Citation: ZHOU Liang-Chun, MENG Xiang-Guang, LI Jian-Mei, HU Wei, LIU Bo, DU Juan. Kinetics and Thermodynamics of Adsorption of Chlorophenols onto β-Cyclodextrin Modified Chitosan[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1615-1622. doi: 10.3866/PKU.WHXB201204282 shu

Kinetics and Thermodynamics of Adsorption of Chlorophenols onto β-Cyclodextrin Modified Chitosan

1.
1College of Chemistry, Sichuan University, Chengdu 610064, P. R. China;
2. School of Chemistry and Pharmaceutical Engineering, Sichuan University of Science & Engineering, Zi ng 643000, Sichuan Province, P. R. China

Received Date: 5 March 2012
Available Online: 28 April 2012
Fund Project: 国家自然科学基金(21073126) (21073126)四川省自贡市科学技术局重点基金(10X01)资助项目 (10X01)

β-Cyclodextrin (β-CD) modified chitosan (CS), β-cyclodextrin-6-chitosan (CS-CD), was prepared and subsequently characterized by Fourier transform-infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) analysis. The CS-CD was used as an adsorbent for the adsorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (DCP), and 2,4,6-tuichlorophenol (TCP) from aqueous solutions. The Langmuir and Freundlich models were applied to describe the adsorption isotherms of the chlorophenols. The adsorption parameters have also been evaluated. The calculated maximum adsorption capacities for 2-CP, DCP, and TCP on CS-CD were 14.51, 50.68, and 74.29 mg·g^-1, respectively, indicating that the introduction of the β-CD moiety greatly increased the adsorption efficiency. Kinetic studies showed that the adsorptions were fast, in that all of the adsorption equilibria were reached within one hour, and that the adsorption processes followed a pseudosecond- order kinetic model. The thermodynamic parameters ΔG⁰, ΔH⁰, and ΔS⁰ were also calculated. The negative ΔG⁰ values indicated that all of the adsorption processes were spontaneous. A possible adsorption mechanism has been provided and discussed. The effects of electrolytes and pH values on adsorption revealed that hydrogen bonding between the chlorophenols and CS-CD dominated the adsorption process, which was further confirmed by FT-IR analysis. The adsorbent could be regenerated by washing with ethanol. Following six cycles of usage and regeneration, the mass and adsorption efficiency of the CS-CD remained at 90% and 82%, respectively. CS, however, showed greater mass loss and efficiency reduction following regeneration.
- Chitosan,
- β-Cyclodextrin,
- Adsorption,
- Chlorophenols,
- Thermodynamics,
- Kinetics
1. [1]
  
