Abstract
Results from three-dimensional lattice Monte Carlo simulations of amphiphile–solvent mixtures are presented. The chemical potential is derived from the monomer distribution in different clusters rather than using a Widom particle insertion approach. The effect of tail and head characteristics on the non-ideality of these systems, aggregation number, and premicellar phenomena is considered. The aggregation number and CMC behavior of the simulated amphiphilic systems are compared with existing experimental results for non-ionic amphiphiles. Two kinds of polydispersity changing with total concentration of surfactants are observed which are related to phase transition phenomena. Shape variations in clusters are studied by calculating the eigenvalues of the gyration matrix; it is shown that large clusters are non-spherical. With the Maclaurin’s expansion of activity coefficient into volume fraction, the distribution of excess chemical potential with changing aggregation number is considered. Study of the degree of non-ideality of these amphiphiles reveals that asymmetric amphiphiles are characterized by greater non-ideality than symmetric amphiphiles. Goldstein’s parameters are calculated taking non-ideality into consideration. The difference between the phenomenological model and the simulation data is investigated.
Similar content being viewed by others
References
Degiorigo V, Corti M. ed. (1985) Physics of amphiphiles: micelles, vesicles and microemulsions. North-Holland, Amsterdam
Gharibi H, Razavizadeh BM, Hashemianzadeh M (2000) Colloids Surf A Physicochem Eng Aspects 174:375
Gharibi H, Javadian S, Hashemianzadeh M (2004) Colloids Surf A Physicochem Eng Aspects 232:77
Penfold J, Staples E, Cummins PG (1992) Physica B 180A:537
Mikhalikin AP (1994) Colloid J 56:336
Razavizadeh BM, Mousavi-Khoshdel M, Gharibi H, Behjatmanesh-Ardakani R, Javadian S, Sohrabi B (2004) J Colloid Interface Sci 276:197
Shimizu K, Iwatsuru M (1990) Chem Pharm Bull 38:1353
Szlifer I, Ben-Shaul A, Gelbart WM (1985) J Chem Phys 83:3597
Nagarajan R, Ruckenstein E (1983) J Colloid Interface Sci 91:500
von Gottberg FK, Smith KA, Hatton TA (1997) J Chem Phys 106:9850
Goldstein RE (1986) J Chem Phys 84:3367
Widom B (1984) J Phys Chem 88:6508
Gunn JR, Dawson KA (1992) J Chem Phys 96:3152
Hansen A, Schick M, Stauffer D (1991) Phys Rev A 44:3686
Karaborni S, O’Connell JP (1990) J Phys Chem 94:2624
Larson RG (1988) J Chem Phys 89:1642
Care CM (1987) J Chem Soc Faraday Trans 83:2905
Wang Y, Mattice WL, Napper DH (1993) Langmuir 9:66
Wang Y, Mattice WL, Napper DH (1992) Macromolecules 25:4073
Bernardes AT, Henriques VB, Bisch PM (1994) J Chem Phys 101:645
Girardi M, Figueiredo W (2000) J Chem Phys 112:4833
Panagiotopoulos AZ, Floriano MA, Kumar SK (2002) Langmuir 18:2940
Lisal M, Hall CK, Gubbins KE, Panagiotopoulos AZ (2002) J Chem Phys 116:1171
Rodriguez-Guadarrama LA, Talsania SK, Mohanty KK, Rajagopalan R (1999) Langmuir 15:437
Metropolis N, Rosenbluth AW, Rosenbluth MN, Teller AH, Teller E (1953) J Chem Phys 21:1087
Nelson PH (1998) PhD Thesis simulation of self-assembled polymer and surfactant systems, Massachusetts Institute of Technology
Binder K (ed) (1995) Monte Carlo and molecular dynamics simulations in polymer science. Oxford University Press, New York
De Gennes PG (1979) Scaling concepts in polymer physics. Cornell University Press, Ithaca
Siepmann JI, Frenkel D (1992) Mol Phys 75:59
Ruckenstein E, Nagarajan R (1975) J Phys Chem 79:2622
Ruckenstein E, Nagarajan R (1981) J Phys Chem 85:3010
Desplat J-C, Care CM (1996) Mol Phys 87:441
Israelachvili JN, Mitchell DJ, Ninham BW (1976) J Chem Soc Faraday Trans 2 72:1525
Zaldivar M, Larson RG (2003) Langmuir 19:10434
Tanford C (1991) The hydrophobic effect: formation of micelle and biological membrane. Krieger, Malabar
Gharibi H, Rafati AA, Feizollahi A, Razavizadeh BM, Safarpour MA (1998) Colloid Surf A Physicochem Eng Aspects 145:47
Rosen MJ (1989) Surfactants and interfacial phenomena, 2nd edn. Wiley, New York
Aniansson EAG (1978) Ber Bunsenges Phys Chem 82:981
Stauffer D, Jan N, He Y, Pandly RB, Marangoni DG, Smith-Palmer E (1994) J Chem Phys 100:6934
Wennerström H, Lindmann B (1979) Phys Rep 52:1
Arfken GB, Weber HJ (2001) Mathematical methods for physicists, 5th edn. Academic, New York
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gharibi, H., Behjatmanesh-Ardakani, R., Hashemianzadeh, S.M. et al. Study of thermodynamic parameters in amphiphilic systems by lattice Monte Carlo: effect of tails and heads. Theor Chem Acc 115, 1–17 (2006). https://doi.org/10.1007/s00214-005-0014-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00214-005-0014-z