气体在混合溶液中溶解度的分子热力学计算

doi:10.11949/0438-1157.20190592

摘要/Abstract

摘要：

开发出一个分子热力学模型来预测低压下难溶于溶剂且不与溶剂发生反应的气体在二元混合溶液的溶解度，混合物中含有缔合作用成分及溶剂化作用成分，即形成配位化合物。在该模型中，Gibbs能为三个等温混合过程的和。溶质的偏摩尔过量Gibbs能由两部分组成，即化学和物理贡献。为了验证该模型的准确性，将该模型用于计算氮气在丙酮和氯仿混合物的溶解度。考虑实验的不确定度，氮气在二元混合溶液中的溶解度与实验数据吻合良好。

关键词: 热力学, 溶解性, 相平衡

Abstract:

A molecular-thermodynamic theory has been developed for predicting the solubility of a sparingly soluble gas in a complex binary liquid mixture at 0.101325 MPa. The binary liquid mixtures contain associating and solvating components whose molecules form weak chemical compounds. The Gibbs energy for the mixing process is the sum of three isothermal steps. The partial molar excess Gibbs energy of the solute is represented by two contributions, chemical and physical. When experimental uncertainties are taken into account, the predicted solubility of nitrogen in the binary solvent is in good agreement with previously published experimental solubility data.

Key words: thermodynamics, solubility, phase equilibria

中图分类号:

TK 121

杨富鑫,王晓坡,陈强,谭厚章. 气体在混合溶液中溶解度的分子热力学计算[J]. 化工学报, 2019, 70(S2): 62-69.

Fuxin YANG,Xiaopo WANG,Qiang CHEN,Houzhang TAN. Molecular thermodynamics for solubility of gas in binary liquid[J]. CIESC Journal, 2019, 70(S2): 62-69.

图/表 5

图1 等温混合过程示意图

Fig.1 Schematic diagram of isothermal mixing process

图2 氮气在丙酮和氯仿混合物的计算溶解度与文献值对比a—实验数据[28]；b—计算值，考虑溶液缔合作用；c—计算值，不考虑溶液缔合作用

Fig.2 Experimental and calculated solubility of nitrogen in acetone-chloroform mixtures

表1 计算模型各参数及氮气（3）在丙酮（1）和氯仿（2）混合物中的计算溶解度与文献值偏差

Table 1 Parameters of model for calculating solubility of nitrogen (3) in mixtures of acetone (1) and chloroform (2)

计算模型	K₁₁	K₁₂	K₂₂	α₃₁/(J·cm^-3)	α₃₂/(J·cm^-3)	α₁₂/(J·cm^-3)	x₃的标准偏差/%
缔合作用	0.083	1.80	0.054	102.8	108.4	9.0	6.08
缔合作用	0.083	1.80	0.16	102.8	104.4	6.5	5.45
缔合作用	0.16	1.80	0.16	100.1	104.4	5.3	4.74
无缔合作用	0	1.30	0	106.8	111.1	5.0	8.29

图3 考虑亨利常数的不确定性，氮气在丙酮和氯仿混合物中的计算溶解度与文献值对比a—实验值[28]； b—考虑溶剂的缔合作用和亨利常数存在-5%的偏差

Fig.3 Experimental and calculated solubility of nitrogen in acetone-chloroform mixtures considering uncertainty for Henry’s constants

图4 由Apelblat等[30]的汽液相平衡实验数据拟合得到的参数K12和α12的关系

Fig.4 Parameters K12 and α12 fitted from experimental vapor-liquid equilibrium data of Ref.[30]

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