Citation: Gao Zhen, Huang Kun, Du Lin, Liu Huizhou. Interfacial Behavior of Acidic Organophosphorus Extractant Monolayer at Air-Water Interface: Subphase pH and Spreading Solvent Effect[J]. Acta Chimica Sinica, ;2019, 77(6): 506-514. doi: 10.6023/A19010006 shu

Interfacial Behavior of Acidic Organophosphorus Extractant Monolayer at Air-Water Interface: Subphase pH and Spreading Solvent Effect

Gao Zhen ^a,d ,
Huang Kun ^b,, ,
Du Lin ^c ,
Liu Huizhou ^a

a.
Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190
b.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083
c.
Environment Research Institute, Shandong University, Qingdao 266237
d.
School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Huang Kun, huangkun@ustb.edu.cn
Received Date: 2 January 2019
Available Online: 18 June 2019
Fund Project: the National Natural Science Foundation of China 51074150the National Natural Science Foundation of China 51574213Project supported by the National Natural Science Foundation of China (Nos. 51574213, 51074150)

Figures(9)

The interfacial properties of extractant molecules have a significant impact on their complexation reaction activity with rare earth ions at liquid-liquid interface during solvent extraction. Although it is known that acidic organophosphorus extractant exists mainly in the form of dimers in nonpolar organic solvent, the research on solvent extraction kinetics has pointed out that the extractant molecules should react with rare earth ions in the form of monomers at the interface. Therefore, understanding the existing forms of acidic organophosphorus extractant at the interface will help comprehend the interfacial reaction process in solvent extraction. Traditionally, the interfacial properties of the extractant molecules were investigated by measuring interfacial tension isotherms and calculating interfacial adsorption parameters. However, this method can not provide the information of interfacial active species and the aggregation behavior of them. In order to clarify the characteristics of the interfacial behavior of organic extractant molecules at the interface, the effect of subphase pH and the polarity of spreading organic solvent on the adsorption and aggregation behavior of P507 molecules at the air-water interface were investigated by surface pressure-area isotherms and infrared reflectance absorption spectroscopy (IRRAS) based on Langmuir monolayer technique. It was found that P507 monolayers spread by n-hexane at the air-water interface had a certain solubility in the subphase water due to the ionization of the polar groups of P507 molecules. And the solubility decreased as the subphase pH decreased. Thus, the surface pressure-area isotherms changed significantly due to the total amount of P507 molecules remaining on the surface of water changed with the subphase pH. When the subphase pH decreased below 2.0, the influence of the solubility of P507 molecules became inapparent and the amount of P507 molecules remaining on the surface water was almost unchanged. The intermolecular hydrogen bonds formed between the polar groups due to the protonation degree of P507 monolayers improved and the hydration ability of P507 polar groups was weakened. The aggregates formed in the monolayer were confirmed by the red shift of P-O-H groups in IRRAS spectra. However, when the P507 monolayers were spread by polar organic solvent (dichloromethane and chloroform), the existing forms of P507 molecules in the monolayers were changed with the polarity of spreading solvent. And the π-A isotherms of P507 monolayers didn't exhibit the shrinkage of molecular area which existed in the monolayers spread by n-hexane when subphase pH decreased. It meant that the existing forms and aggregation behavior of P507 molecules in monolayers could be altered by the spreading solvent and more P507 monomers existed in the monolayer as the polarity of spreading solvent increased. The conclusion was confirmed by the shift of the peak positions of P-O-H with the spreading solvent in IRRAS spectra. The present work highlights the significant influence of the existing forms of P507 molecules on the interfacial properties of P507 monolayer at the air-water interface and the aggregation behavior in the monolayers can be changed by subphase pH and the spreading solvent.
