### Abstract

Language | English |
---|---|

Pages | 1435-1443 |

Number of pages | 9 |

Journal | Molecular Physics |

Volume | 96 |

Issue number | 9 |

DOIs | |

Publication status | Published - 10 May 1999 |

### Fingerprint

### Keywords

- 5th virial-coefficient
- density-functional theory
- phase- separation
- integral-equation
- computer-simulation
- core mixtures
- monte-carlo
- consistent
- colloids

### Cite this

*Molecular Physics*,

*96*(9), 1435-1443. https://doi.org/10.1080/00268979909483087

}

*Molecular Physics*, vol. 96, no. 9, pp. 1435-1443. https://doi.org/10.1080/00268979909483087

**Depletion effects and gelation in a binary hard-sphere fluid.** / Lue, L.; Woodcock, L. V.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Depletion effects and gelation in a binary hard-sphere fluid

AU - Lue, L.

AU - Woodcock, L. V.

N1 - English Article 198HA MOL PHYS

PY - 1999/5/10

Y1 - 1999/5/10

N2 - A study of the binary hard-sphere fluid with size ratio sigma(B)/sigma(A)= 0.1 is reported. Molecular dynamics and Monte Carlo simulations have been carried out over the mole fraction (x(A)) range 0.002-0.1and over the high density range where several recent authors have predicted a thermodynamic demixing transition on the basis of integral equations. In this region, there is no evidence of such first-order thermodynamic phase separation, or two fluid phases. The effect of the depletion force, arising from the entropic exclusion of B spheres from between two A spheres, as x(B) is increased at constant packing fraction y(A), is to cause a large increase in the partial pressure of A and the radial distribution function of A at contact, a reduction on the mobility of A, and eventually, at a sufficient x(B), the gelation of component A to an open, low coordination, amorphous structure.This gelation transition of A shows discontinuities similar to a glass transition; it can be traced back to the hard sphere glass formation as x(B) approaches zero. Thermodynamic properties are reported over the range studied; and used to evaluate the predictions of current theories and the accuracy of equations of state. The Boublik-Mansoori-Carnahan-Starling-Leland equation is found to be remarkably accurate in this region,over the whole fluid range, but shows systematic deviations at high packing densities.

AB - A study of the binary hard-sphere fluid with size ratio sigma(B)/sigma(A)= 0.1 is reported. Molecular dynamics and Monte Carlo simulations have been carried out over the mole fraction (x(A)) range 0.002-0.1and over the high density range where several recent authors have predicted a thermodynamic demixing transition on the basis of integral equations. In this region, there is no evidence of such first-order thermodynamic phase separation, or two fluid phases. The effect of the depletion force, arising from the entropic exclusion of B spheres from between two A spheres, as x(B) is increased at constant packing fraction y(A), is to cause a large increase in the partial pressure of A and the radial distribution function of A at contact, a reduction on the mobility of A, and eventually, at a sufficient x(B), the gelation of component A to an open, low coordination, amorphous structure.This gelation transition of A shows discontinuities similar to a glass transition; it can be traced back to the hard sphere glass formation as x(B) approaches zero. Thermodynamic properties are reported over the range studied; and used to evaluate the predictions of current theories and the accuracy of equations of state. The Boublik-Mansoori-Carnahan-Starling-Leland equation is found to be remarkably accurate in this region,over the whole fluid range, but shows systematic deviations at high packing densities.

KW - 5th virial-coefficient

KW - density-functional theory

KW - phase- separation

KW - integral-equation

KW - computer-simulation

KW - core mixtures

KW - monte-carlo

KW - consistent

KW - colloids

U2 - 10.1080/00268979909483087

DO - 10.1080/00268979909483087

M3 - Article

VL - 96

SP - 1435

EP - 1443

JO - Molecular Physics

T2 - Molecular Physics

JF - Molecular Physics

SN - 0026-8976

IS - 9

ER -