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Mechanism of the reduction of molecular nitrogen to hydrazine by niobium (iii) hydroxide

  • Physical Chemistry
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Abstract

The effect of the concentration of water on the rate of reduction of molecular nitrogen to hydrazine by niobium(iii) hydroxide in alkaline H2O−MeOH and D2O−MeOD mixtures was studied. In both cases, the reaction rate is maximum when [H2O]=4 mol L−1, and the inverse isotopic effect (K D/k H>1) is observed when [H2O]<20 mol L−1. Similar regularity was observed for the reaction of hydrogen elimination. It was found that HD is formed in the H2O−MeOH system in the presence of D2. The conclusion was made that the ratedetermining stage in hydrazine formation is the transfer of a hydride ion to the dinitrogen molecule coordinated to the binuclear NbIII center. A kinetic scheme satisfactorily explaining the effect of the concentration of water ([H2O]=1.5−49.0 mol L−1) on the reaction rate constant was proposed.

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Authors and Affiliations

  1. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russian Federation

    N. T. Denisov, S. I. Kobeleva & A. F. Shestakov

Authors
  1. N. T. Denisov
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  2. S. I. Kobeleva
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  3. A. F. Shestakov
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Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1600–1604, September, 1997.

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Denisov, N.T., Kobeleva, S.I. & Shestakov, A.F. Mechanism of the reduction of molecular nitrogen to hydrazine by niobium (iii) hydroxide. Russ Chem Bull 46, 1526–1530 (1997). https://doi.org/10.1007/BF02502932

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  • DOI: https://doi.org/10.1007/BF02502932

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