Please wait a minute...
Acta Physico-Chimica Sinca  2015, Vol. 31 Issue (8): 1499-1503    DOI: 10.3866/PKU.WHXB201506191
THEORETICALAND COMPUTATIONAL CHEMISTRY     
Surface Absorption of a Solution at Equilibrium
Fei-Wu. CHEN*(),Tian. LU,Zhao. WU
1 Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China
2 Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Beijing 100083, P. R. China
Download: HTML     PDF(3805KB) Export: BibTeX | EndNote (RIS)      

Abstract  

Surface adsorption of a solution is still a challenging problem in the thermodynamics of surfaces. In this work, a new thermodynamic state function is defined. The equilibrium condition of surface adsorption is that the differential of this state function is equal to zero. Based on this condition, we derived a new equation to describe surface adsorption at equilibrium. No hypothetical dividing surface is needed in this derivation. The new equation is quite different from the Gibbs adsorption equation. We also performed molecular dynamic simulations of aqueous sodium chloride solutions. The simulated results are in good agreement with our theoretical predictions.



Key wordsSurface absorption      Equilibrium condition      Gibbs absorption equation      Thermodynamic state function      Solution     
Received: 04 March 2015      Published: 19 June 2015
MSC2000:  O641  
Fund:  the National Natural Science Foundation of China(21173020);the National Natural Science Foundation of China(21473008)
Corresponding Authors: Fei-Wu. CHEN     E-mail: chenfeiwu@ustb.edu.cn
Cite this article:

Fei-Wu. CHEN,Tian. LU,Zhao. WU. Surface Absorption of a Solution at Equilibrium. Acta Physico-Chimica Sinca, 2015, 31(8): 1499-1503.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201506191     OR     http://www.whxb.pku.edu.cn/Y2015/V31/I8/1499

