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Understanding the Different Steps of Surfactant Adsorption at the Oil–Water Interface with Second Harmonic Generation

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† Laboratory of Environmental Science and Technology, Xinjiang Technical Institute of Physics & Chemistry; Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, China
‡ University of Chinese Academy of Sciences, Beijing 100049, China
*E-mail: [email protected] (W.G.).
Cite this: J. Phys. Chem. C 2016, 120, 12, 6515–6523
Publication Date (Web):March 21, 2016
https://doi.org/10.1021/acs.jpcc.5b11278
Copyright © 2016 American Chemical Society
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Abstract

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Probing the behavior of surfactants at oil–water interfaces is crucial to understand their functionality. In this work, we present detection of the adsorption of several common surfactants at the hexadecane–water interface with second harmonic generation (SHG) and zeta potential measurements. Water molecules were used as reliable indicators of the adsorption of ionic surfactants in SHG analysis. With the change of the interfacial potential monitored by both SHG and zeta potential measurements, unique information about the multiple steps involved in the adsorption of typical surfactants at the oil–water interface is provided. It was revealed that the adsorption of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) at the hexadecane–water interface is initialled by a step dominated by the adsorption of the hydrophobic part of the surfactant, and a latter step involves comparable contributions from both the hydrophobic part and the counterion. The adsorption free energies involved in the initial step can be quantitatively analyzed. In addition, the adsorption of two oil-soluble amphiphiles at the hexadecane–water interface was also studied. Analysis of the ionic strength dependent SHG signal at the hexadecane–water interface also reveals that the origin of the SHG emission is mainly the water molecules at the interfacial layer. The preferential orientation of water molecules is with the hydrogen atoms pointing to the oil phase.

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  • The flaw of cylindrical cells in TIR-SHG measurements and the elimination of the flaw with square cells, the fitting of the SHG data, and the calculation of the interfacial charge density with the Graham equation (PDF)

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This article is cited by 24 publications.

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  13. Amit Kumar, Ajay Mandal. Evaluation of Zwitterionic Surfactant for Applicability in Enhanced Oil Recovery. 2019,,https://doi.org/10.2118/194676-MS
  14. Shun-li Chen, Xue-feng Zhu, Fang-yuan Yang, Xue-cong Pan, Wei Gan, Qun-hui Yuan. Order-Disorder transition of carboxyl terminated chains in polydiacetylenes vesicles probed by second harmonic generation and two-photon fluorescence. Chinese Journal of Chemical Physics 2018, 31 (3) , 269-276. https://doi.org/10.1063/1674-0068/31/cjcp1712238
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  16. Yuanzhen Liang, Si Zhang, Wei Wu, Fangyuan Yang, Wei Gan, Hangzhong Jia, Shunli Chen, Xuefeng Zhu, Qunhui Yuan. Lyophobicity may not be the main driving force for long chain surfactants from the bulk phase to the interface. Physical Chemistry Chemical Physics 2018, 20 (15) , 10165-10172. https://doi.org/10.1039/C7CP07322D
  17. Wenjing Dong, Dejun Sun, Yujiang Li, Tao Wu. Rapid removal and recovery of emulsified oil from ASP produced water using in situ formed magnesium hydroxide. Environmental Science: Water Research & Technology 2018, 4 (4) , 539-548. https://doi.org/10.1039/C7EW00568G
  18. Neha Saxena, Nilanjan Pal, Keka Ojha, Swapan Dey, Ajay Mandal. Synthesis, characterization, physical and thermodynamic properties of a novel anionic surfactant derived from Sapindus laurifolius. RSC Advances 2018, 8 (43) , 24485-24499. https://doi.org/10.1039/C8RA03888K
  19. Kyle S. Gustafson, Guoxi Xu, Karl F. Freed, Jian Qin. Image method for electrostatic energy of polarizable dipolar spheres. The Journal of Chemical Physics 2017, 147 (6) , 064908. https://doi.org/10.1063/1.4997620
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  21. Sourav Palchowdhury, B.L. Bhargava. Insights into the structure and dynamics at the hexadecane droplet–water interface in the presence of 1-alkanols as emulsifiers: Molecular dynamics studies. Journal of Molecular Liquids 2017, 234 , 249-259. https://doi.org/10.1016/j.molliq.2017.03.082
  22. Fangyuan Yang, Wei Wu, Shunli Chen, Wei Gan. The ionic strength dependent zeta potential at the surface of hexadecane droplets in water and the corresponding interfacial adsorption of surfactants. Soft Matter 2017, 13 (3) , 638-646. https://doi.org/10.1039/C6SM02174C
  23. Wei Gan, Wei Wu, Fangyuan Yang, Deping Hu, Hui Fang, Zhenggang Lan, Qunhui Yuan. The behavior of hydroxide and hydronium ions at the hexadecane–water interface studied with second harmonic generation and zeta potential measurements. Soft Matter 2017, 13 (43) , 7962-7968. https://doi.org/10.1039/C7SM00813A
  24. Li-bo Zhang, Hui Fang, Shun-li Chen, Xue-feng Zhu, Wei Gan. Orientation Angle of Molecules at Hexadecane-Water Interface Studied with Total Internal Reflection Second Harmonic Generation. Chinese Journal of Chemical Physics 2016, 29 (6) , 650-656. https://doi.org/10.1063/1674-0068/29/cjcp1605111

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