Evaluation of a locus of azeotropes by molecular simulation

Pandit, Sandeep P.; Kofke, David A.

doi:10.1002/aic.690451021

Cited by 11 publications

(13 citation statements)

References 21 publications

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“…Some 17 years ago the late A. Y. Meyer published a review dealing with the sizes of molecules, 1 namely, with their three-dimensional sizes-their volume occupying properties-and also with their one-dimensional extents-their spherical diameters. The sizes of molecules are applicable in many fields of study, such as the Gibbs energy of solvation, 2 adsorption phenomena, 3 absorption in porous media, 4 permeation through polymer membranes, 5 fractal dimensions, 6 dielectric behavior of solvents, 7 evaluation of equations of state, 8 molecular recognition, 9 diffusion rates, 10,11 azeotropic properties of mixtures 12 and guest molecule encapsulation, 13 among many others. 1 They are measures of the maximal proximity of the molecules in either a gaseous or a condensed phase to each other and to solute particles in the latter.…”

Section: Introductionmentioning

confidence: 99%

The sizes of molecules—revisited

Marcus

2003

J of Physical Organic Chem

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epoc ABSTRACT: The size of molecules, be it their volume, surface area or linear extent, is an important quantity in many fields of chemistry. Molecules are often tacitly or explicitly treated as if they were spheres, so that a diameter can be assigned to them. However, the molecules of many kinds of substances are rather cylindrical, being rod-or diskshaped, so that two linear dimensions are needed for their description. The collision diameters obtainable from experimental data on gases and vapors or diameters obtained from the molar volume or the application of an expression for the interaction potential in liquids, e.g. the Lennard-Jones potential, are explored as ways to yield information on molecular sizes. The ratio of the van der Waals volume and surface area is related to a simple expression derived solely from the composition of the molecules for various types of molecular shapes. These approaches were applied to a database of 350 mainly liquid (but also some gaseous and solid) organic (and a few inorganic) substances.

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Section: Introductionmentioning

confidence: 99%

The sizes of molecules—revisited

Marcus

2003

J of Physical Organic Chem

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“…Accuracy is determined by the realism of the inter-atomic interactions (the functional form and parameters of the forcefield) [22], and by the strategies for creating and manipulating the model to provide property predictions (the molecular simulations methods used). Typical molecular simulations approaches that have been used for VLE prediction of mixtures include configurational-bias Monte Carlo simulations (Gibbs ensemble and the combination of GrandCanonical Monte Carlo and histogram reweighting) [23][24][25][26][27], the Gibbs-Duhem integration method [28][29][30], the NPT dynamics plus test particle method (Widom's insertion method) [31,32], the bubble point pseudo-ensemble method [33], and the Grand Equilibrium method [34].…”

Section: The State-condition Transferability Problemmentioning

confidence: 99%

The third industrial fluid properties simulation challenge

Case¹,

Brennan²,

Chaka³

et al. 2007

Fluid Phase Equilibria

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The third industrial fluid properties simulation challenge was held from March to September 2006. As in the previous two events contestants were challenged to predict specific, industrially relevant, properties of fluid systems. Their efforts were judged based on the agreement of the predicted values with previously unpublished experimental data (provided by researchers at ExxonMobil and DuPont). The focus of this contest was on the transferability of modeling methods-the ability to predict properties for materials that are chemically different, or at different state points, to those used in model parameterization and validation. Nine groups attempted to compute bubble point pressures for mixtures of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and ethanol at 343 K, given data for mixtures at 283 K, and given the pure component vapor pressures. They used a range of different techniques including statistical mechanical and molecular simulations-based approaches. Four of the groups were recognized for providing predictions that were significantly more accurate than would be obtained by extrapolation using the NRTL model (the standard engineering approach). Three groups undertook the more challenging "molecular transferability" problem, attempting to predict shear viscosities at two different state points for a range of diols and triols for which little experimental data was available.

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“…The method proposed in this work is detailed in the appendix. Five Lennard-Jones fluid mixtures taken from earlier work of both Panagiotopoulos et al (1988) and Pandit and Kofke (1999) was tested. The corresponding parameters are given in Table I, along with their a priori azeotropic features that we intend to check.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Direct computation of azeotropes has also been done successfully using the Gibbs Duhem integration (GDI) method (Kofke, 1993). This method uses the Clapeyron equation to provide the coexistence information but does not require particle exchange moves to ensure chemical potential equilibrium (Pandit and Kofke, 1999). .…”

Section: Introductionmentioning

confidence: 99%

Azeotrope Prediction by Monte Carlo Molecular Simulation

Hadj-Kali

Gerbaud

Joulia

2012

Chemical Engineering Communications

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This article presents a methodology for checking the existence of the azeotrope and computing its composition, density, and pressure at a given temperature by integrating chemical engineering insights with molecular simulation principles. Liquid-vapor equilibrium points are computed by molecular simulations using the Gibbs ensemble Monte Carlo (GEMC) method at constant volume. The appearance of the azeotropic point is marked by a shift of the equilibrium constant from one side of the unity to the other. After each GEMC simulation, an identity change move is derived in the grand canonical ensemble to progress towards the azeotrope along the equilibrium curve. The effectiveness of the proposed methodology is successfully tested for several binary Lennard-Jones mixtures reported in the literature.

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Evaluation of a locus of azeotropes by molecular simulation

Cited by 11 publications

References 21 publications

The sizes of molecules—revisited

The sizes of molecules—revisited

The third industrial fluid properties simulation challenge

Azeotrope Prediction by Monte Carlo Molecular Simulation

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