电解质MIVM在含Na^(+)或Cl^(-)表面活性剂体系中渗透系数的计算

Calculation of Osmotic Coefficient of Electrolyte MIVM in Na^(+)or Cl^(-)Two Component Ionic Surfactant System

本文采用电解质MIVM(eMIVM)和电解质NRTL模型(eNRTL)分别对含钠和含氯的二组分离子表面活性剂体系的渗透系数进行了计算,并比较了两个模型的计算结果。通过比较发现,不论是在含钠体系还是含氯体系,eMIVM都要比eNRTL具有一定的优势。eMIVM和eNRTL在含钠体系拟合的偏差分别为0.0230、0.0420,拟合的相对误差分别为2.88%、4.98%;在含氯体系拟合的偏差分别为0.0594、0.0606,拟合的相对误差分别为13.19%、13.95%。同时,本文通过渗透系数的计算关联了溶液的渗透压,可以看出在部分含钠的体系中,eMIVM计算的渗透压更接近实验值,计算的偏差相比于eNRTL更小,更符合实际的应用情况。在部分含钠的体系中,eNRTL表现出相反的拟合趋势,这也许是因为eMIVM相较于eNRTL具有更可靠的统计热力学基础,可以同时描述分子相互作用(焓)和分子构型的微观状态数(熵)对过量吉布斯能的贡献。这表明eMIVM可以适用于离子表面活性剂体系,进一步拓展了该模型的适用性。

This paper uses electrolyte MIVM(eMIVM) and electrolyte NRTL model(eNRTL) to calculate the osmotic coefficient of the two-component ionic surfactant system containing sodium and chlorine respectively, and compares the calculation results of the two models. Through comparison, it is found that eMIVM has certain advantages over eNRTL in both the sodium and chlorine systems. The fitting deviations of eMIVM and eNRTL in the sodium-containing system were 0.0230 and 0.0420 respectively, and the relative errors of fitting were 2.88% and 4.98% respectively. In the chlorine-containing system, the fitting deviations was 0.0594 and 0.0606, and the fitting relative errors was 13.19% and 13.95%, respectively. At the same time, the osmotic pressure of the solutions was correlated with the calculation of osmotic coefficient in this paper. It can be seen that in some sodium-based systems, the osmotic pressure calculated by eMIVM is closer to the experimental values, and the calculated deviations is smaller than that of eNRTL, which is more in line with the actual application situation. In addition, in some systems containing sodium, eNRTL shows an opposite fitting trend. This may be because eMIVM has a more reliable statistical thermodynamic basis compared with eNRTL, and can simultaneously describe the contribution of molecular interaction(enthalpy) and the number of microscopic states of molecular configuration(entropy) to excess Gibbs energy. This indicates that eMIVM can be applied to the ionic surfactant system, further expanding the applicability of this model.