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Mechanism of the oxidation of hydrazoic acid by tetrachloroaurate(III) ion

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Abstract

The oxidation of hydrazoic acid in perchloric acid in the absence of added chloride under pseudo first-order conditions ([HN3] » [AuCl −4 ]) is first order in [Au(III)]. Michaelis–Menten type of dependence (linear plots of k −1obs vs [HN3]−1) is observed with respect to [HN3]. The k obs is independent of ionic strength and the plot between k −1obs and [H+] is linear. The inner-sphere mechanism is consistent with the formation of an axial complex (K = 25 dm3 mol−1) between AuCl3(HO)− ion and HN3 prior to its rate determining decomposition (k = 0.0182 s−1). It is inferred that the free radicals N •3 do not oxidise Au(II). The reaction becomes outer-sphere in the presence of added Cl− ions which are inferred to form a cage around the hydronium ion surrounding the AuCl −4 ions. The penetration of N −3 through the cage is rate controlling and within the cage, the electron transfer from N −3 ion to AuCl −4 is fast. The value of the rate determining constant k 2 is 0.547 dm3 mol−1 s−1 and the equilibrium constant K Cl for the cage formation is 5 dm3 mol−1 at 25 °C. It is calculated that the minimum HN3 concentration required before the reaction exhibits zero-order dependence in HN3 is 0.31 mol dm−3 when [H+] = 0.18 mol dm−3 at 25 °C.

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Notes

  1. The instrument having no facility for maintaining the constant temperature was not used for the kinetic study.

  2. In making the calculations [Cl−] equal to the initial gold(III) complex is assumed to be present.

  3. $$ [\hbox{AuCl}_{3}(\hbox{H}_{2}\hbox{O})\hbox{N}_{3}^{-}] =\frac{KK_{\rm a}[\hbox{AuCl}_{3}(\hbox{H}_{2}\hbox{O})][\hbox{HN}_{3}]} {[\hbox{H}^{+}]}=\frac{K_1 K_{\rm H}[\hbox{AuCl}_{3}(\hbox{H}_{2} \hbox{O})][\hbox{HN}_{3}]}{[\hbox{H}^{+}]} $$

  4. The rates reported for the corresponding reaction with IrCl 3−6 in [11] were measured at the Centre for Fast Kinetics Research at the University of Texas at Austin.

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Acknowledgements

Thanks are due to the UGC, F.12-59/1997 and F.12-147/2001, for the financial support of the work. Thanks are also due to Kriti Mehrotra, my grand daughter, at Cornell University, in helping with certain references.

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  1. Department of Chemistry, JNV University, Jodhpur, 342 005, India

    Vimal Soni & Raj N. Mehrotra

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  1. Vimal Soni
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Correspondence to Raj N. Mehrotra.

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Soni, V., Mehrotra, R.N. Mechanism of the oxidation of hydrazoic acid by tetrachloroaurate(III) ion. Transition Met Chem 33, 367–376 (2008). https://doi.org/10.1007/s11243-007-9052-9

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