Thermodynamics of 2-undecanone + n-alkane mixtures

Abstract

Densities and excess molar volumes ($V_{\text{m}}^{\text{E}}$) at (293.15-303.15) K and excess molar enthalpies ($H_{\text{m}}^{\text{E}}$) at 298.15 K are reported for 2-undecanone + heptane, or + octane, or + decane, or + dodecane, or + tetradecane mixtures at 95 kPa. Densities and $H_{\text{m}}^{\text{E}}$ were measured using, respectively, a densitometer Anton Paar DMA 602 and a Tian-Calvet micro-calorimeter. $H_{\text{m}}^{\text{E}}$ results are positive, indicating that interactions between like molecules are dominant. Both $H_{\text{m}}^{\text{E}}$ and $V_{\text{m}}^{\text{E}}$ increase in line with $n$ (number of C atoms of the alkane), which reveals that the increase of $V_{\text{m}}^{\text{E}}$ can be ascribed to an increased interactional contribution. Nevertheless, systems with $n$ = 7,8 show negative $V_{\text{m}}^{\text{E}}$ values, which reveals that $V_{\text{m}}^{\text{E}}$ is determined mainly by structural effects. Isochoric excess molar internal energies ($U_{V\text{m}}^{\text{E}}$) at 298.15 K have been obtained from the present $H_{\text{m}}^{\text{E}}$ and $V_{\text{m}}^{\text{E}}$ data. At equimolar composition, $U_{V\text{m}}^{\text{E}}$is nearly constant for $n$ = 7-10, and then slightly increases. This has been explained in terms of a possible folding of 2-undecanone. From the comparison of $U_{V\text{m}}^{\text{E}}$ results for similar systems involving n-alkanoates, it is shown that folding is more likely in solutions with these compounds.

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