [Formula: see text] for the C—H of a terminal methyl group.The concentration dependence of [Formula: see text] brings out some interesting new features. With most of the alcohols, [Formula: see text] decreases with concentration, in a way related to the degree of hydrophobicity of the alcohol. Solute–solute interactions contribute to reduce [Formula: see text] of the hydrophilic solutes, but the opposite effect is observed with the most hydrophobic alcohols.

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