- P507,
- monolayer,
- air-water interface,
- aggregation behavior,
- surface pressure-area isotherm
1. [1]
  Jha, M. K.; Kumari, A.; Panda, R.; Kumar, J. R.; Yoo, K.; Lee, J. Y. Hydrometallurgy 2016, 165, 2. doi: 10.1016/j.hydromet.2016.01.035
2. [2]
  He, Y.; Chen, K.; Srinivasakannan, C.; Li, S.; Yin, S.; Peng, J.; Guo, S.; Zhang, L. Chem. Eng. J. 2018, 354, 1068. doi: 10.1016/j.cej.2018.07.193
3. [3]
  Qiao, B. F.; Muntean, J. V.; de la Cruz, M. O.; Ellis, R. J. Langmuir 2017, 33, 6135. doi: 10.1021/acs.langmuir.7b01230
4. [4]
  Chen, K.; He, Y.; Srinivasakannan, C.; Li, S.; Yin, S.; Peng, J.; Guo, S.; Zhang, L. Chem. Eng. J. 2019, 356, 453. doi: 10.1016/j.cej.2018.09.039
5. [5]
  Miyake, Y.; Matsuyama, H.; Nishida, M.; Nakai, M.; Nagase, N.; Teramoto, M Hydrometallurgy 1990, 23, 19.
6. [6]
  Vandegrift, G. F.; Horwitz, E. P. J. Inorg. Nuck. Chem. 1980, 42, 119. doi: 10.1016/0022-1902(80)80056-X
7. [7]
  Kanki, T.; Kim, H.; Tomita, A.; Asano, T.; Sano, N. Sep. Purif. Technol. 2000, 19, 93. doi: 10.1016/S1383-5866(99)00081-7
8. [8]
  Shen, J. L.; Xi, Z. K.; Gao, Z. L.; Sun, S. X.; Song, Q. S.; Guo, L. Q. Chin. J. Appl. Chem. 1984, 4, 57.
9. [9]
  Su, W. R.; Chen, J. Ind. Eng. Chem. Res. 2016, 55, 8424. doi: 10.1021/acs.iecr.6b01709
10. [10]
  Wang, W. T.; Ye, S. J. Phys. Chem. Chem. Phys. 2017, 19, 4488. doi: 10.1039/C6CP07827C
11. [11]
  Zhang, T.; Cathcart, M. G.; Vidalis, A. S.; Allen, H. C. Chem. Phys. Lipids 2016, 200, 24. doi: 10.1016/j.chemphyslip.2016.06.001
12. [12]
  Chen, Y. Y.; Sun, R. G.; Wang, F. Y.; Pan, Q. Acta Chim. Sinica 2011, 69, 2299.
13. [13]
  Zhang, B. B.; Ma, C.; Wang, X. G.; Hu, M. B.; Wang, X. L.; Wang, W. Acta Chim. Sinica 2015, 73, 441. doi: 10.3866/PKU.WHXB201412301
14. [14]
  Zhang, T.; Brantley, S. L.; Verreault, D.; Dhankani, R.; Corcelli, S. A.; Allen, H. C. Langmuir 2018, 34, 530. doi: 10.1021/acs.langmuir.7b03579
15. [15]
  Adams, E. M.; Wellen, B. A.; Thiraux, R.; Reddy, S. K.; Vidalis, A. S.; Paesani, F.; Allen, H. C. Phys. Chem. Chem. Phys. 2017, 19, 10481. doi: 10.1039/C7CP00167C
16. [16]
  Song, C. S.; Ye, R. Q.; Mu, B. Z. Acta Chim. Sinica 2009, 67, 2038. doi: 10.3321/j.issn:0567-7351.2009.17.016
17. [17]
  Fang, L. M. M.S. Thesis, Harbin University of Science and Technology, Harbin, 2013.
18. [18]
  Li, S. Y.; Du, L.; Tsona, N. T.; Wang, W. X. Chemosphere 2018, 196, 323. doi: 10.1016/j.chemosphere.2017.12.157
19. [19]
  Adams, E. M.; Verreault, D.; Jayarathne, T.; Cochran, R. E.; Stone, E. A.; Allen, H. C. Phys. Chem. Chem. Phys. 2016, 18, 32345. doi: 10.1039/C6CP06887A
20. [20]
  Yang, H. W.; Zhu, P. X.; Feng, Y. J.; Chen, Z.; Zhou, D. L.; Wu, D. C. Acta Chim. Sinica 2007, 65, 2081.
