Reactions of alcohols adsorbed on MgO. Part I. Heterogeneous reactions with hydrogen atoms and trapped electrons at room temperature: a new technique in surface chemistry

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Abstract
A series of alcohols, adsorbed on MgO powder, have been bombarded by a stream of hydrogen atoms at room temperature and the radicals thus formed are detected by electron spin resonance. Methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and allyl alcohol have been studied. The radical species produced have been identified and radical lifetimes varying from minutes to hours at 300 °K have been observed. For methanol, the first monolayer appears to be chemisorbed as methoxy groups whereas the ethanol data indicate that some of the molecules in the first monolayer are physically adsorbed. The higher alcohols form secondary radicals via hydrogen elimination from the primary radical; the isopropyl alcohol radical appears to isomerize before losing hydrogen. Allyl alcohol undergoes hydrogen atom abstraction in preference to addition to the double bond and yields the α-hydroxy-allyl radical. Methanol and ethanol have also been reacted with electrons trapped on a MgO surface to form stable alkoxide ion radicals trapped at oxygen ion vacancies on the surface of the lattice.

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