We present a coarse-grained model for n-alkanes in a supercritical solution, which is exemplified by a mixture of hexadecane and For pure hexadecane, the Monte Carlo simulations of the coarse-grained model reproduce the experimental phase diagram and the interfacial tension with good accuracy. For the mixture, the phase behavior sensitively depends on the compatibility of the polymer with the solvent. We present a global phase diagram with critical lines, which is in semiquantitative agreement with experiments. In this context we developed two computational schemes: The first adopts Wang-Landau sampling to the off-lattice grand canonical ensemble, the second combines umbrella sampling with an extrapolation scheme to determine the weight function. Additionally, we use Wertheim’s theory (TPT1) to obtain the equation of state for our coarse-grained model of supercritical mixtures and discuss the behavior for longer alkanes.
REFERENCES
1.
P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, 1953).
2.
H. Tompa, Polymer Solutions (Butterworths, London, 1956).
3.
P. G. deGennes, Scaling Concepts in Polymer Physics (Cornell University Press, Ithaca, 1979).
4.
Materials Science and Technology, edited by E. J. Kramer, Structure and Properties of Polymers, Vol. 12 (VCH Verlag, Weinheim, 1992).
5.
6.
K. Binder, M. Müller, P. Virnau, and L. G. MacDowell, Adv. Polym. Sci. (in press).
7.
Supercritical Fluids, edited by E. Kiran and J. M. H. Levelt-Sengers (Kluwer, Dordrecht, 1994).
8.
J. J.
Potoff
, J. R.
Errington
, and A. Z.
Panagiotopoulos
, Mol. Phys.
97
, 1073
(1999
).9.
10.
11.
12.
M. P. Allen and D. J. Tildesley, Computer Simulations of Liquids (Clarendon, Oxford, 1987).
13.
P. J.
Hoogerbrugge
and J. M. V. A.
Koelman
, Europhys. Lett.
19
, 155
(1992
).14.
J. M. V. A.
Koelman
and P. J.
Hoogerbrugge
, Europhys. Lett.
21
, 363
(1993
).15.
P.
Virnau
, M.
Müller
, L. G.
MacDowell
, and K.
Binder
, Comput. Phys. Commun.
147
, 378
(2002
).16.
P.
Virnau
, M.
Müller
, L. G.
MacDowell
, and K.
Binder
, New J. Phys.
6
, 7
(2003
).17.
18.
C.
Bennemann
, W.
Paul
, K.
Binder
, and B.
Dünweg
, Phys. Rev. E
57
, 843
(1998
).19.
S. O.
Nielsen
, C. F.
Lopez
, G.
Srinivas
, and M. L.
Klein
, J. Chem. Phys.
119
, 7043
(2003
).20.
21.
22.
P. Virnau and M. Müller (unpublished).
23.
R. B. Bird, Dynamics of Polymeric Liquids (Wiley, New York, 1977), Vols. 1 and 2.
24.
CRC Handbook of Chemistry and Physics, edited by R. C. Weast, 63rd ed. (CRC, Boca Raton, FL, 1985).
25.
26.
27.
M. J.
Anselme
, M.
Gude
, and A. S.
Teja
, Fluid Phase Equilib.
57
, 317
(1990
).28.
29.
30.
31.
G. C. Maitland, M. Rigby, E. B. Smith, and W. A. Wakeham, Intermolecular Forces (Clarendon, Oxford, 1987).
32.
N.
Metropolis
, A. W.
Rosenbluth
, M. N.
Rosenbluth
, A. H.
Teller
, and E.
Teller
, J. Chem. Phys.
21
, 1087
(1953
).33.
D. P. Landau and K. Binder, A Guide to Monte Carlo Simulations in Statistical Physics (Cambridge University Press, Cambridge, 2000).
34.
D. Frenkel and B. Smit, Understanding Molecular Simulation (Academic, London, 2002).
35.
M.
Müller
, L. G.
MacDowell
, P.
Virnau
, and K.
Binder
, J. Chem. Phys.
117
, 5480
(2002
).36.
L. G.
MacDowell
, P.
Virnau
, M.
Müller
, and K.
Binder
, J. Chem. Phys.
117
, 6360
(2002
).37.
J. P. Hansen and I. R. McDonald, Theory of Simple Liquids (Academic, New York, 1986).
38.
39.
J. J.
de Pablo
, M.
Laso
, and U. W.
