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烷基芳基磺酸盐分子量及其分布对微乳液结构参数及热力学函数的影响

丁伟1*,王会敏1,罗石琼1,张志伟1,董志龙1,于涛1,曲广淼1,程杰成2   

  1. (1.东北石油大学化学化工学院 大庆 163318；2.大庆油田有限责任公司科技发展部 大庆 163453)
  • 收稿日期:2011-08-10 修回日期:2011-10-26 出版日期:2012-07-10 发布日期:2012-07-10
  • 通讯作者: 丁伟，教授; Tel/Fax:0459-6504071; E-mail:dingwei40@126.com; 研究方向：油田应用化学
  • 基金资助:
    国家重点基础研究发展规划“973”(2005CB221300)和黑龙江省研究生创新科研(YJSCX2008-044 HLJ)资助项目

Effects of Average Molecular Mass and Its Distribution of Alkyl Aryl Sulfonate on the Structural Parameters and Thermodynamic Functions of Microemulsion

DING Wei1*, WANG Huimin1,  LUO Shiqiong1, ZHANG Zhiwei1, DONG Zhilong1, YU Tao1, QU Guangmiao1, CHENG Jiecheng2   

  1. (1.College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing 163318,China；
    2.Development Department of Science and Technology,Daqing Oil Field Corp.Ltd,Daqing 163453,China)
  • Received:2011-08-10 Revised:2011-10-26 Published:2012-07-10 Online:2012-07-10

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摘要： 用稀释法求得了由自制的7种烷基芳基磺酸盐复配体系（AAS）/正丁醇/正癸烷/水组成的W/O型微乳液的结构参数，还求得了醇从油相转移到界面时的标准自由能，并计算出标准焓变和标准熵变。 探讨了烷基芳基磺酸盐平均分子量及其分布对结构参数及热力学函数的影响。 结果表明，分散相有效半径Re，内核水半径Rw，二者之差di和表面活性剂分子在每个液滴中的平均聚集数n值均呈现为正态分布＜递减分布＜均匀分布＜递增分布＜反正态分布；分散相颗粒总数Nd和分散相界面外层总面积Ad值均呈现为正态分布＞递减分布＞均匀分布＞递增分布＞反正态分布；-ΔG0o→i值呈现为正态分布(5.36 kJ/mol)＜递减分布(5.49 kJ/mol)＜均匀分布(5.64 kJ/mol)＜递增分布(5.78 kJ/mol)＜反正态分布(6.01 kJ/mol);ΔS0o→i值呈现为正态分布(26.88 J/(mol·K))＜递减分布(27.12 J/(mol·K))＜均匀分布(27.60 J/(mol·K))＜递增分布(28.06 J/(mol·K))＜反正态分布(29.23 J/(mol·K));Rw、Re、n、di、-ΔG0o→i、ΔH0o→i和ΔS0o→i值均随磺酸盐平均分子量的增大而增大；Nd、Ad值均随磺酸盐平均分子量的增大而减小；且在实验范围内，结构参数、-ΔG0o→i、ΔS0o→i与磺酸盐平均分子量均呈线性关系;后两者分别为y=0.0586x-17916，y=0.2203x-61.275。

关键词: 烷基芳基磺酸盐, 平均分子量, 分子量分布, 微乳液, 结构参数, 热力学函数

Abstract: The structural parameters of complex systems of seven kinds of aryl sulfonate(synthesized in the laboratory) alkyl aryl sulfonate(AAS)/n-butanol/n-decane/water microemulsions were obtained by means of a dilution method. We also calculated the standard free energy ΔG0o→i of transfer from the continuous oil phase to the interfacial region, the standard enthalpy ΔH0o→i and the standard entropy ΔS0o→i values. The effects of the average molecular mass and its distribution of AAS on the structural parameters and thermodynamic functions were investigated. The results show that the effective radius of dispersive phase Re, the radius of inner sphere water Rw, their difference di, the average aggerate number of surfactant molecules per drop n, have the tendency of normal distribution＜descending distribution＜uniform distribution＜incremental distribution＜reversed normal distribution. The total number of dispersion phase particles Nd and the total interface area of dispersion phase outer sphere Ad appear to be contrary to the above consequence. The values of -ΔG0o→i exhibit the tendency of normal distribution(5.36 kJ/mol)＜descending distribution(5.49 kJ/mol)＜uniform distribution(5.64 kJ/mol)＜incremental distribution(5.78 kJ/mol)＜reversed normal distribution(6.01 kJ/mol). The values of ΔS0o→i have the tendency of normal distribution(26.88 J/(mol·K))＜descending distribution(27.12 J/(mol·K))＜uniform distribution(27.60 J/(mol·K))＜incremental distribution(28.06 J/(mol·K))＜reversed normal distribution(29.23 J/(mol·K)). With the increase of average molecular mass, the values of Rw, Re, n, di, -ΔG0o→i, ΔH0o→i, ΔS0o→i increase while the values of Nd, Ad decrease. In addition, the values of structural parameters, -ΔG0o→i and ΔS0o→i change linearly with the average molecular mass of the AAS, the latter two are y=0.0586x-17916 and y=0.2203x-61.275, respectively.

Key words: alkyl aryl sulfonates, average molecular mass, molecular mass distribution, microemulsion, structural parameter, thermodynamic functions

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