The decomposition of various oxygen‐containing organic compounds including alcohols, ketones and ethers was studied in a microwave discharge at 0.3–2.0 torr in the absence of a diluent. Both gases and polymeric films were formed in each case and the extent of decomposition approached 100%. Hydrogen and carbon monoxide accounted for 90% of the total gaseous products. Trace amounts of gaseous low molecular‐weight hydrocarbons were also observed. The effect of pressure on the distribution of gaseous products was small. The gaseous products were similar to those predicted from reported high‐temperature equilibrium calculations.
The C:O and the H:C ratios in the parent molecules were important parameters which determined the amount and the composition of the polymer film, respectively. The polymeric films formed in the discharge were characterised by several techniques including carbon‐hydrogen analysis, and i.r. and e.s.r. spectroscopy. The films were shown to have an average empirical formula of CH1.41O0.06 and to contain structural moieties of CO, CH3, CH2, CH and CC. The insoluble films were amorphous and contained free radicals. The polymeric films were thermally stable up to 200°c and decomposed at higher temperatures. The polymeric films formed were similar in all cases and independent of the nature of the parent molecule.
It was inferred from the decomposition products that both the gases and the polymeric films were‐formed by the reaction of simple species such as CH and H in the microwave discharge.