- Physical Review Journals
All JournalsPhysics Magazine
Access Provided by Xinjiang University

Physical Review E

Export citation

Export citation

Choose format for download:

Download Citation
  • Access by Xinjiang University

Simulational and theoretical study of the spherical electrical double layer for a size-asymmetric electrolyte: The case of big coions

G. Iván Guerrero-García, Enrique González-Tovar, and Martín Chávez-Páez

  • Instituto de Física, Universidad Autónoma de San Luis Potosí, Álvaro Obregón 64, 78000 San Luis Potosí, S.L.P., México

PDF

Phys. Rev. E 80, 021501 – Published 12 August, 2009

DOI: https://doi.org/10.1103/PhysRevE.80.021501

Abstract

Monte Carlo simulations of a spherical macroion, surrounded by a size-asymmetric electrolyte in the primitive model, were performed. We considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice the size of counterions), for several surface charge densities of the macrosphere. The radial distribution functions, electrostatic potential in all the space and at the Helmholtz surfaces, and integrated charge are reported. We compare these simulational data with original results obtained from the Ornstein-Zernike integral equation, supplemented by the hypernetted chain–hypernetted chain (HNC-HNC) and hypernetted chain–mean spherical approximation (HNC-MSA) closures, and with the corresponding calculations using the modified Gouy-Chapman and unequal-radius modified Gouy-Chapman theories. The HNC-HNC and HNC-MSA integral equations formalisms show good concordance with Monte Carlo “experiments,” whereas the notable limitations of point-ion approaches are evidenced. Most importantly, the simulations confirm our previous theoretical predictions of the nondominance of the counterions in the size-asymmetric spherical electrical double layer [J. Chem. Phys. 123, 034703 (2005)], the appearance of anomalous curvatures at the outer Helmholtz plane, and the enhancement of the charge reversal and screening at high colloidal surface charge densities due to the ionic size asymmetry.

View figure in article

Article Text

References (69)

