SIOC 中文
ACS
Adv search

Acta Chimica Sinica >

2012 , Vol. 0 >Issue 04: 445 - 452

DOI: https://doi.org/10.6023/A1105313

Full Papers

Structure of Aqueous Potassium Tetraborate Solutions

  • Zhu Fayan ,
  • Fang Chunhui ,
  • Fang Yan ,
  • Zhou Yongquan ,
  • Xu Sha ,
  • Tao Song ,
  • Cao Lingdi
Expand
  • a Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008;
    b Graduate University of Chinese Academy of Sciences, Beijing 100049

Received date: 2011-05-31

  Revised date: 2011-08-03

  Online published: 2011-09-26

Supported by

Project supported by Joint Fund for Large Science Project of the National Natural Science Foundation of China and the Chinese Academy of Sciences (No. 11079047) and Main Direction Program of Knowledge Innovation of Chinese Academy of Sciences (No. KZCX2-EW-307).

Fold

Abstract

The pH of aqueous K2B4O7 solutions at 298.15 and 323.15 K at a wide range of concentration has been determined and the chemical species distribution of the solutions calculated from equilibrium constants by Newton iterative algorithm. The chemical species of typical samples were confirmed by Raman spectrum. The results show that the major species B4O5(OH)42? and the minor chemical species B3O3(OH)4? and B(OH)4? exist in highly concentrated aqueous solutions. The structure of highly concentrated aqueous K2B4O7 solutions at 298 and 323 K was studied by X-ray scattering further. The interactions of intra-anion, interionic and intermolecular of B4O5(OH)42?, B3O3(OH)4? and B(OH)4? were descripted quantitatively by geometrical model and calculated by least square method. The model calculation and refinement provided distance and coordination number between atoms in boroxol six-member ring, which are in good agreement with the crystal structure. The order degree in intra-anion is high in concentrated aqueous solutions. At the same time, we gained information about the hydration number and hydration distance of K+, borate ions and contact ion-pair. We also briefly discussed the effect of temperature and concentration on solvent structure.

Key words： potassium tetraborate; solution structure; x-ray scattering; contact ion-pair; chemical species distribution

Cite this article

Zhu Fayan , Fang Chunhui , Fang Yan , Zhou Yongquan , Xu Sha , Tao Song , Cao Lingdi . Structure of Aqueous Potassium Tetraborate Solutions[J]. Acta Chimica Sinica, 2012 , 0(04) : 445 -452 . DOI: 10.6023/A1105313

References

1 Marcus, Y. J. Solution Chem. 1996, 25, 455.  

2 Bakker, H. J.; Skinner, J. L. Chem. Rev. 2010, 110, 1498.  

3 Megyes, T.; Balint, S.; Peter, S.; Grosz, T.; Bako, I.; Krienke, H.; Bellissent-Funel, M. C. J. Phys. Chem. B 2009, 113, 4054.  

4 Fang, C. H. Prog. Chem. 1996, 8, 318 (in Chinese). (房春晖, 化学进展, 1996, 8,318.)

5 Marcus, Y.; Hefter, G. Chem. Rev. 2006, 106, 4585.  

6 Zhou, Y. Q.; Fang, C. H.; Fang, Y. Acta Phys.-Chim. Sin. 2010, 26, 2323 (in Chinese). (周永全, 房春晖, 房艳, 物理化学学报, 2010, 26, 2323.)

7 Liu, Z. H.; Gao, B.; Hu, M. C.; Li, S. N.; Xia, S. P. Spectrochim. Acta, Part A 2003, 59, 2741.  

8 Takekiyo, T.; Yoshimura, Y. J. Phys. Chem. A 2007, 111, 6039.  

9 Li, J.; Xia, S. P.; Gao, S. Y. Spectrochim. Acta 1995, 51A, 519.  

10 Toledano, P. Rev. Chim. Miner. 1964, 1, 372.

11 Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Analysis of Salt and Brine, Science Press, Beijing, 1988, pp. 55～57 (in Chinese). (中国科学院青海盐湖研究所, 卤水和盐的分析方法, 科 学出版社, 北京, 1988, pp. 55～57.)  

12 Xu, J. X.; Fang, Y.; Fang, C. H. Comput. Appl. Chem. 2009, 26, 553 (in Chinese). (徐继香, 房艳, 房春晖, 计算机与应用化学, 2009, 26, 553.)

13 Fang, C. H.; Ma, P. H.; Fang, Y.; Yang, B.; Lei, Y. C. Acta Chim. Sinica 2000, 58, 1393 (in Chinese). (房春晖, 马培华, 房艳, 杨波, 雷亚川, 化学学报, 2000, 58, 1393.)

14 Prince, E. International Tables for Crystallography, Vol. C, 3rd ed., Kluwer Academic Publishers, London, 2004, pp. 230～235; 255; 555～556; 658.

15 Ingri, N. Acta Chem. Scand. 1963, 17, 573.  

16 Spessard, J. E. J. Inorg. Nucl. Chem. 1970, 32, 2607.  

17 Liu, Z. H.; Gao, B.; Li, S. N.; Hu, M. C.; Xia, S. P. Spectrochim. Acta, Part A 2004, 60, 3125.  

18 Christ, C. L.; Clark, J. R. Phys. Chem. Miner. 1977, 2, 59.  

19 Levy, H. A.; Lisensky, G. C. Acta Cryst. 1978, B34, 3502.  

20 Martinez-Ripoll, M.; Martinez-Carrera, S.; Garcia-Blanco, S. Acta Cryst. 1971, B27, 672.  

21 Menchetti, S.; Sabelli, C. Acta Cryst. 1978, B34, 1080.  

22 Ohtomo, N.; Arakawa, K.; Takeuchi, M.; Yamaguchi, T.; Ohtaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 1314.  

23 Impey, R. W.; Maden, P. A.; McDonald, I. R. J. Phys. Chem. 1983, 87, 5071.  

24 Migliore, M.; Fornili, S. L.; Spohr, E.; PBlinkL, G.; Heinzinger, K. Z. Naturforsch 1986, A41, 826.

25 Tongraar, A.; Liedl, K. R.; Rode, B. M. J. Phys. Chem. A 1998, 102, 10340.  
Options
Outlines

/

〈 〉