Citation: YAN Bo, ZHOU Huan, LI Wen-Xuan. Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy[J]. Acta Physico-Chimica Sinica, ;2016, 32(2): 405-414. doi: 10.3866/PKU.WHXB201511192 shu

Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy

YAN Bo ¹ ,
ZHOU Huan ^2,, ,
LI Wen-Xuan ²

1.
1 Tianjin Key Laboratory of Marine Resource and Chemistry, College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, P. R. China;
2.
2 Tianjin Key Laboratory of Marine Resource and Chemistry, College of Chemical Engineering and Materials Sciences, Tianjin University of Science & Technology, Tianjin 300457, P. R. China

Corresponding author: ZHOU Huan,
Received Date: 27 July 2015
Available Online: 16 November 2015
Fund Project: 国家自然科学基金(21176189,U1407204) (21176189,U1407204)天津市应用基础与前沿技术研究计划(15JCYBJC23200) (15JCYBJC23200)教育部科研创新团队培育计划([2013]373) ([2013]373)天津市高等学校创新团队培养计划(TD12-5004)资助项目 (TD12-5004)

Stable and metastable solid-liquid equilibria phenomena and complex salt-forming behaviors exist in complex salt-water systems. To realize the relationship between salt-forming behavior and liquid structure, the characteristics of ion association structures of SO₄^2- in Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O system and its binary, ternary subsystems were studied by Raman spectroscopy, combined with a Gauss-Lorentz peak fitting program. The spectrum experimental results show that there were two ion association structures of SO₄^2- as non-associated SO₄^2- and SO₄^2- groups in the Na₂SO₄-H₂O system, while in the MgSO₄-H₂O, MgSO₄-MgCl₂-H₂O, and Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O systems, there were also Mg²⁺-H₂O-SO₄^2- and Mg²⁺-OSO₃^2- structures. Non-associated SO₄^2- was the main structure in the ν₁-SO₄^2- band of binary (MgSO₄ Na₂SO₄) and ternary (MgSO₄-MgCl₂-H₂O) subsystems, and with varying SO₄^2- concentration, these four types of SO₄^2- ion association structure varied regularly. Likewise, the ion association structures of SO₄^2- in the Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O system changed regularly during both the processes of NaCl crystallization and isothermal evaporation. This was evident when, during the process of decreasing NaCl concentration and increasing MgSO₄, the content of non-associated SO₄^2- decreased, the chance of Mg²⁺-H₂O-SO₄^2- and Mg²⁺-OSO₃^2- structure formation increased, and the SO₄^2- group structure appeared in the astrachanite region. More importantly, the adaptive changes in solution structure during the progress of evaporation can result in the appearance of metastable phenomena. Further linear analysis showed that the concentration and Jänecke index (J) value of SO₄^2- were positively related to the intensity and peak area of the ν₁-SO₄^2- band, and the concentration of Mg²⁺ affected the contents of four ion association structures in the ν₁-SO₄^2- band mainly.
- SO₄^2-,
- Ion association structure,
- Raman spectroscopy,
- Solid-liquid phase equilibrium
1. [1]
  (1) Precht, H.; Cohen, E. Investigations on the Conditions of Formation of Oceanic Salt Deposits, Especially of the Stassfurt Deposit (the Papers of Hoff, V); AkademischeVeriagsgeselischaft m.b.H.: Leipzing, 1912; pp 10-35.
2. [2]
  (2) Voigt, W. Pure Appl. Chem. 2011, 83 (5), 1015.
3. [3]
  (3) Balarew, C.; Karaivanova, V.; Commun.T. Dept. Chem. Bulg. Acad. Sci. 1970, 3, 637.
