Hydrogen Formation in the Radiation Chemistry of Water

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Abstract
The molecular hydrogen yields in concentrated aqueous sodium nitrate solutions by cobalt‐60 gamma‐ray irradiation have been observed and correlated with the molecular hydrogen yields observed in dilute solutions. The G(H2) plotted as the cube root of the NaNO3 activity exhibits a sharp break indicative of a change in the mechanism of formation. The predominant process, designated E1, is readily affected by a scavenging solute. A process of lessor magnitude, designated E2, is less susceptible to solute scavenging. The sharp break is interpreted as the cessation of the E1 process. The G(H2) observed in the NaNO3 solutions at 298° K is correlated with the G(H2) observed in ice at 77° K. Of paramount importance is the observation that the hydrogen formed by the E1 process may be eliminated by irradiation of aqueous nitrate solutions at 77° K. The G(D2) data observed in comparable D2O–NaNO3 solutions also exhibit the same mechanisms of formation. The isotope effect on the formation of D2 in D2O is in qualitative agreement with two initial distributions of the H atoms.

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