  (1) Moradi, M.; Yamini, Y.; Esrafili, A.; Seidi, S. Talanta 2010, 82,1864. doi: 10.1016/j.talanta.2010.08.002
2. [2]
  (2) Hamad, B. K.; Noor, A. M.; Afida, A. R.; Asri, M. N. M.Desalination 2010, 257, 1. doi: 10.1016/j.desal.2010.03.007
3. [3]
  (3) Tsutsui, T.; Hayashi, N.; Maizumi, H.; Huff, J.; Barrett, J. C.Mutat. Res-Fund. Mol. M. 1997, 373, 113. doi: 10.1016/S0027-5107(96)00196-0
4. [4]
  (4) Dominguez-Vargas, J. R.; Navarro-Rodriguez, J. A.; de Herediaa,J. B.; Cuerda-Correa, E. M. J. Hazard. Mater. 2009, 169, 302.doi: 10.1016/j.jhazmat.2009.03.075
5. [5]
  (5) Sampa, M. H. D. O.; Rela, P. R.; Las Casas, A.; Mori, M. N.;Duarte, C. L. Radiat. Phys. Chem. 2004, 71, 459. doi: 10.1016/j.radphyschem.2004.03.023
6. [6]
  (6) Jain, S.; Jayaram, R. V. Sep. Sci. Technol. 2007, 42, 2019. doi: 10.1080/15275920701313608
7. [7]
  (7) Hu, Q. H.; Qiao, S. Z.; Haghseresht, F.;Wilson, M. A.; Lu, G.Q. Ind. Eng. Chem. Res. 2006, 45, 733. doi: 10.1021/ie050889y
8. [8]
  (8) Maugans, C. B.; Akgerman, A. Water Res. 2003, 37, 319. doi: 10.1016/S0043-1354(02)00289-0
9. [9]
  (9) Chiou, S. H.;Wu,W. T.; Huang, Y. Y.; Chung, T.W.J. Microencapsul. 2001, 18, 613. doi: 10.1080/02652040010019497
10. [10]
  (10) Chiu, S. H.; Chung, T.W.; Giridhar, R.;Wu,W. T. Food Res. Int. 2004, 37, 217. doi: 10.1016/j.foodres.2003.12.001
11. [11]
  (11) Milhome, M. A. L.; de Keukeleire, D.; Ribeiro, J. P.; Nascimento,R. F.; Carvalho, T. V.; Queiroz, D. C. Quim. Nova 2009, 32,2122. doi: 10.1590/S0100-40422009000800025
12. [12]
  (12) Crini, G.; Badot, P. M. Prog. Polym. Sci. 2008, 33, 399. doi: 10.1016/j.progpolymsci.2007.11.001
13. [13]
  (13) Dotto, G. L., Pinto, L. A. A. J. Hazard. Mater. 2011, 187, 164.doi: 10.1016/j.jhazmat.2011.01.016
14. [14]
  (14) Guibal, E. Sep. Purif. Technol. 2004, 38, 43. doi: 10.1016/j.seppur.2003.10.004
15. [15]
  (15) Zhou, L. M.; Shang, C.; Liu, Z. R. Acta Phys. -Chim. Sin. 2011,27, 677. [周利民, 尚超, 刘峙嵘. 物理化学学报, 2011, 27,677.] doi: 10.3866/PKU.WHXB20110314
16. [16]
  (16) Zheng, J. N.; Xie, H. G.; Yu,W. T.; Liu, X. D.; Xie,W. Y.; Zhu,J.; Ma, X. J. Langmuir 2010, 26, 17156. doi: 10.1021/la1030203
17. [17]
  (17) Zhang, X. Y.;Wang, Y. T.; Yi, Y. J. Appl. Polym. Sci. 2004, 94,860. doi: 10.1002/app.20759
18. [18]
  (18) Prabaharan, M.; Mano, J. F. Carbohyd. Polym. 2006, 63, 153.doi: 10.1016/j.carbpol.2005.08.051
19. [19]
  (19) Sharma, A. K.; Mishra, A. K. Int. J. Biol. Macromol. 2010, 47,410. doi: 10.1016/j.ijbiomac.2010.06.012
20. [20]
  (20) Hall, L. D.; Yalpani, M. Carbohyd. Res. 1980, 83, C5.
21. [21]
  (21) Ozmen, E. Y.; Sezgin, M.; Yilmaz, A.; Yilmaz, M. Bioresource Technol. 2008, 99, 526. doi: 10.1016/j.biortech.2007.01.023
22. [22]
  (22) Li, J. M.; Meng, X. G.; Hu, C.W.; Du, J. Bioresource Technol.2009, 100, 1168. doi: 10.1016/j.biortech.2008.09.015
23. [23]
  (23) Wang, H.; Fang, Y.; Ding, L. P.; Gao, L. N.; Hu, D. D. Thin Solid Films 2003, 440, 255. doi: 10.1016/S0040-6090(03)00812-5
24. [24]
  (24) Dubois, M.; Gilles, K. A.; Hamilton, J. K.; Rebers, P. A.; Smith,F. Anal. Chem. 1956, 28, 350. doi: 10.1021/ac60111a017
25. [25]
  (25) Ghiaci, M.; Abbaspur, A.; Kia, R.; Seyedeyn-Azad, F. Sep. Purif. Technol. 2004, 40, 217. doi: 10.1016/j.seppur.2004.03.001
26. [26]
  (26) Ma, J.W.;Wang, H.;Wang, F. Y.; Huang, Z. H. Sep. Sci. Technol. 2010, 45, 2329. doi: 10.1080/01496395.2010.504482
27. [27]
  (27) Wu, X. B.;Wu, D. C.; Fu, R.W. J. Hazard. Mater. 2007, 147,1028. doi: 10.1016/j.jhazmat.2007.01.139
28. [28]
  (28) Chen, C. Y.; Chen, C. C.; Chung, Y. C. Bioresource Technol.2007, 98, 2578. doi: 10.1016/j.biortech.2006.09.009
29. [29]
  (29) Alkaram, U. F.; Mukhlis, A. A.; Al-Dujaili, A. H. J. Hazard. Mater. 2009, 169, 324. doi: 10.1016/j.jhazmat.2009.03.153
30. [30]
  (30) Ho, Y. S.; McKay, G. Water Res. 2000, 34, 735. doi: 10.1016/S0043-1354(99)00232-8
31. [31]
  (31) Feng, Y. J.; Zhang, Z. H.; Gao, P.; Su, H.; Yu, Y. L.; Ren, N. Q.J. Hazard. Mater. 2010, 175, 970. doi: 10.1016/j.jhazmat.2009.10.105
