Diethyl peroxide, combustion

A mixture of sodium peroxide and diethyl ether combusts when water is present. This accident is caused by ether oxidation by hydrogen peroxide, which is formed by the effect of water on alkaline peroxide. 

E 0 0) in hydrogen peroxide may be deduced to be 35 kcal O 3 2. It has been suggested that it is unsatisfactory to put E OH) in H2O2 equal to JE (OH) in water, and various estimates of the correct value to be taken for E OH) have resulted in E 00) =52 kcal 2 nd 64 kcal 550 13 these suggestions are rather speculative. E 0 -O) in diethyl peroxide may be deduced to be 47 kcal, if the heat of formation of this substance obtained by Rebbert and Laidler io is correct. It should be noted that heats of combustion of organic peroxides are difficult to obtain reliably. 

Figure 6 shows the variation of peroxide concentration in methyl ethyl ketone slow combustion, and similar results, but with no peracid formed, have been found for acetone and diethyl ketone. The concentrations of the organic peroxy compounds run parallel to the rate of reaction, but the hydrogen peroxide concentration increases to a steady value. There thus seems little doubt that the degenerate branching intermediates at low temperatures are the alkyl hydroperoxides, and with methyl ethyl ketone, peracetic acid also. The tvfo types of cool flames given by methyl ethyl ketone may arise from the twin branching intermediates (1) observed in its combustion. 

The ignition di am for diethyl ether—oxygen mixtures has been determined [68] and the slow combustion has been studied in some detail. The low temperature oxidation becomes appreciable at 120 °C and Lemay and Ouellet [69], working at 160—175 °C which was below the lower limit of cool flame for in their pyrex reaction vessel, observed an initial pressure drop during which oxygen was consumed by a zero-order process with an activation energy of about 50 kcal. mole. Peroxides... 

Vovelle et al. [83] showed that the cool-flame region for diethyl ether was considerably extended by the addition of di-tert-butyl peroxide. The products of the normal combustion, cool flames and two-stage ignition were all examined [84] and found to include carbon monoxide and dioxide, water, acetaldehyde, methanol and methane, ethylene and acetylene. 

DIETHYL CARBINOL (112-36-7) C,H 03 Combustible liquid (flash point 130°F/54°C autoignition temp 401 F/205°C Fire Rating 2). May form imstable peroxides during storage. Violent reaction with strong acids or strong... 

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