21. [21]
  Uphaus, R. A.; Vandegrift, G. F.; Horwitz, E. P. J. Colloid Interface Sci. 1982, 90, 380. doi: 10.1016/0021-9797(82)90306-X
22. [22]
  Gershfeld, N. L.; Pak, C. Y. J. Colloid Interface Sci. 1967, 23, 215. doi: 10.1016/0021-9797(67)90105-1
23. [23]
  Zhang, L. R.; Chen, S. M.; Jin, D. S.; Motoko, U.; Tisato, K. Acta Chim. Sinica 1992, 50, 868.
24. [24]
  Zeng, Z. X.; Chen, Q.; Xue, W. L.; Nie, F. Chin. J. Chem. Eng. 2004, 12, 263.
25. [25]
  Yao, Y. L.; Zeng, Z. X.; Xue, W. L.; Huang, S. D. Acta Chim. Sinica 2005, 63, 1939. doi: 10.3321/j.issn:0567-7351.2005.21.001
26. [26]
  Cratin, P. D. J. Dispersion Sci. Technol. 1993, 14, 559. doi: 10.1080/01932699308943427
27. [27]
  Binghua, Y.; Nagaosa, Y.; Satake, M.; Nomura, A.; Horita, K. Solvent Extr. Ion Exch. 1996, 14, 849. doi: 10.1080/07366299608918372
28. [28]
  Petty, M. C. Langmuir-Blodgett films:An introduction, Cambridge University Press, Cambridge, 1996, pp. 55~57.
29. [29]
  Guennouni, Z.; Cousin, F.; Faure, M. C.; Perrin, P.; Limagne, D.; Konovalov, O.; Goldmann, M. Langmuir 2016, 32, 1971. doi: 10.1021/acs.langmuir.5b02652
30. [30]
  Ibrahim, T. H. Sep. Sci. Technol. 2011, 46, 2157. doi: 10.1080/01496395.2011.594478
31. [31]
  Sun, G. X.; Yang, Y. H.; Bao, M.; Cui, Y.; Sun, S. X. J. Inorg. Chem. 1996, 2, 212. doi: 10.3321/j.issn:1001-4861.1996.02.021
32. [32]
  Kusaka, R.; Watanabe, M. Phys. Chem. Chem. Phys. 2018, 20, 29588. doi: 10.1039/C8CP04558E
33. [33]
  Nukada, K.; Naito, K.; Maeda, U. Bull. Chem. Soc. Jpn. 1960, 33, 894. doi: 10.1246/bcsj.33.894
34. [34]
  Wu, J. G.; Shi, N.; Gao, H. C.; Chen, D.; Guo, H.; Weng, S. F.; Xu, G. X. Sci. China, Ser. B 1983, 12, 1071.
35. [35]
  Xu, Z. H.; Wong, S. F.; Guo, H.; Wu, J. G.; Xu, G. X. Acta Sci. Nat. Univ. Pekin. 1983, 6, 45.
36. [36]
  Zhang, C.; Wang, L.; Huang, X.; Dong, J.; Long, Z.; Zhang, Y. Hydrometallurgy 2014, 147, 7.