Fig 1 Ten density profiles (ranging from 0.2 to 2.0 mol·L-1 with incremental size of 2.0 mol·L-1) of NaCl with respect to the distance in z direction N: number density of Nacl pairs
Fig 2 Snapshot of molecular dynamic trajectory in simulation
Fig 3 Simulated surface tension versus the number of moles of NaCl in the surface region
Fig 4 Simulated concentration of NaCl in the bulk region versus concentration of NaCl in the surface region
1 Cheng X. H. ; Zhao O. D. ; Zhao H. N. ; Huang J. B. Acta Phys. -Chim. Sin. 2014, 30, 917.
1 程新皓; 赵欧狄; 赵海娜; 黄建滨.. 物理化学学报, 2014, 30, 917.
2 Hu S. Q. ; Ji X.J. ; Fan Z. Y. ; Zhang T. T. ; Sun S. Q. Acta Phys. -Chim. Sin. 2015, 31, 83.
2 胡松青; 纪贤晶; 范忠钰; 张田田; 孙霜青. 物理化学学报, 2015, 31, 83.
3 Wang K. ; Yu Y. X. ; Gao G. H. J.Chem. Phys. 2008, 128, 185101.
4 Peng, B.; Yu, Y. X. J. Chem. Phys. 2009, 131, 134703. doi: 10.1063/1.3243873
5 Ghosh S. ; Roy A. ; Banik D. ; Kundu N. ; Kuchlyan J. ; Dhir A. ; Sarkar N. Langmuir 2015, 31, 2310.
6 Bera M. K. ; Antonio M. R. Langmuir 2015, 31, 5432.
7 Atkins, P.; de Paula, J. Atkins' Physical Chemistry, 7th Ed.; Oxford University Press: Oxford, 2002.
8 Menger, F. M.; Shi, L.; Rizvi, S. A. A. J. Am. Chem. Soc. 2009, 131, 10380. doi: 10.1021/ja9044289
9 Menger F. M. ; Shi L. ; Rizvi S. A. A. Langmuir 2010, 26, 1588.
10 Menger F. M. ; Rizvi S. A. A. Langmuir 2011, 27, 13975.
11 Laven J. ; de With G. Langmuir 2011, 27, 7958.
12 Menger F. M. ; Rizvi S. A. A. ; Shi L. Langmuir 2011, 27, 7963.
13 Li P. X. ; Li Z. X. ; Shen H. H. ; Thomas R. K. ; Penfold J. ; Lu J. R. Langmuir 2013, 29, 9324.
14 Nath S. J.Colloid Interface Sci. 1999, 209, 116.
15 Li Z. B. ; Li Y. G. ; Lu J. F. Ind. Eng. Chem. Res. 1999, 38, 1133.
16 Yu Y. X. ; Gao G. H. ; Li Y. G. Fluid Phase Equilibr. 2000, 173, 23.
17 Gromacs Program, Version 4.6.5. http://www.gromacs.org (accessed on Sep 14, 2014).
18 Hess, B.; Kutzner, C.; van der Spoel, D.; Lindahl, E. J. Chem. Theory Comput. 2008, 4, 435. doi: 10.1021/ct700301q
19 Hoover W. G. Phys. Rev. A 1985, 31, 1695.
20 Nosé S. Mol. Phys. 1984, 52, 255.
21 Weerasinghe S. ; Smith P. E. J.Chem. Phys. 2003, 119, 11342.
22 Ploetz E. A. ; Bentenitis N. ; Smith P. E. Fluid Phase Equilib. 2010, 290, 43.
23 Berendsen H. J. C. ; Grigera J. R. ; Straatsma T. P. J.Phys. Chem. 1987, 91, 6269.
24 Miyamoto, S.; Kollman, P. A. J. Comput. Chem. 1992, 13, 952.
25 Darden T. ; York D. ; Pedersen L. J.Chem. Phys. 1993, 98, 10089.
26 Chen F. ; Smith P. E. J.Phys. Chem. B 2008, 112, 8975.
27 Jarvis N. L. ; Scheiman M. A. J.Phys. Chem. 1968, 72, 74.
28 Weissenborn P. K. ; Pugh R. J. Langmuir 1996, 11, 1422.
[1] Yongquan ZHOU,Yoshie SOGA,Toshio YAMAGUCHI,Yan FANG,Chunhui FANG. Structure of Aqueous RbCl and CsCl Solutions Using X-Ray Scattering and Empirical Potential Structure Refinement Modelling[J]. Acta Physico-Chimica Sinca, 2018, 34(5): 483-491.
[2] Jiale XU,Lei HU,Lu WANG,Jinxia DENG,Jun CHEN,Xianran XING. Controllable Thermal Expansion and Crystal Structure of (Fe1-xNix)ZrF6 Solid Solutions[J]. Acta Physico-Chimica Sinca, 2018, 34(4): 339-343.
[3] Dan-Hui LÜ,Dan-Cheng ZHU,Chuan-Hong JIN. Preferential Substitution of Selenium along the Grain Boundaries in Monolayer MoS2(1-x)Se2x Alloy[J]. Acta Physico-Chimica Sinca, 2017, 33(8): 1514-1519.
[4] Xu LI,Qiang-Guo LI,Jian-Hong JIANG,Hui-Wen GU,Chuan-Hua LI,Sheng-Xiong XIAO,Xia LI. Design and Application of a Precise Isoperibol Combus-tion-Solution-Reaction Microcalorimeter[J]. Acta Physico-Chimica Sinca, 2017, 33(6): 1114-1122.
[5] Jing TONG,Lu LIU,Duo ZHANG,Xu ZHENG,Xia CHEN,Jia-Zhen YANG. Parameters of the Activation of Viscous Flow of Aqueous[C2mim] [Ala][J]. Acta Physico-Chimica Sinca, 2017, 33(3): 513-519.
[6] Qing-Hua YI,Jie ZHAO,Yan-Hui LOU,Gui-Fu ZOU,Zhong-Fan LIU. Design and Growth of High-Quality Multifunctional Thin Films by Polymer-Assisted Deposition[J]. Acta Physico-Chimica Sinca, 2017, 33(2): 314-328.
[7] Tao JING,Ying DAI. Development of Solid Solution Photocatalytic Materials[J]. Acta Physico-Chimica Sinca, 2017, 33(2): 295-304.
[8] Meng-Xi LIU,Shi-Chao LI,Ze-Qi ZHA,Xiao-Hui QIU. Research Progress and Applications of qPlus Noncontact Atomic Force Microscopy[J]. Acta Physico-Chimica Sinca, 2017, 33(1): 183-197.
[9] Hao CHEN,Tao YANG,Jie-Wei LI,Xin-Wen ZHANG,Yan QIAN,Ling-Hai XIE,Wei HUANG. Synthesis and Optoelectronic Properties of a Solution-Processable Anthraquinone/Fluorene Hybrid Bipolar Fluorescent Material[J]. Acta Physico-Chimica Sinca, 2016, 32(9): 2346-2354.
[10] Dong GUO,Jia-Xi SONG,Dan LI,Jia-Mei CHEN,Li-Rong LIN,Tong-Bu LU,Hui ZHANG. Determination and Correlation of the Absolute Configurations of Chiral Nimodipine[J]. Acta Physico-Chimica Sinca, 2016, 32(9): 2241-2254.
[11] Qian ZHOU,Jian-Qiang YU,Li-Bo ZHAO,De-Sheng LI,Kui WU,Jian-Hua ZHU,Jing-He YUAN,Xiao-Hong FANG. Super-Resolution Optical Subtraction Microscopy Using Optical Scattering Imaging[J]. Acta Physico-Chimica Sinca, 2016, 32(5): 1123-1128.
[12] Jun-Sheng YUAN,Zi-Yu LIU,Fei LI,Shen-Yu LI. Study of the Hydrated Structure of KCl and NaCl Mixed Solutions Using X-ray Diffraction and Raman Spectroscopy[J]. Acta Physico-Chimica Sinca, 2016, 32(5): 1143-1150.
[13] Xu-Li GONG,Chang-Qiao ZHANG,Peng-Ge NING,Hong-Bin CAO,Yi ZHANG. Solubility of NH4VO3 in NH4H2PO4-H2O and (NH4)3PO4-H2O Systems[J]. Acta Physico-Chimica Sinca, 2016, 32(5): 1134-1142.
[14] Hui-Yong WANG,Hong-Pei LI,Guo-Kai CUI,Zhi-Yong LI,Jian-Ji WANG. Recent Progress in Self-Assembly of Ionic Liquid Surfactants and Its Regulation and Control in Aqueous Solutions[J]. Acta Physico-Chimica Sinca, 2016, 32(1): 249-260.
[15] CHEN Jun-Jie, XIAO Qian, Lü Zhan-Peng, AHSAN Ejaz, XIA Xiao-Feng, LIU Ting-Guang. Effects of Sulfate Ions on Anodic Dissolution and Passivity of Iron in Slightly Alkaline Solutions[J]. Acta Physico-Chimica Sinca, 2015, 31(6): 1093-1104.