Suter
, J. Chem. Phys.
96
, 6157
(1993
).40.
J. I.
Siepmann
, S.
Karaborni
, and B.
Smit
, Nature (London)
365
, 330
(1993
).41.
J. I.
Siepmann
, S.
Karaborni
, and B.
Smit
, J. Am. Chem. Soc.
115
, 6454
(1993
).42.
43.
B.
Smit
, S.
Karaborni
, and J. I.
Siepmann
, J. Chem. Phys.
102
, 2126
(1995
).44.
45.
46.
H.-P.
Hsu
, V.
Mehra
, W.
Nadler
, and P.
Grassberger
, J. Chem. Phys.
118
, 444
(2003
).47.
S.
Consta
, N. B.
Wilding
, D.
Frenkel
, and Z.
Alexandrowicz
, J. Chem. Phys.
110
, 3220
(1999
).48.
S.
Consta
, T. J. H.
Vlugt
, J. W.
Hoeth
, B.
Smit
, and D.
Frenkel
, Mol. Phys.
97
, 1243
(1999
).49.
50.
51.
52.
53.
54.
55.
A. M.
Ferrenberg
and R. H.
Swendsen
, Phys. Rev. Lett.
61
, 2635
(1988
).56.
57.
58.
59.
Q.
Yan
and J. J.
de Pablo
, Phys. Rev. Lett.
90
, 035701
(2003
).60.
U. H. E.
Hansmann
and L. T.
Wille
, Phys. Rev. Lett.
88
, 068105
(2002
).61.
62.
63.
R. L. C. Vink and J. Horbach, J. Chem. Phys. (in press).
64.
L. G.
MacDowell
, P.
Virnau
, M.
Müller
, and K.
Binder
, J. Chem. Phys.
120
, 5293
(2004
).65.
66.
M.
Biskup
, L.
Chayes
, and R.
Kotecky
, Europhys. Lett.
60
, 21
(2002
).67.
68.
69.
B.
Berg
, U.
Hansmann
, and T.
Neuhaus
, Z. Phys. B: Condens. Matter
90
, 229
(1993
).70.
P. Virnau, L. G. MacDowell, M. Müller, and K. Binder, High Performance Computing in Science and Engineering ’03 (Berlin, Springer, 2003), p. 125.
71.
72.
73.
74.
75.
76.
77.
78.
B. D. Smith and R. Srivastava, Thermodynamic Data for Pure Compounds: Hydrocarbons and Ketones (Elsevier, Amsterdam, 1986).
79.
R. L.
Scott
and P. H.
van Konynenburg
, Discuss. Faraday Soc.
49
, 87
(1970
).80.
P. H.
van Konynenburg
and R. L.
Scott
, Philos. Trans. R. Soc. London, Ser. A
298
, 495
(1980
).81.
J. A.
Schouten
, A.
Deerenberg
, and N. J.
Trappeniers
, Physica A
81
, 151
(1975
).82.
83.
84.
85.
86.
87.
G.
Schneider
, Z.
Alwani
, W.
Heim
, E.
Horvath
, and E. U.
Franck
, Chemie-Ing.-Techn.
39
, 649
(1967
).88.
J. D.
Hottovy
, K. D.
Luks
, and J. P.
Kohn
, J. Chem. Eng. Data
26
, 256
(1981
).89.
90.
91.
R.
Enick
, G. D.
Holder
, and B. I.
Morsi
, Fluid Phase Equilib.
22
, 209
(1985
).92.
93.
J. Garcı́a, L. Lugo, and J. Fernández, J. Phys. Chem. B (to be published).
94.
J. S. Rowlinson and F. L. Swinton, Liquids and Liquid Mixtures, 3rd ed. (Butterworth, London, 1982).
95.
T.
Charoensombut-Amon
, R. J.
Martin
, and R.
Kobayashi
, Fluid Phase Equilib.
31
, 89
(1986
).96.
97.
W. G.
Chapman
, G.
Jackson
, and K. E.
Gubbins
, Mol. Phys.
65
, 1057
(1988
).98.
99.
B.
Rathke
, Fortschritts-Berichte VDI 770 (2003).100.
101.
G. T.
Dee
and B. B.
Sauer
, J. Colloid Interface Sci.
152
, 85
(1992
).102.
This content is only available via PDF.
© 2004 American Institute of Physics.
2004
American Institute of Physics
You do not currently have access to this content.
