Abstract
In the 185 nm photolysis of liquid O2-free isopropanol the following products (quantum yields) are formed: hydrogen (0.75), acetone (0.72), pinacol (0.036), methane (0.046), acetaldehyde (0.04), propane (0.02β), ane (0.0023) and carbon monoxide (0.0015). A detailed reaction scheme is proposed. The major primary processes are the formation of H-atoms by homolytic scission of the O —H-bond (61 — 69%), elimination of molecular hydrogen (21%) and molecular methane (5%). Φ(Η2) is strongly decreased by adding water which does not absorb an appreciable portion of the 185 nm light in the mixtures down to 1 mole/l isopropanol (Φ(Η2) =0.21). In contrast to the strong effect of water there is no effect on Φ(Η2) by diluting isopropanol with n-hexane. From experiments with isopropanol-OD and 2-deutero-isopropanol it is tentatively concluded that H-atoms stemming from the O—H-group of the alcohol are to about 65% the precursors of the hydrogen in these mixtures.
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