液体的表面吸附:表面相厚度和热效应的理论研究
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摘要
本文定量研究了6种纯液体的表面张力与温度的关系,进一步预测了这些液体从体相到表面相的相变过程中所放出的热量,并提出放热的根源是分子在表面相更有序的排列引起了熵的减少。本文还研究了CaCl_2和K_2CO_3水溶液的表面张力随浓度的变化关系,理论模拟结果与实验数据非常一致;同时,在给定β值的情况下,还对16种强电解质溶液的表面层厚度进行了估算,对所揭示的溶液表面层增厚现象给出了理论解释。
In this article the relationship between the surface tension and temperature for six pure liquids were studied quantitatively,and the heat released by the phase transition of these liquids from bulk to surface has been further predicted.We elucidate that the fundamental cause of exothermicity is that the entropy is reduced due to that molecules are arranged in a more ordered way in the surface phase.The relationships between the surface tension and concentrations of CaCl_2 and K_2CO_3 aqueous solutions were also investigated and the simulated results were in very close agreement with the experimental data.Meanwhile,we also estimated the surface layer thickness of 16 strong electrolyte solutions at given β values,and a theoretical explanation for the phenomenon of the surface layer thickening of solutions was given.
In this article the relationship between the surface tension and temperature for six pure liquids were studied quantitatively,and the heat released by the phase transition of these liquids from bulk to surface has been further predicted.We elucidate that the fundamental cause of exothermicity is that the entropy is reduced due to that molecules are arranged in a more ordered way in the surface phase.The relationships between the surface tension and concentrations of CaCl_2 and K_2CO_3 aqueous solutions were also investigated and the simulated results were in very close agreement with the experimental data.Meanwhile,we also estimated the surface layer thickness of 16 strong electrolyte solutions at given β values,and a theoretical explanation for the phenomenon of the surface layer thickening of solutions was given.
引文
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[3]F M Menger,S A A Rizvi.Langmuir,2011,27:13975~13977.
[4]F M Menger,L Shi,S A A Rizvi.Langmuir,2009,26:1588~1589.
[5]J Laven,G de With.Langmuir,2011,27:7958~7962.
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[7]I Mukherjee,S P Moulik,A K Rakshit.J.Colloid Interf.Sci.,2013,394:329~336.
[8]P X Li,Z X Li,H H Shen et al.Langmuir,2013,29:9324~9334.
[9]H Xu,P X Li,K Ma et al.Langmuir,2013,29:9335~9351.
[10]P X Li,R K Thomas,J Penfold.Langmuir,2014,30:6739~6747.
[11]K D Danov,R D Stanimirova,P A Kralchevsky et al.J.Colloid Interf.Sci.,2015,457:307~318.
[12]H Xu,P Li,K Ma et al.Langmuir,2017,33:9944~9953.
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[15]Z B Li,Y G Li,J F Lu.Ind.Eng.Chem.Res.,1999,38:1133~1139.
[16]Y X Yu,G H Gao,Y G Li.Fluid Phase Equilibr.,2000,173:23~38.
[17]Y Levin,A P Dos Santos,A Diehl.Phys.Rev.Lett.,2009,103:257802.
[18]陈飞武,卢天,武钊.物理化学学报,2015,31:1499~1503.
[19]R Wang,Z G Wang.J.Chem.Phys.,2016,144:134902.
[20]A Casandra,R Y Tsay,C M Phan et al.Colloid.Surf.A,2017,512:137~144.
[21]F W Chen,Q Ren.Chem.Phys.Lett.,2017,685:438~441.
[22]傅献彩,沈文霞,姚天扬等.物理化学(上、下册).第5版.北京:高等教育出版社,2009.
[23]B Xin,J Hao.Chem.Soc.Rev.,2014,43:7171~7187.
[24]宋冰蕾,翟兆兰,赵剑曦等.物理化学学报,2015,31:2324~2331.
[25]V I Petrenko,M V Avdeev,V M Garamus et al.Colloid.Surf.A,2015,480:191~196.
[26]H F Wang,L Velarde,W Gan et al.Annu.Rev.Phys.Chem.,2015,66:189~216.
[27]K Lv,L Lin,X Wang et al.J.Phys.Chem.Lett.,2015,6:1719~1723.
[28]S L Chen,L Fu,W Gan et al.J.Chem.Phys.,2016,144:034704.
[29]C X He,H Zhang,C G Lin et al.Chem.Phys.Lett.,2017,676:144~149.
[30]束宁凯,徐志成,刘子瑜等.物理化学学报,2017,33:803~809.
[31]Y Marcus.J.Chem.Eng.Data,2010,55:3641~3644.
[32]J Wu,Z Liu,F Wang et al.J.Chem.Eng.Data,2003,48:1571~1573.
[33]S Bi,G Zhao,J Wu.J.Chem.Eng.Data,2010,55:1523~1526.
[34]W Gao,X Zhao,Z Liu.J.Chem.Eng.Data,2009,54:1761~1763.
[35]H Kahl,T Wadewitz,J Winkelmann.J.Chem.Eng.Data,2003,48:580~586.
[36]X Zhao,W Duan,X Zeng et al.J.Chem.Eng.Data,2018,63:21~26.
[37]E W Washburn.International Critical Tables of Numerical Data,Physics,Chemistry and Technology(Volume 4),1st electronic edition,Knovel,Norwich,New York,2003.
[38]H F Wang,W Gan,R Lu et al.Int.Rev.Phys.Chem.,2005,24:191~256.