A re-appraisal of the concept of ideal mixtures through a computer simulation study of the methanol-ethanol mixtures

@article{Poar2016ARO,
  title={A re-appraisal of the concept of ideal mixtures through a computer simulation study of the methanol-ethanol mixtures},
  author={Martina Po{\vz}ar and Bernarda Lovrin{\vc}evi{\'c} and Larisa Zoranic and Marijana Mijakovi{\'c} and F. Sokolic and Aur{\'e}lien Perera},
  journal={Journal of Chemical Physics},
  year={2016},
  volume={145},
  pages={064509}
}
Methanol-ethanol mixtures under ambient conditions of temperature and pressure are studied by computer simulations, with the aim to sort out how the ideality of this type of mixtures differs from that of a textbook example of an ideal mixture. This study reveals two types of ideality, one which is related to simple disorder, such as in benzene-cyclohexane mixtures, and another found in complex disorder mixtures of associated liquids. It underlines the importance of distinguishing between… 
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References

SHOWING 1-10 OF 58 REFERENCES
Simple and complex disorder in binary mixtures with benzene as a common solvent.
TLDR
Substituting benzene for water in computer simulations of binary mixtures allows one to study the various forms of disorder, without the complications often encountered in aqueous mixtures, and confirms the existence of a pre-peak in the structure factor associated with the micro-heterogeneity.
Revisiting aqueous-acetone mixtures through the concept of molecular emulsions.
TLDR
It is demonstrated, through a proper handling of the tail of the correlation functions, that these high values of the Kirkwood-Buff integrals represent in fact a transient regime within the segregated spatial domains, and that they asymptotically settle down to values in much better agreement with the experimental ones.
A comparison of force fields for ethanol–water mixtures
Aqueous ethanol mixtures are studied through molecular dynamics simulations with the focus on exploring how various force field models reproduce the association and its influence on selected…
On the nature of the molecular ordering of water in aqueous DMSO mixtures.
TLDR
The study shows that these mixtures become closer to the emulsion type seen in aqueous alcohol mixtures, with more globular clustering of the water molecules, long range domain oscillations in the water-water correlations and increased water- water Kirkwood-Buff integrals.
Fluctuations and micro-heterogeneity in aqueous mixtures.
TLDR
This study provides a new insight for the large values of the experimental Kirkwood-Buff integrals for many aqueous mixtures, in a Lifshitz-type regime, where concentration fluctuations compete with water domain formation.
Modeling nonionic aqueous solutions: the acetone-water mixture.
TLDR
It is argued herein that deficiencies of existing classical water and acetone models provide an insightful picture of the microscopic structure of the solution, particularly into the relation between the hydrogen-bond network and the concentration fluctuations, as well as the role played by the solute in their spatial organization.
Effect of a third component on the interactions in a binary mixture determined from the fluctuation theory of solutions
Inversion of the Kirkwood–Buff theory of solutions: Application to the water–ethanol system
A general procedure is outlined whereby experimental data such as partial molar volumes, isothermal compressibilities, and partial vapor pressures may be processed to obtain information on the extent…
The Kirkwood-Buff theory of solutions and the local composition of liquid mixtures.
TLDR
The application of the new procedure to the ternary mixture water/protein/cosolvent at infinite dilution of the protein led to almost the same results as the methods involving a reference state.
Aqueous tert-butanol mixtures: a model for molecular-emulsions.
TLDR
The issue of whether or not the Kirkwood-Buff integrals represent solely concentration fluctuations is settled by showing the contribution of the micro-heterogeneity to these integrals through the presence of an associated pre-peak in the structure factors.
...
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