Primitive model electrolytes. A comparison of the HNC approximation for the activity coefficient with Monte Carlo data

• Published in: Condensed matter physics 2011-01, Vol.14 (3), p.33003
• Main Authors: Gutiérrez-Valladares, Lukšič, Millán-Malo, Hribar-Lee, Vlachy
• Format: Article
• Language: English
• Subjects: Debye-Hückel theory; hypernetted-chain approximation; mean activity coefficient; mean spherical approximation; Monte Carlo simulation; Pitzer's approach; primitive model electrolyte
• ISSN: 1607-324X
• DOI: 10.5488/CMP.14.33003

Accuracy of the mean activity coefficient expression (Hansen-Vieillefosse-Belloni equation), valid within the hypernetted chain (HNC) approximation, was tested in a wide concentration range against new Monte Carlo (MC) data for +1:-1 and +2:-2 primitive model electrolytes. The expression has an advantage that the excess chemical potential can be obtained directly, without invoking the time consuming Gibbs-Duhem calculation. We found the HNC results for the mean activity coefficient to be in good agreement with the machine calculations performed for the same model. In addition, the thermodynamic consistency of the HNC approximation was tested. The mean activity coefficients, calculated via the Gibbs-Duhem equation, seem to follow the MC data slightly better than the Hansen-Vieillefosse-Belloni expression. For completeness of the calculation, the HNC excess internal energies and osmotic coefficients are also presented. These results are compared with the calculations based on other theories commonly used to describe electrolyte solutions, such as the mean spherical approximation, Pitzer's extension of the Debye-Hückel theory, and the Debye-Hückel limiting law.