32. [32]
  (32) Sheng, G. D.; Shao, D. D.; Ren, X. M.;Wang, X. Q.; Li, J. X.;Chen, Y. X.;Wang, X. K. J. Hazard. Mater. 2010, 178, 505. doi: 10.1016/j.jhazmat.2010.01.110
33. [33]
  (33) Pan, J. M.; Zou, X. H.;Wang, X.; Guan,W.; Yan, Y. S.; Han, J.A. Chem. Eng. J. 2010, 162, 910. doi: 10.1016/j.cej.2010.06.039
34. [34]
  (34) Liu, Y. J. Chem. Eng. Data 2009, 54, 1981. doi: 10.1021/je800661q
35. [35]
  (35) Liu, Q. S.; Zheng, T.;Wang, P.; Jiang, J. P.; Li, N. Chem. Eng. J.2010, 157, 348. doi: 10.1016/j.cej.2009.11.013
36. [36]
  (36) Hamdaoui, O.; Naffrechoux, E. J. Hazard. Mater. 2007, 147,401. doi: 10.1016/j.jhazmat.2007.01.023
1. [1]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
2. [2]
  Dong-Bing Cheng , Junxin Duan , Haiyu Gao . Experimental Teaching Design on Chitosan Extraction and Preparation of Antibacterial Gel. University Chemistry, 2024, 39(2): 330-339. doi: 10.3866/PKU.DXHX202308053
3. [3]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
4. [4]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
5. [5]
  Jing Wang , Pingping Li , Yuehui Wang , Yifan Xiu , Bingqian Zhang , Shuwen Wang , Hongtao Gao . Treatment and Discharge Evaluation of Phosphorus-Containing Wastewater. University Chemistry, 2024, 39(5): 52-62. doi: 10.3866/PKU.DXHX202309097
6. [6]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
7. [7]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
8. [8]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
9. [9]
  Xiaohui Li , Ze Zhang , Jingyi Cui , Juanjuan Yin . Advanced Exploration and Practice of Teaching in the Experimental Course of Chemical Engineering Thermodynamics under the “High Order, Innovative, and Challenging” Framework. University Chemistry, 2024, 39(7): 368-376. doi: 10.3866/PKU.DXHX202311027
10. [10]
  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
11. [11]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093
12. [12]
  Ruming Yuan , Pingping Wu , Laiying Zhang , Xiaoming Xu , Gang Fu . Patriotic Devotion, Upholding Integrity and Innovation, Wholeheartedly Nurturing the New: The Ideological and Political Design of the Experiment on Determining the Thermodynamic Functions of Chemical Reactions by Electromotive Force Method. University Chemistry, 2024, 39(4): 125-132. doi: 10.3866/PKU.DXHX202311057
13. [13]
  Jinfu Ma , Hui Lu , Jiandong Wu , Zhongli Zou . Teaching Design of Electrochemical Principles Course Based on “Cognitive Laws”: Kinetics of Electron Transfer Steps. University Chemistry, 2024, 39(3): 174-177. doi: 10.3866/PKU.DXHX202309052
14. [14]
  Yeyun Zhang , Ling Fan , Yanmei Wang , Zhenfeng Shang . Development and Application of Kinetic Reaction Flasks in Physical Chemistry Experimental Teaching. University Chemistry, 2024, 39(4): 100-106. doi: 10.3866/PKU.DXHX202308044
15. [15]
  Xuzhen Wang , Xinkui Wang , Dongxu Tian , Wei Liu . Enhancing the Comprehensive Quality and Innovation Abilities of Graduate Students through a “Student-Centered, Dual Integration and Dual Drive” Teaching Model: A Case Study in the Course of Chemical Reaction Kinetics. University Chemistry, 2024, 39(6): 160-165. doi: 10.3866/PKU.DXHX202401074
16. [16]
  Dexin Tan , Limin Liang , Baoyi Lv , Huiwen Guan , Haicheng Chen , Yanli Wang . Exploring Reverse Teaching Practices in Physical Chemistry Experiment Courses: A Case Study on Chemical Reaction Kinetics. University Chemistry, 2024, 39(11): 79-86. doi: 10.12461/PKU.DXHX202403048
17. [17]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
18. [18]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
19. [19]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458
20. [20]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047

Get Citation

PDF

XML

Metrics

PDF Downloads(795)
Abstract views(3066)
HTML views(35)

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