The Mercury Photo-Sensitized Reactions of Diethyl Ether

Abstract

The mercury photo‐sensitized reactions of diethyl ether have been investigated in a circulatory system at 35°C and between 9‐ and 193‐mm pressure. The principal products are hydrogen and C₈H₁₈O₂; smaller amounts of CO, CH₄, C₂H₆, and aldehydes are formed. The quantum yield for ether disappearance is about 2.0 initially but decreases with the duration of the experiment. In low pressure experiments the hydrogen produced initially is consumed in the later stages of the experiment and ultimately vanishes. The decrease in rate and the consumption of hydrogen in the late stages of the reaction are not caused by the accumulation either of polymer on the wall or to hydrogen and/or CO in the system. The nature of the reaction is altered by interrupting the experiment thus indicating the occurrence of a dark reaction. The initial stages may be explained by either a C–H split followed by ``atomic cracking'' or by reactions involving an active ether molecule.