Experimental study of nucleation in binary mixtures: The methanol–water and <i>n</i>-propanol–water systems

Flageollet, C.; Cao, Mingmin; Mirabel, Philippe

doi:10.1063/1.438941

Cited by 53 publications

(11 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(7) into Eq. (11 ) is the supersaturation and Psat is the saturation pressure at T. Having estimated t:..f.L in Eq. (4), we suggest a generalized phenomenological form for the difference Mi of Helmholtz free energies F j and if 00 as (it is well known that M; cannot totally be determined from thermodynamics or statistical mechanics)…”

Section: ( Iflu)mentioning

confidence: 99%

A semiphenomenological droplet model of homogeneous nucleation from the vapor phase

Delale

Meier²

1993

The Journal of Chemical Physics

View full text Add to dashboard Cite

A refined droplet approach to the problem of homogeneous nucleation from the vapor phase A semiphenomenological droplet model, which corrects for the macroscopic surface tension and monomer-monomer interactions from real gas behavior (second virial coefficient) and for the correlation between the mean surface area of a cluster and the number of molecules constituting the cluster over all ranges of temperature below the critical point, is proposed by modifying Fisher's droplet theory of condensation. A steady-state nucleation rate equation is derived and compared with expansion and diffusion cloud chamber data for a variety of substances. An overall good agreement is achieved for the range of temperatures investigated in contrast to comparison with the classical nucleation rate equation. 9850 J. Chern. Phys. 98 (12), 15 June 1993 ".~~. implicit that the interactions between clusters of size t;.2 and the monomers are neglected; therefore, real gas effects

show abstract

Section: ( Iflu)mentioning

confidence: 99%

A semiphenomenological droplet model of homogeneous nucleation from the vapor phase

Delale

Meier²

1993

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Historically, the use of the classical homogeneous theory has successfully predicted critical activities of a number of pure systems and binary mixtures . However, very poor agreement with experiment has been found for nonideal mixtures. ,,, It was first Renninger et al and then Wilemski , who, in the early 1980s, showed that the classical theory was inconsistent when the surface tension of the system changes significantly with composition. Wilemski proposed a “revised classical theory” using the Gibbs adsorption equation, which takes into account surface-enrichment effects.…”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Study of Two-Component Systems: The Shape and Surface Structure of Water/Ethanol Droplets

Tarek

Klein

1997

J. Phys. Chem. A

View full text Add to dashboard Cite

Molecular dynamics simulations have been performed at T = 260 K on three different sized ethanol/water droplets with a mole fraction of ethanol x = 12%. The calculations were initiated from near spherical configurations taken from simulations of the bulk mixture with the same composition. The results are discussed in comparison to the microphysical models used in nucleation theories. For the droplet having a comparable size to the so-called “critical” cluster, all the ethanol molecules repartition to the surface. The shapes and surface structure of the droplets have been characterized and exhibit increasing fluctuations with decreasing size. These two observations may help explain the present discrepancy between the predicted and calculated rates of nucleation for ethanol/water droplets.

show abstract

“…7 The experimental data on the composition dependence of the surface tension were fitted by the expression…”

Section: Numerical Evaluations For a Water-methanol Systemmentioning

confidence: 99%

“…1-4 Nevertheless, the development of an adequate macroscopic nucleation theory remains of great importance because it provides a simple and virtually universal formalism applicable to first-order phase transitions in most complex systems. 5,6 It has been known for quite a while that experimental data on the binary nucleation rate can differ by many orders of magnitude [7][8][9][10][11] from the predictions of binary classical nucleation theory ͑BCNT͒, based on the capillarity approximation. 6 As one possible explanation of these discrepancies, it was suggested 7 that such large discrepancies between BCNT and experiment are due to adsorption effects.…”

Section: Introductionmentioning

confidence: 99%

On the closure conjectures for the Gibbsian approximation model of a binary droplet

Djikaev

Napari

Laaksonen

2004

The Journal of Chemical Physics

View full text Add to dashboard Cite

Within the framework of Gibbsian thermodynamics, a binary droplet is regarded to consist of a uniform interior and dividing surface. The properties of the droplet interior are those of the bulk liquid solution, but the dividing surface is a fictitious phase whose chemical potentials cannot be rigorously determined. The state of the nucleus interior and free energy of nucleus formation can be found without knowing the surface chemical potentials, but the latter are still needed to determine the state of the whole nucleus (including the dividing surface) and develop the kinetics of nucleation. Thus it is necessary to recur to additional conjectures in order to build a complete, thermodynamic, and kinetic theory of nucleation within the framework of the Gibbsian approximation. Here we consider and analyze the problem of closing the Gibbsian approximation droplet model. We identify micro- and Gamma-closure conjectures concerning the surface chemical potentials and excess surface coverages, respectively, for the droplet surface of tension. With these two closure conjectures, the Gibbsian approximation model of a binary droplet becomes complete so that one can determine both the surface and internal characteristics of the whole nucleus and develop the kinetic theory, based on this model. Theoretical results are illustrated by numerical evaluations for binary nucleation in a water-methanol vapor mixture at T=298.15 K. Numerical results show a striking increase in the droplet surface tension with decreasing droplet size at constant overall droplet composition. A comparison of the Gibbsian approximation with density functional calculations for a model surfactant system indicate that the excess surface coverages from the Gibbsian approximation are accurate enough for large droplets and droplets that are not too concentrated with respect to the solute.

show abstract

Experimental study of nucleation in binary mixtures: The methanol–water and n-propanol–water systems

Cited by 53 publications

References 22 publications

A semiphenomenological droplet model of homogeneous nucleation from the vapor phase

A semiphenomenological droplet model of homogeneous nucleation from the vapor phase

Molecular Dynamics Study of Two-Component Systems: The Shape and Surface Structure of Water/Ethanol Droplets

On the closure conjectures for the Gibbsian approximation model of a binary droplet

Contact Info

Product

Resources

About