Thermodynamics of acetone—chloroform mixtures

Apelblat, Alexander; Tamir, Abraham; Wagner, Moshe

doi:10.1016/0378-3812(80)80018-5

Cited by 55 publications

(36 citation statements)

References 35 publications

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“…[1][2][3] The acetone-chloroform azeotrope is a popular text book example of a negative or maximumboiling azeotrope displaying negative deviations from Raoult's law, as shown in Figure 1(a), as well as an exothermic enthalpy of mixing. 7,8,[10][11][12][13][14][15][16][17][18] The non-ideality of acetone-chloroform mixtures is often attributed to the formation of C-H···O hydrogen bonds between chloroform and acetone. In fact, this system was one of the first for which a hydrogen bond with a C-H donor was proposed.…”

Section: Figurementioning

confidence: 99%

“…Pressure-composition phase diagrams of (a) acetone-chloroform 7,8 and (b) benzene-methanol 9 at 25°C. The azeotropic compositions are indicated by dotted vertical lines at xA=0.405 and xM=0.550, respectively.…”

Section: Figurementioning

confidence: 99%

“…2,23 Despite the general importance of azeotropes relatively little is known about their microstructures. Acetone-chloroform mixtures have been studied, although not always at the azeotropic composition, by analysis of thermodynamic excess functions, 7,8,[10][11][12][13][14][15][16][17][18] NMR, [24][25][26][27] Raman, 28,29 FT-IR, 27,28,30 NIR, 31 terahertz time-domain 32 and inelastic neutron spectroscopy 29 as well as Monte Carlo simulations. 22 There is general consensus that hydrogen bonding interactions are likely to be present.…”

Section: Figurementioning

confidence: 99%

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Microstructures of negative and positive azeotropes

Shephard

Callear

Imberti

et al. 2016

Phys. Chem. Chem. Phys.

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Azeotropes famously impose fundamental restrictions on distillation processes, yet their special thermodynamic properties make them highly desirable for a diverse range of industrial and technological applications. Using neutron diffraction, we investigate the structures of two prototypical azeotropes, the negative acetone-chloroform and the positive benzenemethanol azeotrope. C-H···O hydrogen bonding is the dominating interaction in the negative azeotrope but C-Cl···O halogen bonding contributes as well. Hydrogen-bonded chains of methanol molecules, which are on average longer than in pure methanol, are the defining structural feature of the positive azeotrope illustrating the fundamentally different local mixing in the two kinds of azeotropes. The emerging trend for both azeotropes is that the more volatile components experience the more pronounced structural changes in their local environments as the azeotropes form. The mixing of the acetonechloroform azeotrope is essentially random above 20 Å where the running Kirkwood-Buff integrals of our structural model converge closely to the ones expected from thermodynamic data. The benzene-methanol azeotrope on the other hand displays extended methanol-rich regions and consequently, the running Kirkwood-Buff integrals oscillate up to at least 60 Å. Our study provides first insights into the microstructures of azeotropes and a direct link with their thermodynamic properties. Ultimately, this will provide a route for creating tailored molecular environments in azeotropes to improve and fine-tune their performances.

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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Microstructures of negative and positive azeotropes

Shephard

Callear

Imberti

et al. 2016

Phys. Chem. Chem. Phys.

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“…There is no doubt as to formation of equimolar complex AB [1]. The formation of AB complex explains qualitatively the negative values of the excess thermodynamic functions [2]. But there are evidences of existence of AB 2 complex [3][4][5][6].…”

Section: Model-based Analysismentioning

confidence: 99%

“…So it has been the subject of many theoretical and experimental researches [1][2][3][4][5][6]. The main problem is the structure and composition of associated species of these mixtures.…”

Section: Introductionmentioning

confidence: 99%

Study of Complexation in Acetone-Chloroform Mixtures by Infrared Spectroscopy

Ilchenko

Kutsyk

Obukhovsky

2014

Journal of Atomic and Molecular Physics

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FTIR spectra of acetone-chloroform system with various component ratios were investigated within the spectral range 3950-4550 cm −1 . Methods of multivariate curve resolution were applied to decompose the FTIR spectra into specific components of different composition. A method of decomposition based on structural model of solution which contains acetone, chloroform, and complex acetone/chloroform (1 : 1) was proposed. Results of both approaches are in good agreement within the range of measuring error.

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Local Fluctuations in Solution: Theory and Applications

Ploetz¹,

Smith²

2013

Advances in Chemical Physics

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Thermodynamics of acetone—chloroform mixtures

Cited by 55 publications

References 35 publications

Microstructures of negative and positive azeotropes

Microstructures of negative and positive azeotropes

Study of Complexation in Acetone-Chloroform Mixtures by Infrared Spectroscopy

Local Fluctuations in Solution: Theory and Applications

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