Chemical Reactions of Organic Compounds with X-Ray Activated Water

Gas free solutions of carbon monoxide, alcohols, aldehydes, ketones and acids were irradiated in the concentration range 10 μM to 1 M, between pH=1 to 13 and the reactions studied principally by gas analysis and potentiometric acid analysis. One organic component systems and, to a more limited extent, two organic component systems were investigated. To obtain significant results, foreign organic matter must be strictly excluded from the low concentration solutions and the methods used to accomplish this are described. Organic impurities in the water can be detected by irradiating the water with x‐rays and measuring the evolved hydrogen and carbon dioxide. The reactions cannot be briefly abstracted, but oxidation and condensation reactions with the evolvement of gaseous hydrogen are important in the effect of the rays. Carbon dioxide was produced from certain acids, particularly strongly from those having an oxygen containing group in the α‐position. No liberation of carbon monoxide, hydrocarbons or oxygen was found. The effect of the rays on all the compounds studied depends on the hydrogen ion concentration, this factor affecting reaction rates as well as the nature of the reactions. The relation of reaction rate to pH can in some cases be represented by $${\text{[P]=A(1+10}}^{\mathrm{-p}\mathrm{H}\mathrm{+\alpha }}{\text{/1+10}}^{\mathrm{-p}\mathrm{H}\mathrm{+\alpha }}\mathrm{).}$$ The rates of the reactions are in many cases independent of concentration, at high concentrations, but generally the rates decrease at low concentrations. The reason for this decrease may be the deactivation of the activated water, although this interpretation would, because of the form of the reaction product concentration curves, lead to the conclusion that the deactivation is approximately monomolecular (rather than bimolecular) during its initial stage. The same conclusion is indicated since the reaction rates are independent of x‐ray intensity down to the lowest concentrations used. The x‐ray reactions show some similarity to, but they are generally more complex than, the reactions produced by water activated with light inside the absorption band at 1900A. The irradiation of formic acid in the presence of oxygen at pH=3, results in a smaller decomposition of the formic acid than is produced in the absence of oxygen and a higher production of hydrogen peroxide than is obtained when oxygen is irradiated alone. This increased hydrogen peroxide production can be accounted for as resulting from the reaction of the oxygen with the nascent hydrogen liberated in the organic reaction.