Abstract
The gaseous carbon dioxide has been irradiated with Co-60 gamma-radiation in the presence and absence of various alcohols, and the radiolysis products analyzed by gas chromatography. Experimental results indicate that no detectable amount of carbon monoxide is formed when pure carbon dioxide is irradiated. By adding small quantities of alcohols to carbon dioxide, however, considerable amount of carbon monoxide, ketones, alcohols and other organic products have been detected. By adding 0.1% of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 2-butanol, and 2-methyl-2-propanol, G(CO) values obtained are 4.4, 4.5, 5.2, 4.4, 5.2, 5.0, 4.7 and 4.1, respectively. These high yields of carbon monoxide suggest that the oxidation reactions of carbon monoxide may be suppressed by scavenging oxygen atom with the alcohols. The main radiolytic decomposition reactions of the alcohols present in small quantity in carbon dioxide may be supposed to be the reactions with the oxygen atom produced by the radiolysis of carbon dioxide. The decomposition reactions seems to follow pseudo-first order kinetics with respect to the alcohols. The decomposition rate measured with 2-propanol is the fastest and that with 2-methyl-2-propanol the slowest. The mechanisms of the radiolytic decomposition reactions of the alcohols present in carbon dioxide are discussed on the basis of the experimental results of the present study.