ISSN 1608-4039 (Print)
ISSN 1680-9505 (Online)


For citation:

Romanova V. O., Churikov A. V., Zapsis K. V., Gamayunova I. M., Churikov M. A., Vasil'kov M. Y. The kinetic research of hydrolysis in the systems used in borohydride hydrogen power engineering. Electrochemical Energetics, 2013, vol. 13, iss. 1, pp. 3-11. DOI: 10.18500/1608-4039-2013-13-1-3-11, EDN: RDMWJL

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).
Full text:
(downloads: 118)
Language: 
Russian
Heading: 
Article type: 
Article
EDN: 
RDMWJL

The kinetic research of hydrolysis in the systems used in borohydride hydrogen power engineering

Autors: 
Romanova Veronika Olegovna, Saratov State University
Churikov Aleksei Vladimirovich, Saratov State University
Zapsis Konstantin Vasil'evich, Saratov State University
Gamayunova Irina Mikhailovna, Saratov State University
Churikov Mikhail Alekseevich, Saratov State University
Vasil'kov Mikhail Yur'evich, Saratov State University
Abstract: 

The paper studies the influence of temperature (50–100°C) and alkalinity (C OH – = 2.33–9.53 M) of aqueous solutions on the hydrolysis (self-destruction) kinetics of borohydride ions BH4 Characteristic peculiarities of the kinetic curve have been established and formulae to approximate the temperature-concentration dependence of the hydrolysis rate are proposed. An increase in temperature leads to an increase in the rate constant k of borohydride hydrolysis, and the temperature dependence of k satisfactorily obeys Arrhenius' equation. The influence of solution alkalinity on the borohydride hydrolysis rate was explored. Within the temperature range studied, the k = f(C OH -) curve consists of two fragments, each with the prevalence of one of two different mechanisms (paths) of borohydride hydrolysis. In highly-alkaline aqueous solutions, non-catalytic hydrolysis mainly occurs, whose rate is determined by temperature, being p?-independent. At lower alkalinity, the hydrolysis rate sharply increases due to catalysis by ? + ions. A power dependence of k on the ? + concentration has been found; the point where the mechanisms are switched is determined by temperature.

Reference: 

1. Gardiner J. A., Collat J. W. // J. Amer. Chem. Soc. 1965. Vol. 87. P. 1692–1700.
2. Gardiner J. A., Collat J. W. // Inorg. Chem. 1965. Vol. 4. P. 1208–1212.
3. Wang F. T., Jolly W. L. // Inorg. Chem. 1972. Vol. 11. P. 1933–1941.
4. Levine L. A., Kreevoy M. M. // J. Amer. Chem. Soc. 1972. Vol. 94. P. 3346–3349.
5. Kreevoy M. M., Hutchins JEC. // J. Amer. Chem. Soc. 1972. Vol. 94. P. 6371–6376.
6. Abts L. M., Langland J. T., Kreevoy M. M. // J. Amer. Chem. Soc. 1975. Vol. 97. P. 3181–3185.
7. Прокопчик А. Ю., Шалкаускене Ю. А. // Журн. физ. химии. 1970. Т. 44, № 11. С. 2941.
8. Мочалов К. Н., Хаин В. С., Гильманшин Г. Г. // Кинетика и катализ. 1965. Т. 6. С. 541.
9. Goudon J. P., Bernard F., Renouard J., Yvart P. // Intern. J. Hydrogen Energy. 2010. Vol. 35. P. 11071–11076.
10. Hung A. J., Tsai S. F., Hsu Y. Y., Ku J. R., Chen Y. H., Yu C. C. // Intern. J. Hydrogen Energy. 2008. Vol. 33. P. 6205–6215.
11. Andrieux J., Demirci U. B., Hannauer J., Gervais Ch., Goutaudier Ch., Miele Ph. // Inttern. J. Hydrogen Energy. 2011. Vol. 36. P. 224–233.
12. Чуриков А. В., Запсис К. В., Сычева В. О., Иванищев А. В., Храмков В. В., Чуриков М. А. // Заводская лаборатория. 2011. Т. 77. C. 3–10.
13. Churikov A. V., Zapsis K. V., Khramkov V. V., Churikov M. A., Smotrov M. P., Kazarinov I. A. // J. Chem. and Eng. Data. 2011. Vol. 56, № 1. P. 9–13.
14. Churikov A. V., Zapsis K. V., Khramkov V. V., Churikov M. A., Gamayunova I. M. // J. Chem. and Eng. Data. 2011.Vol. 56, № 3. P. 383–389.
15. Churikov A. V., Zapsis K. V., Ivanishchev A. V., Sychova V. O. // J. Chem. and Eng. Data. 2011. Vol. 56, № 5.P. 2543–2552.
16. Churikov A. V., Ivanishchev A. V., Gamayunova I. M., Ushakov A. V. // J. Chem. and Eng. Data. 2011. Vol. 56, № 11. P. 3984–3993.
17. Дамаскин Б. Б., Петрий О. А., Цирлина Г. А. Электрохимия. М.: Химия, 2001.
18. Отто М. Современные методы аналитической химии / пер. с нем.; под ред. А. В. Гармаша. М.: Техносфера, 2003. Т. 1. С. 53.
19. Churikov A. V., Romanova V. O., Churikov M. A., Gamayunova I. M. // Intern. Review Chem. Eng. (I.RE.CH. E.). 2012. Vol. 4, № 3. P. 263–268.
20. Байрамов В. М. Основы химической кинетики и катализа.М.: Академия, 2003.
21. Churikov A. V., Gamayunova I. M., Zapsis K. V., Churikov M. A., Ivanishchev A. V. // Intern. J. Hydrogen Energy. 2012. Vol. 37, № 1. P. 335–344

Received: 
29.11.2012
Accepted: 
28.02.2013
Published: 
28.02.2013