Li2B4O7-MgCl2(B)-H2O体系热力学性质的等压研究及离子相互作用模型

化学学报 ›› 2004, Vol. 62 ›› Issue (12): 1089-1094. 下一篇

研究论文

Li₂B₄O₇-MgCl₂(B)-H₂O体系热力学性质的等压研究及离子相互作用模型

张爱云^1,2,3, 姚燕¹, 杨吉民¹, 宋彭生¹

1. 中国科学院青海盐湖研究所, 西宁, 810008;
2. 中国科学院研究生院, 北京, 100039;
3. 黑龙江科技学院, 哈尔滨, 160000

投稿日期:2003-12-08 修回日期:2004-03-02 发布日期:2014-02-17
通讯作者: 姚燕,E-mail:yanyao@pub.xaonline.com E-mail:yanyao@pub.xaonline.com
基金资助:
国家自然科学基金(Nos.29871034;20373084)和中国科学院基础局重点基础资助项目.

Isopiestic Studies of Thermodynamic Properties and Representation with Ion-interaction Model for Li₂B₄O₇-MgCl₂(B)-H₂O System at 298.15 K

ZHANG Ai-Yun^1,2,3, YAO Yan¹, YANG Ji-Min¹, SONG Peng-Sheng¹

1. Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008;
2. Graduate School of Chinese Academy of Sciences, Beijing 100039;
3. Heilongjiang Science and Technology College, Harbin 160000

Received:2003-12-08 Revised:2004-03-02 Published:2014-02-17

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摘要/Abstract

采用等压法测定了298.15 K下Li-Mg-Cl-borate-H₂O体系离子强度范围为0.0581～0.6320 mol·kg^-1,MgCl₂不同离子浓度分数的等压摩尔平衡浓度、水活度,计算了Li₂B₄O₇和MgCl₂混合溶液的饱和水蒸汽压、渗透系数等热力学性质.考虑了在不同的总硼浓度范围的硼酸(H₃BO₃)和硼氧配阴离子[B(OH)-4,B₃O₃(OH)₄^-,B₄O₅(OH)₄^2-]的不同生成反应平衡.由实验结果对修正的Pitzer渗透系数方程进行了参数化研究,提出了一简化的参数化模型,减少了模型的经验参数量,获得了锂、镁、氯离子与硼物种组合之间、及不同硼氧配阴离子之间的组合相互作用参数,用该模型计算的渗透系数值与实验结果取得合理的一致性,从而将离子作用模型扩展到对含硼、锂、镁的复杂体系的表述.对完善含锂、硼的盐湖卤水体系的热力学模型和盐湖资源的综合开发利用具有重要意义.

关键词: Li₂B₄O₇-MgCl₂-H₂O体系, 等压法, 渗透系数, 离子相互作用模型

The isopiestic molalities and the water activities have been measured by isopiestic method and the water vapor pressures and the osmotic coefficients have been calculated from the measurements in the ion-strength range from 0.0581 mol·kg^-1 to 0.6320 mol·kg^-1 at T=298.15 K for the system Li-Mg-Cl-borate-H₂O. The formation reaction equilibria of boron species of boric acid (H₃BO₃) and borate anions [B(OH)₄^-, B₃O₃(OH)₄^- and B₄O₅(OH)₄^2-] have been taken into account for the system in different total boron concentration ranges. A simplified model based on Pitzer's osmotic coefficient equations with minor modifications has been proposed by combining the same kinds of ion-interactions related to the different borate anions, which reduced the number of ion-interaction parameters from 52 in the primary model to 23 in the simplified model. The ion-interaction parameters among the groups of borate anions, Cl^-, Li⁺ and Mg²⁺ for the simplified model have been estimated using the experimental data taken from this work and references. The osmotic coefficient values determined experimentally and those calculated by using the model with the parameters are in reasonable agreement. Pitzer's ion-interaction model has been extended to represent the thermodynamic properties of the complex system containing various borate anions. These studies are useful to improve the thermodynamic model for salt lake brine systems containing lithium and borates.

Key words: Li₂B₄O₇-MgCl₂-H₂O system, isopiestic method, osmotic coefficient, ion-interaction model

引用此文

张爱云, 姚燕, 杨吉民, 宋彭生. Li₂B₄O₇-MgCl₂(B)-H₂O体系热力学性质的等压研究及离子相互作用模型[J]. 化学学报, 2004, 62(12): 1089-1094.

ZHANG Ai-Yun, YAO Yan, YANG Ji-Min, SONG Peng-Sheng. Isopiestic Studies of Thermodynamic Properties and Representation with Ion-interaction Model for Li₂B₄O₇-MgCl₂(B)-H₂O System at 298.15 K[J]. Acta Chimica Sinica, 2004, 62(12): 1089-1094.

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Li₂B₄O₇-MgCl₂(B)-H₂O体系热力学性质的等压研究及离子相互作用模型

Isopiestic Studies of Thermodynamic Properties and Representation with Ion-interaction Model for Li₂B₄O₇-MgCl₂(B)-H₂O System at 298.15 K

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