Methyl peroxy nitrate

Alkyl peroxy nitrates ro2no2 CH302N02, methyl peroxynitrate... 

Attention has been given to possible adverse effects of incorporating tert-butyl methyl ether into antomobile fuels. tert-Butyl formate is an established product of photolysis, and it has been shown that photolysis in the presence of NO can produce the relatively stable tert-butoxyformyl peroxynitrate. This has a stability comparable to that of peroxy-acetyl nitrate, and may therefore increase the potential for disseminating NO (Kirchner et al. 1997). 

Photolytic. When synthetic air containing gaseous nitrous acid and 2-methylbutane was exposed to artificial sunlight (X = 300-450 nm), acetone, acetaldehyde, methyl nitrate, peroxy-acetal nitrate, propyl nitrate, and pentyl nitrate were formed (Cox et al, 1980). 

Isoprene and the terpenes may be attacked by OH, NO3 and O3. The rate coefficients at room temperature for reaction with isoprene are of the order of 10 , 10 and 10 cm molecule" s , respectively. In the case of attack by OH, and in the presence of oxygen, a peroxy-hydroxy radical is formed up to six isomers may be produced. Product studies indicate that the initial addition is to one of the terminal carbon atoms. The peroxy-hydroxy radical may then either react with NO or with other RO2 radicals (including HO2) to form a variety of products, as indicated in Fig. 11. Under conditions where the peroxy-hydroxy radical reacts exclusively with NO, approximately 50 % of the carbon balance is accounted for by three main products methacrolein, methyl vinyl ketone and formaldehyde. Other carbonyl products and hydroxy-nitrates are thought to make up the carbon balance although there is presently no clear indication of the exact identity of these compounds or their yields. 

The reaction with NO leads to the formation of CO2 and a methyl radical that is oxidized to formaldehyde by reactions (16)-(20). In addition, the oxidation of CH3 regenerates HO c so that the oxidation cycle continues. Association with NO2 produces peroxyacetyl nitrate (PAN). Its lifetime is longer than that of alkylperoxy nitrates, but strongly temperature dependent, ranging from 1 hr at 298 K to 140 d at 250 K. Thus, PAN can be transported over a great distance before undergoing thermal decomposition. Under conditions of lowNOj concentrations acetyl peroxy radicals interact also with HO2 radicals... 

The 2-butoxy, and 1-butoxy radicals formed in the reactions of 2-butyl and 1-butyl peroxy radicals with NO (path (d) and (j)), react with O2 to produce HO2 together with carbonyl compounds such as methyl ethyl ketone and butanal (path (g) and (1)), and complete the HO cycle. Under the typical NO concentrations in the polluted atmosphere, the formation rate of alkyl nitrates by the reactions of alkoxy radicals with NO2 is negligible, the recombination isomerization reaction by the alkylperoxy radicals with NO is the major pathway as the formation process of alkyl nitrate. 

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