4. [4]
  (4) Wollmann, G.; Voigt, W. Fluid Phase Equilib. 2010, 291 (2), 151. doi: 10.1016/j.fluid.2009.12.005
5. [5]
  (5) Teeple, J. E. The Industrial Development of Searles Lake Brines, with Equilibrium Data; The Chemical CatalogCompany Inc.: New York, 1929; pp 112-154.
6. [6]
  (6) Kurnakow, N. S.; Nikolaew, V. I. Izv. Sekt. Fiz.-Khim Anal. Akad. Nauk SSSR 1938, 10, 333.
7. [7]
  (7) Jin, Z. M.; Shang, X. Z.; Liang, S. M. Acta Chim. Sin. 1980, 38(4), 313. [金作美, 尚显志, 梁式梅. 化学学报, 1980, 38 (4), 313.]
8. [8]
  (8) Jin, Z. M.; Zhou, H. N.; Wang, L. S. Chem. J. Chin. Univ. 2001, 22 (4), 634. [金作美, 周惠南, 王励生. 高等学校化学学报, 2001, 22 (4), 634.]
9. [9]
  (9) Jin, Z. M.; Zhou, H. N.; Wang L. S. Chem. J. Chin. Univ. 2002, 23 (4), 690. [金作美, 周惠南, 王励生. 高等学校化学学报, 2002, 23 (4), 690.]
10. [10]
  (10) Zhou, H.; Zhang, H. L.; Chen, Y. D. J. Chem. Eng. Data 2012, 57 (3), 943. doi: 10.1021/je201196q
11. [11]
  (11) Zhou, H.; Zhang, J. B.; Zhang, H. L. J. Chem. Eng. Data 2012, 57 (4), 1192. doi: 10.1021/je201239s
12. [12]
  (12) Zhou, H.; Cui, S. G.; Sha, Z. L. Acta Chim. Sin. 2008, 66 (12), 1483. [周桓, 崔世广, 沙作良.化学学报, 2008, 66 (12), 1483.]
13. [13]
  (13) Zhou, H.; Cui, S. G.; Sha, Z. L. Chem. J. Chin. Univ. 2008, 29(10), 2049. [周桓, 崔世广, 沙作良. 高等学校化学学报, 2008, 29 (10), 2049.]
14. [14]
  (14) Zhou, H.; Chen, Y. D.; Kang, Q. Y. Chin. J. Chem. Eng. 2014, 18 (4), 635.
15. [15]
  (15) Zhou, H.; Bao, Y. J.; Bai, X. Q. Fluid Phase Equilibria 2014, 362, 281. doi: 10.1016/j.fluid.2013.10.025
16. [16]
  (16) Zhou, H. Product Sodium Chloride and Epsom Salt by Brine.ZL Patent 200810054198.6. 2010-02-10. [周桓. 用卤水生产氯化钠及七水硫酸镁方法: 中国, ZL 200810054198.6[P].2010-02-10.]
17. [17]
  (17) Fang, C. H.; Fang, Y.; Gou, Y. M.; Yang, B.; Lei, Y. C. Acta Chim. Sin. 2004, 62 (3), 268. [房春晖, 房艳, 郭亚梅, 杨波, 雷亚川. 化学学报, 2004, 62 (3), 268.]
18. [18]
  (18) Rull, F. Pure Appl. Chem. 2002, 74 (10), 1859.
19. [19]
  (19) Tepavitcharova, S.; Balarew, C.; Rull, F. J. Raman Spectrosc. 2005, 36, 891.
20. [20]
  (20) Guo, X.; Chen, S. H.; Shang, Z. J.; Guo, Y. C.; Zhang, Y. H.Acta Phys. -Chim. Sin. 2012, 28 (4), 766. [郭鑫, 陈斯华, 商志军, 郭郁葱, 张韬宏. 物理化学学报, 2012, 28 (4), 766.] doi: 10.3866/PKU.WHXB201202021
21. [21]
  (21) Dong, J. L.; Li, X. H.; Zhao, L. J.; Xiao, H. S.; Wang, F.; Guo, X.; Zhang, Y. H. J. Phys. Chem. B 2007, 111 (10), 12170.
22. [22]
  (22) Zhang, Y. H.; Chan, C. K. J. Phys. Chem. A 2002, 106 (2), 285. doi: 10.1021/jp012694j
23. [23]
  (23) Wang, F.; Zhang, Y. H.; Li, S. H.; Wang, L.Y.; Zhao, L. J. Anal. Chem. 2005, 77 (22), 7148. doi: 10.1021/ac050938g
24. [24]
  (24) Li, X. H.; Zhao, L. J.; Dong, J. L.; Xiao, H. S.; Zhang, Y. H.J. Phys. Chem. B 2008, 112 (16), 5032. doi: 10.1021/jp709938x
25. [25]
  (25) Zhang, H.; Zhang, Y. H.; Wang, F. J. Comput. Chem. 2009, 30(3), 493. doi: 10.1002/jcc.v30:3
26. [26]
  (26) Guo, X.; Shou, J. J.; Zhang, Y. H.; Reid, J. P. Analyst 2010, 135 (3), 495. doi: 10.1039/b918978e
27. [27]
  (27) Syed, K. A.; Pang, S. F.; Zhang, Y.; Zhang, Y. H. J. Chem. Phys. 2013, 138 (2), 024901. doi: 10.1063/1.4773585
28. [28]
  (28) Rudolph, W.W.; Brooker, M. H.; Tremaine, P. R. J. Solution Chem. 1999, 28 (7), 621.
29. [29]
  (29) Hayes, A. C.; Kruus, P.; Adams, W. A. J. Solution Chem. 1984, 13 (1), 61. doi: 10.1007/BF00648592
30. [30]
