JCP Nameplate
  • Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

You Tube Flickr Twitter UniPHY Group iResearch App Facebook

Journal of Chemical Physics / Volume 127 / Issue 16 / ARTICLES / Surfaces, Interfaces, and Materials

J. Chem. Phys. 127, 164720 (2007); doi:10.1063/1.2799515 (14 pages)

Gradient theory computation of the radius-dependent surface tension and nucleation rate for n-nonane clusters

J. Hrubý1, D. G. Labetski2, and M. E. H. van Dongen2

1Institute of Thermomechanics AS CR, v.v.i., Dolejškova 5, CZ-18200 Prague 8, Czech Republic
2Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

View MapView Map

(Received 15 June 2007; accepted 24 September 2007; published online 30 October 2007)

The Van der Waals-Cahn-Hilliard gradient theory (GT) is applied to determine the structure and the work of formation of clusters in supersaturated n-nonane vapor. The results are analyzed as functions of the difference of pressures of the liquid phase and vapor phase in chemical equilibrium, which is a measure for the supersaturation. The surface tension as a function of pressure difference shows first a weak maximum and then decreases monotonically. The computed Tolman length is in agreement with earlier results [ L. Gránásy, J. Chem. Phys. 109, 9660 (1998) ] obtained with a different equation of state. A method based on the Gibbs adsorption equation is developed to check the consistency of GT results (or other simulation techniques providing the work of formation and excess number of molecules), and to enable an efficient interpolation. A cluster model is devised based on the density profile of the planar phase interface. Using this model we analyze the dependency of the surface tension on the pressure difference. We find three major contributions: (i) the effect of asymmetry of the density profile resulting into a linear increase of the surface tension, (ii) the effect of finite thickness of the phase interface resulting into a negative quadratic term, and (iii) the effect of buildup of a low-density tail of the density profile, also contributing as a negative quadratic term. Contributions (i)–(iii) fully explain the dependency of the surface tension on the pressure difference, including the range relevant to nucleation experiments. Contributions (i) and (ii) can be predicted from the planar density profile. The work of formation of noncritical clusters is derived and the nucleation rate is computed. The computed nucleation rates are closer to the experimental nucleation rate results than the classical Becker-Döring theory, and also the dependence on supersaturation is better predicted.

© 2007 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY
    1. Gibbsian droplet model
    2. Gradient theory
  3. RESULTS OF THE GRADIENT THEORY COMPUTATIONS
  4. DEPENDENCE OF THE SURFACE TENSION OF CRITICAL CLUSTERS ON THE PRESSURE DIFFERENCE Δp
    1. A cluster model based on the density profileof the planar phase interface
    2. Effect of the low-density tail of the density profile
  5. VAPOR-LIQUID NUCLEATION OF n -NONANE
    1. Noncritical clusters and nucleation kinetics
    2. Comparison with experimental nucleation rates
  6. CONCLUSIONS

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

adsorption, chemical equilibrium, equations of state, gradient methods, molecular clusters, nucleation, organic compounds, surface tension

PACS

  • 82.33.Hk

    Reactions on clusters

  • 82.60.Nh

    Thermodynamics of nucleation

  • 82.60.Hc

    Chemical equilibria and equilibrium constants

ARTICLE DATA

Permalink
http://link.aip.org/link/doi/10.1063/1.2799515

PUBLICATION DATA

ISSN:

0021-9606 (print)  
1089-7690 (online)

Publisher:

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    R. Becker and W. Döring, Ann. Phys. 24, 719 (1935)JCPSA6000051000002000635000001.

    J. W. Cahn and J. E. Hilliard, J. Chem. Phys. 28, 258 (1958)JCPSA6000028000002000258000001.

    J. W. Cahn and J. E. Hilliard, J. Chem. Phys. 31, 688 (1959)JCPSA6000031000003000688000001.

    V. G. Baidakov, S. P. Protsenko, G. G. Chernykh, and G. S. Boltachev, Phys. Rev. E 65, 041601 (2002).

    D. W. Oxtoby and R. Evans, J. Chem. Phys. 89, 7521 (1988)JCPSA6000089000012007521000001.

    R. C. Tolman, J. Chem. Phys. 17, 333 (1949)JCPSA6000017000003000333000001.

    A. Dillmann and G. E. A. Meier, J. Chem. Phys. 94, 3872 (1991)JCPSA6000094000005003872000001.

    C. F. Delale and G. E. A. Meier, J. Chem. Phys. 98, 9850 (1993)JCPSA6000098000012009850000001.

    A. Laaksonen, I. J. Ford, and M. Kulmala, Phys. Rev. E 49, 5517 (1994).

    V. I. Kalikmanov, J. Chem. Phys. 124, 124505 (2006)JCPSA6000124000012124505000001.

    K. N. H. Looijmans, C. C. M. Luijten, and M. E. H. van Dongen, J. Chem. Phys. 103, 1714 (1995)JCPSA6000103000004001714000001.

