Molecular simulation of the surface tension of simple aqueous electrolytes and the Gibbs adsorption equation

被引：34

作者：

Bhatt, D ^{[1
]}

Chee, R ^{[1
]}

Newman, J ^{[1
]}

Radke, CJ ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem Engn, Berkeley, CA 94720 USA

来源：

CURRENT OPINION IN COLLOID & INTERFACE SCIENCE | 2004年 / 9卷 / 1-2期

关键词：

molecular dynamics; explicit water; positive salt adsorption; surface-tension maximum; Gibbs adsorption equation;

D O I：

10.1016/j.cocis.2004.05.020

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We present molecular dynamics simulations of the surface tension of aqueous NaCl and NaBr electrolyte solutions as a function of concentration at 300 K. With explicit water and Lennard-Jones/Coulomb ions of fixed charge, we find a positive Gibbs adsorption of both salts at higher concentrations of several molar. Although the calculated surface tensions are larger than that of pure water, positive salt adsorption is in agreement with the classic Gibbs adsorption equation because our simulations reveal a local maximum in the surface-tension isotherm. Experimental surface tensions for NaCl and NaBr, however, demonstrate a linear increase with increasing electrolyte concentration, calling into question the accuracy of the intermolecular-potential parameters chosen to represent the sodium halide salts. (C) 2004 Elsevier Ltd. All rights reserved.

引用

页码：145 / 148

页数：4

共 21 条

[1] THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS [J].

BERENDSEN, HJC ;

GRIGERA, JR ;

STRAATSMA, TP .

JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (24) :6269-6271

[2] Molecular dynamics simulations of surface tensions of aqueous electrolytic solutions [J].

Bhatt, D ;

Newman, J ;

Radke, CJ .

JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (26) :9077-9084

[3] Surface tension of electrolytes:: Specific ion effects explained by dispersion forces [J].

Boström, M ;

Williams, DRM ;

Ninham, BW .

LANGMUIR, 2001, 17 (15) :4475-4478

[4] THE HOFMEISTER EFFECT AND THE BEHAVIOR OF WATER AT INTERFACES [J].

COLLINS, KD ;

WASHABAUGH, MW .

QUARTERLY REVIEWS OF BIOPHYSICS, 1985, 18 (04) :323-422

[5] STICKY IONS IN BIOLOGICAL-SYSTEMS [J].

COLLINS, KD .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1995, 92 (12) :5553-5557

[6] SIMULATION OF ELECTROSTATIC SYSTEMS IN PERIODIC BOUNDARY-CONDITIONS .1. LATTICE SUMS AND DIELECTRIC-CONSTANTS [J].

DELEEUW, SW ;

PERRAM, JW ;

SMITH, ER .

PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 1980, 373 (1752) :27-56

[7]

FRENKEL D, 1991, UNDERSTANDING MOL SI, pCH6

[8] Ions at the air/water interface [J].

Garrett, BC .

SCIENCE, 2004, 303 (5661) :1146-1147

[9]

HEINZINGER K, 1986, ACTA CHIM HUNG, V121, P27

[10]

Heydweiller A, 1910, ANN PHYS-BERLIN, V33, P145

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