  (30) Kruus, P.; Hayes, A. C.; Adams, W. A. J. Solution Chem. 1985, 14 (2), 117. doi: 10.1007/BF00648900
31. [31]
  (31) Dong, J. L.; Xiao, H. S.; Zhao, L. J.; Zhang, Y. H. J. Raman Spectrosc. 2009, 40, 338. doi: 10.1002/jrs.v40:3
32. [32]
  (32) Vizcayno, C.; Garcia-Gonzalez, M. T. Acta Crystallogr. Sect. C 1999, 55, 8. doi: 10.1107/S0108270198011135
1. [1]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
2. [2]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
3. [3]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075
4. [4]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
5. [5]
  Jingyi Chen , Fu Liu , Tiejun Zhu , Kui Cheng . Practice of Integrating Ideological and Political Education into Raman Spectroscopy Analysis Experiment Course. University Chemistry, 2024, 39(2): 140-146. doi: 10.3866/PKU.DXHX202310111
6. [6]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
7. [7]
  Zhaoyue Lü , Zhehao Chen , Yi Ni , Duanbin Luo , Xianfeng Hong . Multi-Level Teaching Design and Practice Exploration of Raman Spectroscopy Experiment. University Chemistry, 2024, 39(11): 304-312. doi: 10.12461/PKU.DXHX202402047
8. [8]
  Shuangxi Li , Huijun Yu , Tianwei Lan , Liyi Shi , Danhong Cheng , Lupeng Han , Dengsong Zhang . NO_x reduction against alkali poisoning over Ce(SO₄)₂-V₂O₅/TiO₂ catalysts by constructing the Ce⁴⁺–SO₄²⁻ pair sites. Chinese Chemical Letters, 2024, 35(5): 108240-. doi: 10.1016/j.cclet.2023.108240
9. [9]
  Chongjing Liu , Yujian Xia , Pengjun Zhang , Shiqiang Wei , Dengfeng Cao , Beibei Sheng , Yongheng Chu , Shuangming Chen , Li Song , Xiaosong Liu . Understanding Solid-Gas and Solid-Liquid Interfaces through Near Ambient Pressure X-Ray Photoelectron Spectroscopy. Acta Physico-Chimica Sinica, 2025, 41(2): 100013-. doi: 10.3866/PKU.WHXB202309036
10. [10]
  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
11. [11]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
12. [12]
  Yanhui Zhong , Ran Wang , Zian Lin . Analysis of Halogenated Quinone Compounds in Environmental Water by Dispersive Solid-Phase Extraction with Liquid Chromatography-Triple Quadrupole Mass Spectrometry. University Chemistry, 2024, 39(11): 296-303. doi: 10.12461/PKU.DXHX202402017
13. [13]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
14. [14]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . 钠离子电池中铁基异质结构负极材料的最新研究进展. Acta Physico-Chimica Sinica, 2025, 41(3): 2311015-. doi: 10.3866/PKU.WHXB202311015
15. [15]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-. doi: 10.3866/PKU.WHXB202408007
16. [16]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
17. [17]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
18. [18]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
19. [19]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
20. [20]
  Yutong Dong , Huiling Xu , Yucheng Zhao , Zexin Zhang , Ying Wang . The Hidden World of Surface Tension and Droplets. University Chemistry, 2024, 39(6): 357-365. doi: 10.3866/PKU.DXHX202312022

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(331)
HTML views(29)

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

Studies on the Characteristics and Behaviors of the Ion Association Structures of SO42- in Na+,Mg2+//SO42-, Cl-,H2O System by Raman Spectroscopy

Metrics

通讯作者: 陈斌, bchen63@163.com

Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy