Thermodynamics of amide+ketone mixtures. 2. Volumetric, speed of sound and refractive index data for N,N-dimethylacetamide+2-alkanone systems at several temperatures. Application of Flory's model to tertiary amide+n-alkanone systems

Ana Cobos, Juan Antonio González, Fernando Hevia, Isaías García de la Fuente, Cristina Alonso Tristán
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Abstract

Data on density, $\rho$, speed of sound, $c$, and refractive index, $n_{\text{D}}$, have been reported at (293-303.15) K for the N,N-dimethylacetamide (DMA) + CH$_3$CO(CH$_2$)$_{u-1}$CH$_3$ ($u$ = 1, 2, 3) systems, and at 298.15 K for the mixture with $u$ = 5. These data have been used to compute excess molar volumes, $V_{\text{m}}^{\text{E}}$, excess adiabatic compressibilities, $\kappa_S^{\text{E}}$, and excess speeds of sound $c^{\text{E}}$. Negative $V_{\text{m}}^{\text{E}}$ values indicate the existence of structural effects and interactions between unlike molecules. From excess molar enthalpies, $H_{\text{m}}^{\text{E}}$, available in the literature for N,N-dimethylformamide (DMF), or N-methylpyrrolidone (NMP) + n-alkanone systems, it is shown: (i) amide-ketone interactions are stronger in DMF systems than in those with NMP; (ii) they become weaker when $u$ increases in mixtures with a given amide. Structural effects largely contribute to $H_{\text{m}}^{\text{E}}$ and are more relevant in mixtures containing NMP. The application of the Flory's model reveals that the random mixing hypothesis is valid to a large extent for DMF solutions, while NMP systems are characterized by rather strong orientational effects. From values of molar refraction and of the product $P_{\text{int}} V_{\text{m}}$ (where $P_{\text{int}}$ is the internal pressure and $V_{\text{m}}$ the molar volume), it is concluded that dispersive interactions increase with $u$, or when DMF is replaced by DMA in mixtures with a fixed ketone.
酰胺+酮混合物的热力学。2.若干温度下 N,N-二甲基乙酰胺+2-烷酮体系的体积、声速和折射率数据。弗洛里模型在叔胺+2-烷酮体系中的应用
报告了 N,N-二甲基乙酰胺 (DMA) + CH$_3$CO(CH$_2$)$_{u-1}$CH$_3$ ($u$ = 1, 2, 3)体系在 (293-303.15) K 下的密度、$\rho$、声速 $c$ 和折射率 $n_{\text{D}}$,以及 $u$ = 5 的混合物在 298.15 K 下的密度、$\rho$、声速 $c$ 和折射率 $n_{\text{D}}$。这些数据被用来计算过量摩尔体积 $V_{\text{m}}^{text{E}}$、过量绝热压缩率 $\kappa_S^\{text{E}}$ 和过量声速 $c^{\text{E}}$。负$V_{text{m}}^{text{E}}$值表明存在结构效应和不同分子之间的相互作用。文献中关于 N,N-二甲基甲酰胺(DMF)或 N-甲基吡咯烷酮(NMP)+ 正烷酮体系的过量摩尔焓 $H_{text{m}}^{text{E}}$显示:(i) DMF 体系中的酰胺酮相互作用强于 NMP 体系;(ii) 在含有特定酰胺的混合物中,当 $u$ 增加时,酰胺酮相互作用变弱。结构效应在很大程度上影响了$H_{text{m}}^{text{E}}$,并且在含有 NMP 的混合物中更为相关。弗洛里模型的应用表明,随机混合假说在很大程度上适用于 DMF 溶液,而 NMP 体系则具有相当强的定向效应。从摩尔折射率和乘积 $P_{\text{int}} 的值来看V_{\text{m}}$(其中$P_{\text{int}}$为内压,$V_{\text{m}}$为摩尔体积)得出的结论是,分散相互作用随$u$的增加而增加,或者当 DMF 被带有固定酮的 DMA 混合物所取代时。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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