A kinetic study of the influence of alcohols on the nitrosation of morpholine in acid media. Equilibrium constants for the formation of alkyl nitrites

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Abstract
The effect of the aliphatic alcohols methanol, ethanol, propanol, isopropanol, 2-butanol, isobutanol, and tert-butanol on the rate of nitrosation of morpholine at pH 3 and 25 °C has been studied. The inhibition observed is attributed to the formation of alkyl nitrites, which are poor nitrosating agents in acid media. The equilibrium constants for the formation of alkyl nitrites from nitrous acid and alcohols have been calculated both spectrophotometrically and from kinetic data for the inhibitory effect, and there is agreement between the two sets of results. The molar absorptivities at 265 nm of the alkyl nitrites have also been determined. When the concentration of alkyl nitrite is very low, a slight catalytic effect considered to be an effect of the medium has been observed.

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