Transition Metal Chemistry

, Volume 21, Issue 6, pp 503–506 | Cite as

The mechanism of directional oxidation of hydrazine by silver coordination compounds

  • Deping Cheng
  • Shijun Xia
  • Jiulu Tong
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Summary

The reactions of different Ag complexes with hydrazine have been studied and it has been shown that a trace amount of CuII ion can increase the rate, greatly raising the percentage of N2 formed by the four-electron oxidation of hydrazine (Reaction 4). In the absence of the CuII ion, the percentage of N2 formed is linearly related to log β2 of the Ag complex. In the presence of the CuII ion, the percentage of N2 formed by the one-electron oxidation of hydrazine is likewise linearly related to 1/log β2:
$$\begin{gathered} 4Ag^ + \left( {AgL_2^{q \pm } } \right) + N_2 H_4 \rightleftharpoons 4Ag + N_2 \hfill \\ {\text{ }} + 4H^{\text{ + }} \left( { + 8L^{\left[ {q \pm \left( { - 1} \right)} \right]/2} } \right) \hfill \\ \hfill \\ \end{gathered} $$
(4)
$$\begin{gathered} 4Ag^ + \left( {AgL_2^{q \pm } } \right) + N_2 H_4 \rightleftharpoons Ag + {1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}N_2 + NH_3 \hfill \\ {\text{ }} + H^{\text{ + }} \left( { + 2L^{\left[ {q \pm \left( { - 1} \right)} \right]/2} } \right) \hfill \\ \end{gathered} $$
(5) A mechanism is proposed in which the first oxidation product is a hydrazyl radical, which further oxidizes or dimerizes. When a catalytic quantity of CuII ion was added to the system, Reaction 4 is accelerated and Reaction 5 inhibited.

Keywords

Oxidation Physical Chemistry Inorganic Chemistry Hydrazine Oxidation Product 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References

  1. (1).
    L. Yiyuan and C. Qingbang, Zhongnan Kuangye Xueyuan Xuebao, 3, 44 (1981).Google Scholar
  2. (2).
    E. M. Jost, US 4456474 (1984); E. M. Jost, Chem. Abstr., 101, 155554 m (1984).Google Scholar
  3. (3).
    X. Shijun, H. Xiaoming and F. Wengye, J. Hangzhou Univ., 3, 342 (1984).Google Scholar
  4. (4).
    F. A. Cotton and G. Wilknson, Advanced Inorganic Chemistry, 5th Edit., Wiley-Interscience, New York, 1988, p. 315.Google Scholar
  5. (5).
    L. Andriech and A. B. Ogg, The Chemistry of Hydrazine, Wiley, New York, 1951.Google Scholar
  6. (6).
    K. K. Sengupta, P. K. Sen and S. Sengupta, Inorg. Chem., 16, 1396 (1977).Google Scholar
  7. (7).
    K. K. Sengupta and P. K. Sen, Inorg. Chem., 18, 979 (1979).Google Scholar
  8. (8).
    K. K. Sengupta and B. Basu, Transition Met. Chem., 8, 3 (1983).Google Scholar
  9. (9).
    D. F. C. Morris and T. J. Piller, J. Chem. Soc., Dalton Trans., 216 (1980).Google Scholar
  10. (10).
    D. M. Stanburg, Inorg. Chem., 23, 2879 (1984).Google Scholar
  11. (11).
    J. W. Cahn and R. E. Powell, J. Am. Chem. Soc., 76, 2568 (1954).Google Scholar
  12. (12).
    Department of Chemistry, Hangzhou University, Handbook of Analytical Chemistry, Chemical and Engineeing Press, Beijing, 1979, vol. 1, p. 60.Google Scholar
  13. (13).
    W. C. E. Higginson, D. Sutton and P. Wright, J. Chem. Soc., 1380 (1953).Google Scholar
  14. (14).
    W. C. E. Higginson and P. Wright, J. Chem. Soc., 1551 (1955).Google Scholar
  15. (15).
    E. Hayon and M. Simic, J. Am. Chem. Soc., 94, 42 (1972).Google Scholar

Copyright information

© Chapman & Hall 1996

Authors and Affiliations

  • Deping Cheng
    • 1
  • Shijun Xia
    • 1
  • Jiulu Tong
    • 1
  1. 1.Department of ChemistryHangzhou UniversityHangzhouPeople's Republic of China

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