    C. C. M. Luijten, R. G. P. van Hooy, J. W. F. Janssen, and M. E. H. van Dongen, J. Chem. Phys. 109, 3553 (1998)JCPSA6000109000009003553000001.

    G. W. Adams, J. L. Schmitt, and R. A. Zalabsky, J. Chem. Phys. 81, 5074 (1984)JCPSA6000081000011005074000001.

    P. E. Wagner and R. Strey, J. Chem. Phys. 80, 5266 (1984)JCPSA6000080000010005266000001.

    Y. Viisanen, P. E. Wagner, and R. Strey, J. Chem. Phys. 108, 4257 (1998)JCPSA6000108000010004257000001.

    J. L. Katz, J. Chem. Phys. 52, 4733 (1970)JCPSA6000052000009004733000001.

    C.-H. Hung, M. J. Krasnopoler, and J. L. Katz, J. Chem. Phys. 90, 1856 (1989)JCPSA6000090000003001856000001.

    C.-H. Hung, M. J. Krasnopoler, and J. L. Katz, J. Chem. Phys. 92, 7722 (1990)JCPSA6000092000012007722000002.

    M. M. Rudek, J. A. Fisk, V. M. Chakarov, and J. L. Katz, J. Chem. Phys. 105, 4707 (1996)JCPSA6000105000011004707000001.

    R. M. Nyquist, V. Talanquer, and D. W. Oxtoby, J. Chem. Phys. 103, 1175 (1995)JCPSA6000103000003001175000001.

    L. Gránásy, J. Chem. Phys. 104, 5188 (1996)JCPSA6000104000013005188000001.

    L. Gránásy, J. Chem. Phys. 109, 9660 (1998)JCPSA6000109000022009660000001.

    N. F. Carnahan and K. E. Starling, J. Chem. Phys. 51, 635 (1969)JCPSA6000051000002000635000001.

    J. Barrett, J. Chem. Phys. 107, 7989 (1997)JCPSA6000107000019007989000001.

    S. Natarajan, S. A. Harris, and I. J. Ford, J. Chem. Phys. 124, 044318 (2006)JCPSA6000124000004044318000001.

    A. Obeidat, J.-S. Li, and G. Wilemski, J. Chem. Phys. 121, 9510 (2004)JCPSA6000121000019009510000001.

    G. Wilemski and J.-S. Li, J. Chem. Phys. 121, 7821 (2004)JCPSA6000121000016007821000001.

    R. K. Bowles, D. Reguera, Y. Djikaev, and H. Reiss, J. Chem. Phys. 115, 1853 (2001)JCPSA6000115000004001853000001.

    W. Band, J. Chem. Phys. 7, 324 (1939)JCPSA6000007000005000324000001.

    F. H. Stillinger, Jr., J. Chem. Phys. 38, 1486 (1963)JCPSA6000038000007001486000001.

    D. W. Oxtoby and D. Kashchiev, J. Chem. Phys. 100, 7665 (1994)JCPSA6000100000010007665000001.

    S. L. Girshick and C.-P. Chiu, J. Chem. Phys. 93, 1273 (1990)JCPSA6000093000002001273000001.

    J. A. Fisk and J. L. Katz, J. Chem. Phys. 104, 8649 (1996)JCPSA6000104000021008649000001.

    E. W. Lemmon and A. R. H. Goodwin, J. Phys. Chem. Ref. Data 29, 1 (2000)JPCRBU000029000001000001000001.


For access to citing articles, you need to log in.


Figures (11)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)



Close

Google Calendar

ADVERTISEMENT

Your Recent History Recent History Help

Recently Viewed

  1. Gradient theory computation of the radius-dependent surface tension and nucleation rate for n-nonane clusters
  2. The permanent electric dipole moment of chromium monodeuteride, CrD
  3. Photonic reagent control of dynamically homologous quantum systems
  4. A conductivity study and calorimetric analysis of dried poly(sodium 4-styrene sulfonate)/poly(diallyldimethylammonium chloride) polyelectrolyte complexes
  5. Infrared spectra of SF6−⋅HCOOH⋅Arn (n = 0–2): Infrared triggered reaction and Ar-induced reactive inhibition
Go to AIP Home
Copyright © American Institute of Physics
close