37. [37]
  Ta, A. T.; Hegde, G. A.; Etz, B. D.; Baldwin, A. G.; Yang, Y.; Shafer, J. C.; Jensen, M. P.; Maupin, C. M.; Vyas, S. J. Phys. Chem. B 2018, 122, 5999. doi: 10.1021/acs.jpcb.8b03165
1. [1]
  Fang Niu , Rong Li , Qiaolan Zhang . Analysis of Gas-Solid Adsorption Behavior in Resistive Gas Sensing Process. University Chemistry, 2024, 39(8): 142-148. doi: 10.3866/PKU.DXHX202311102
2. [2]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
3. [3]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
4. [4]
  Chunai Dai , Yongsheng Han , Luting Yan , Zhen Li , Yingze Cao . Ideological and Political Design of Solid-liquid Contact Angle Measurement Experiment. University Chemistry, 2024, 39(2): 28-33. doi: 10.3866/PKU.DXHX202306065
5. [5]
  Jiao CHEN , Yi LI , Yi XIE , Dandan DIAO , Qiang XIAO . Vapor-phase transport of MFI nanosheets for the fabrication of ultrathin b-axis oriented zeolite membranes. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 507-514. doi: 10.11862/CJIC.20230403
6. [6]
  Xinyu ZENG , Guhua TANG , Jianming OUYANG . Inhibitory effect of Desmodium styracifolium polysaccharides with different content of carboxyl groups on the growth, aggregation and cell adhesion of calcium oxalate crystals. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1563-1576. doi: 10.11862/CJIC.20230374
7. [7]
  Lan Ma , Cailu He , Ziqi Liu , Yaohan Yang , Qingxia Ming , Xue Luo , Tianfeng He , Liyun Zhang . Magical Surface Chemistry: Fabrication and Application of Oil-Water Separation Membranes. University Chemistry, 2024, 39(5): 218-227. doi: 10.3866/PKU.DXHX202311046
8. [8]
  Xinlong WANG , Zhenguo CHENG , Guo WANG , Xiaokuen ZHANG , Yong XIANG , Xinquan WANG . Enhancement of the fragile interface of high voltage LiCoO₂ by surface gradient permeation of trace amounts of Mg/F. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 571-580. doi: 10.11862/CJIC.20230259
9. [9]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
10. [10]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
11. [11]
  Congying Lu , Fei Zhong , Zhenyu Yuan , Shuaibing Li , Jiayao Li , Jiewen Liu , Xianyang Hu , Liqun Sun , Rui Li , Meijuan Hu . Experimental Improvement of Surfactant Interface Chemistry: An Integrated Design for the Fusion of Experiment and Simulation. University Chemistry, 2024, 39(3): 283-293. doi: 10.3866/PKU.DXHX202308097
12. [12]
  Laiying Zhang , Yinghuan Wu , Yazi Yu , Yecheng Xu , Haojie Zhang , Weitai Wu . Innovation and Practice of Polymer Chemistry Experiment Teaching for Non-Polymer Major Students of Chemistry: Taking the Synthesis, Solution Property, Optical Performance and Application of Thermo-Sensitive Polymers as an Example. University Chemistry, 2024, 39(4): 213-220. doi: 10.3866/PKU.DXHX202310126
13. [13]
  Yang YANG , Pengcheng LI , Zhan SHU , Nengrong TU , Zonghua WANG . Plasmon-enhanced upconversion luminescence and application of molecular detection. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 877-884. doi: 10.11862/CJIC.20230440
14. [14]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
15. [15]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
16. [16]
  Shule Liu . Application of SPC/E Water Model in Molecular Dynamics Teaching Experiments. University Chemistry, 2024, 39(4): 338-342. doi: 10.3866/PKU.DXHX202310029
17. [17]
  Rui Gao , Ying Zhou , Yifan Hu , Siyuan Chen , Shouhong Xu , Qianfu Luo , Wenqing Zhang . Design, Synthesis and Performance Experiment of Novel Photoswitchable Hybrid Tetraarylethenes. University Chemistry, 2024, 39(5): 125-133. doi: 10.3866/PKU.DXHX202310050
18. [18]
  Wenbing Hu , Jin Zhu . Flipped Classroom Approach in Teaching Professional English Reading and Writing to Polymer Graduates. University Chemistry, 2024, 39(6): 128-131. doi: 10.3866/PKU.DXHX202310015
19. [19]
  Shicheng Yan . Experimental Teaching Design for the Integration of Scientific Research and Teaching: A Case Study on Organic Electrooxidation. University Chemistry, 2024, 39(11): 350-358. doi: 10.12461/PKU.DXHX202408036
20. [20]
  Yanhui Sun , Junmin Nan , Guozheng Ma , Xiaoxi Zuo , Guoliang Li , Xiaoming Lin . Exploration and Teaching Practice of Ideological and Political Elements in Interface Physical Chemistry: Taking “Additional Pressure on Curved Surfaces” as an Teaching Example. University Chemistry, 2024, 39(11): 20-27. doi: 10.3866/PKU.DXHX202402023

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(1007)
HTML views(152)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142