  1. S. S. Dukhin and B. V. Derjaguin, in Surface and Colloid Science, edited by E. Matijevic (Wiley, New York, 1974), Vol. 7, Chaps. 1 and 2.
  2. R. J. Hunter, Zeta Potential in Colloid Science (Academic Press, New York, 1981).
  3. R. D. Vold and M. J. Vold, Colloid and Interface Chemistry (Addison-Wesley, Reading, MA, 1983).
  4. R. J. Hunter, Foundations of Colloid Science (Clarendon, Oxford, 1987).
  5. F. Fenell-Evans and H. Wennerström, The Colloidal Domain: Where Physics, Chemistry, Biology and Technology Meet (Wiley-VCH, New York, 1994).
  6. P. C. Hiemenz and R. Rajagopalan, Principles of Colloid and Surface Chemistry (Marcel Dekker, New York, 1997).
  7. Y. Levin, Rep. Prog. Phys. 65, 1577 (2002).
  8. M. Quesada-Pérez, E. González-Tovar, A. Martín-Molina, M. Lozada-Cassou, and R. Hidalgo-Álvarez, ChemPhysChem 4, 234 (2003).
  9. R. Messina, J. Phys.: Condens. Matter 21, 113102 (2009).
  10. R. Kjellander, T. Åkesson, B. Jönsson, and S. Marčelja, J. Chem. Phys. 97, 1424 (1992).
  11. H. Greberg, R. Kjellander, and T. Åkesson, Mol. Phys. 87, 407 (1996).
  12. H. Greberg, R. Kjellander, and T. Åkesson, Mol. Phys. 92, 35 (1997).
  13. C. N. Patra and S. K. Ghosh, J. Chem. Phys. 117, 8938 (2002).
  14. L. B. Bhuiyan, C. W. Outhwaite, and D. Henderson, J. Chem. Phys. 123, 034704 (2005).
  15. F. Jiménez-Ángeles and M. Lozada-Cassou, J. Chem. Phys. 128, 174701 (2008).
  16. E. Gonzales-Tovar, M. Lozada-Cassou, and D. Henderson, J. Chem. Phys. 83, 361 (1985); 87, 5581 (1987).
  17. F. Jiménez-Ángeles, G. Odriozola, and M. Lozada-Cassou, J. Chem. Phys. 124, 134902 (2006).
  18. T. Goel, C. N. Patra, S. K. Ghosh, and T. Mukherjee, J. Chem. Phys. 129, 154707 (2008).
  19. T. Goel, C. N. Patra, S. K. Ghosh, and T. Mukherjee, J. Chem. Phys. 129, 154906 (2008).
  20. E. González-Tovar and M. Lozada-Cassou, J. Phys. Chem. 93, 3761 (1989).
  21. C. W. Outhwaite and L. B. Bhuiyan, Mol. Phys. 74, 367 (1991).
  22. Léo Degrève, M. Lozada-Cassou, Enrique Sánchez, and E. González-Tovar, J. Chem. Phys. 98, 8905 (1993).
  23. R. Messina, E. González-Tovar, M. Lozada-Cassou, and C. Holm, Europhys. Lett. 60, 383 (2002).
  24. E. González-Tovar, F. Jiménez-Ángeles, R. Messina, and M. Lozada-Cassou, J. Chem. Phys. 120, 9782 (2004).
  25. Y. X. Yu, J. Z. Wu, and G. H. Gao, J. Chem. Phys. 120, 7223 (2004).
  26. A. Diehl and Y. Levin, J. Chem. Phys. 125, 054902 (2006).
  27. T. Goel and C. N. Patra, J. Chem. Phys. 127, 034502 (2007).
  28. A. Diehl and Y. Levin, J. Chem. Phys. 129, 124506 (2008).
  29. O. Lenz and C. Holm, Eur. Phys. J. E 26, 191 (2008).
  30. J. P. Valleau and G. M. Torrie, J. Chem. Phys. 76, 4623 (1982).
  31. L. B. Bhuiyan, L. Blum, and D. Henderson, J. Chem. Phys. 78, 442 (1983).
  32. J. J. Spitzer, J. Colloid Interface Sci. 92, 198 (1983).
  33. A. F. Khater, D. Henderson, L. Blum, and L. B. Bhuiyan, J. Phys. Chem. 88, 3682 (1984).
  34. U. Marini Bettolo Marconi, J. Wiechen, and F. Forstmann, Chem. Phys. Lett. 107, 609 (1984).
  35. C. W. Outhwaite and L. B. Bhuiyan, J. Chem. Phys. 84, 3461 (1986).
  36. H. Greberg and R. Kjellander, J. Chem. Phys. 108, 2940 (1998).
  37. M. Valiskó, D. Henderson, and D. Boda, J. Phys. Chem. B 108, 16548 (2004).
  38. D. Gillespie, M. Valiskó, and D. Boda, J. Phys.: Condens. Matter 17, 6609 (2005).
  39. G. I. Guerrero-García, E. González-Tovar, M. Lozada-Cassou, and F. de J. Guevara-Rodríguez, J. Chem. Phys. 123, 034703 (2005).
  40. K. Wang, Y.-X. Yu, G.-H. Gao, and G.-S. Luo, J. Chem. Phys. 123, 234904 (2005).
  41. M. Valiskó, D. Boda, and D. Gillespie, J. Phys. Chem. C 111, 15575 (2007).
  42. K. Wang, Y.-X. Yu, G.-H. Gao, and G.-S. Luo, J. Chem. Phys. 126, 135102 (2007).
  43. R. Messina, J. Chem. Phys. 127, 214901 (2007).
  44. R. Messina, J. Chem. Phys. 117, 11062 (2002).
  45. S. L. Carnie and G. M. Torrie, Adv. Chem. Phys. 56, 141 (1984).
  46. L. B. Bhuiyan and C. W. Outhwaite, Phys. Chem. Chem. Phys. 6, 3467 (2004).
  47. G. N. Patey, J. Chem. Phys. 72, 5763 (1980).
  48. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Oxford University Press, New York, 1989).
  49. D. Frenkel and B. Smit, Understanding Molecular Simulation (Academic Press, London, 2002).
  50. J. Z. Wu, D. Bratko, H. W. Blanch, and J. M. Prausnitz, J. Chem. Phys. 111, 7084 (1999).
  51. T. Terao and T. Nakayama, Phys. Rev. E 63, 041401 (2001).
  52. D. Boda, D. Henderson, P. Plaschko, and W. R. Fawcett, Mol. Simul. 30, 137 (2004).
  53. L. Blum, J. L. Lebowitz, and D. Henderson, J. Chem. Phys. 72, 4249 (1980).
  54. L. Blum and D. Henderson, J. Chem. Phys. 74, 1902 (1981).
  55. P. Attard, D. Wei, and G. N. Patey, J. Chem. Phys. 96, 3767 (1992).
  56. G. M. Torrie, J. Chem. Phys. 96, 3772 (1992).
  57. M. B. Partenskii and P. C. Jordan, J. Chem. Phys. 99, 2992 (1993).
  58. M. B. Partenskii and P. C. Jordan, Condens. Matter Phys. 8, 397 (2005).
  59. M. S. Kilic, M. Z. Bazant, and A. Ajdari, Phys. Rev. E 75, 021502 (2007).
  60. M. B. Partenskii and P. C. Jordan, Phys. Rev. E 77, 061117 (2008).
  61. A. Martín-Molina, M. Quesada-Pérez, F. Galisteo-González, and R. Hidalgo-Álvarez, J. Phys. Chem. B 106, 6881 (2002).
  62. K. Besteman, M. A. G. Zevenbergen, H. A. Heering, and S. G. Lemay, Phys. Rev. Lett. 93, 170802 (2004).
  63. K. Besteman, M. A. G. Zevenbergen, and S. G. Lemay, Phys. Rev. E 72, 061501 (2005).
  64. A. Fernández-Nieves, A. Fernández-Barbero, and F. J. de las Nieves, J. Chem. Phys. 123, 054905 (2005).
  65. F. H. J. van der Heyden, D. Stein, K. Besteman, S. G. Lemay, and C. Dekker, Phys. Rev. Lett. 96, 224502 (2006).
  66. P. Attard, J. Phys. Chem. 99, 14174 (1995).
  67. M. Quesada-Pérez, E. González-Tovar, A. Martín-Molina, M. Lozada-Cassou, and R. Hidalgo-Álvarez, Colloids Surf., A 267, 24 (2005).
  68. M. Trulsson, B. Jönsson, T. Åkesson, J. Forsman, and C. Labbez, Phys. Rev. Lett. 97, 068302 (2006).
  69. A. Martín-Molina, C. Rodríguez-Beas, R. Hidalgo-Álvarez, and M. Quesada-Pérez, J. Phys. Chem. B 113, 6834 (2009).

Outline

Information

Phys. Rev. E 80, 021501– Published 12 August, 2009
  • Received 26 April 2009

© 2009 American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation