H2o2 o2

According to this mechanism, most of the nitrogen in the hydrazine would form N2, which would not have been detected in this system. The diazene HN=NH would be expected to react with OH radicals:

and ultimately form N2 and H202 via reactions (96)—(98).

Interestingly, this reaction has been used as a non-photolytic OH source for kinetic studies because of the production of OH in the initial reaction (92) between 03 and N2H4 (Tuazon et al., 1983a).

Figure 6.21 shows an FTIR spectrum taken during the studies by Tuazon et al. (1981) of the reaction of CH3NHNH2 with 03 (the absorption bands from NH3 which form from the slow decay of the hydrazine in the dark have been subtracted from the spectra). After initial injection of 03, with the hydrazine present in excess, the observed products were methyl hydroperoxide (CH3OOH), diazomethane (CH2N2), H202, meth-yldiazene (CH3N=NH), HCHO, CH3OH, and traces of CH30N02. After a second injection of 03 into the system so that 03 was in excess, CH3N=NH and CH2N2 disappear, and higher yields of CH3OOH, CH3OH, and HCHO result. Ninety-two percent of the initial carbon atoms could be accounted for in the

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FIGURE 6.21 FTIR spectra taken during reaction of CH3NHNH2 with 03: (a) 3.68 ppm CH3NHNH2 before reaction; (b) 2 min after injection of 2.8 ppm 03; (c) 2.8 ppm 03 injected 38 min after first injection (spectrum taken 2 min after second injection). NH3 absorptions have been subtracted from (a) and (b), and both NH3 and 03 absorptions from (c) (adapted from Tuazon et al, 1981).


800 1000 1200 2000 Wavenumber (cm"1)

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